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Additives in Acidizing Fluids

Syed A. Ali, Chevron U.S.A. Production Co.

Jerald J. Hinkel, Schlumberger Dowell

15-1. Introduction and their interactions with fluids. Clay minerals are
important because of their large surface area and
Proper fluid selection is critical to the success of because the surface carries an electrical charge.
a matrix treatment. Figure 15-1 shows the types of Although relatively minor, some surface charge
damage that may occur and what types of treatment results from ionic substitution and structural imper-
would be required. The treatment may be a failure if fections. For instance, the substitution of Al3+ for
the proper additives are not used. The treating fluid Si4+ in tetrahedral sheets or Mg2+ or Fe2+ for Al3+ in
is designed to effectively remove or bypass the dam- octahedral sheets is the origin of negative charges in
age, whereas additives are used to prevent excessive the lattice of smectites. These are unaltered by
corrosion, prevent sludging and emulsions, prevent changes in the solutions that contact them.
iron precipitation, improve cleanup, improve cover- Silicon and aluminum oxides, the principle ingre-
age of the zone and prevent precipitation of reaction dients of sandstone and clays, exhibit amphoteric
products. Additives are also used in preflushes and behavior. Therefore, the surface charges of these
overflushes to stabilize clays and disperse paraffins minerals depend on the pH of the solutions in con-
and asphaltenes. The functions of some of the addi- tact with them. The surface charge changes from
tives are discussed briefly in this chapter. positive to negative as the pH increases. The point
Throughout this chapter references are made at which the surface charge is neutral is known as
to the interactions of additives with the formation. the point of zero charge (pzc). Table 15-1 provides
Schechter (1992) provided an excellent discussion the approximate values of the pzc for several com-
of the chemical properties of formation materials mon minerals.

Types of damage

Emulsions Wettability change Water block Scales Organic deposits Mixed organic/ Silts and clays
Mutual solvent ± Mutual solvent ± Aromatic solvents inorganic deposits Depend on
de-emulsifier water-wetting Carbonates Solvent in acid mineralogy
surfactant CaCO3 dispersion
High temperature (>250°F): Aqueous acetic acid
Low temperature (<250°F): HCl
FeCO3 – HCl + reducing/sequestering agents

Oil well Gas well Sulfates

Acid + alcohols CaSO4 – EDTA
BaSO4 – EDTA
SrSO4 – EDTA

Fe scales
Low to medium temperature (≤250°F) High temperature (>250°F) FeS – HCl + reducing + sequestering
Acid + solvent Nonaqueous acetic acid Fe2O3 – HCl + EDTA
Acid + surfactant FeCO3 – HCl + reducing/sequestering

Chloride
NaCl – H2O, 1%–3% HCl

Hydroxide
Mg(OH)2 – HCl
Ca(OH)2 – HCl

Silica – mud acid

Figure 15-1. Types of damage.

Reservoir Stimulation 15-1

 Table 15-1. Point of zero charge of some
Fe2+ H2 H+
representative reservoir materials.

Material Point of Zero Charge

Quartz (SiO2) 2.7

Corundum (Al2O3) 9.0
Hematite (Fe2O3) 5.0 al
et
Calcite (CaCO3) 9.5 M

Kaolinite (AI4Si4O10(OH)8) 4.6

Montmorillonite
(Al,Mg,Fe)4(Al, Si)8O20(OH)4 · nH2O 2.0 Figure 15-2. A metal surface composed of both anodic
Albite (NaAlSi3O8) 2.0 and cathodic sites (Schechter, 1992).

Thus, the way in which additives interact with the on the metal surfaces, along with the reduction of
reservoir actually depends on the pH. Under the con- hydrogen ions and formation of hydrogen at the
ditions normally associated with the matrix acidiza- cathodic sites.
tion of sandstones, the pH of the acid is less than the The equations for an anodic reaction (oxidation):
pzc of the reservoir constituents, which causes the
formation materials to behave as positively charged. Fe → Fe2+ + 2e–
It is important to keep this concept in mind. metallic iron ionic iron electrons
and a cathodic reaction (reduction):

15-2. Corrosion inhibitors 2H+ + 2e– → H2

ionic hydrogen electrons hydrogen
The most important acid additives are corrosion
inhibitors. A corrosion inhibitor is a chemical that can be combined to show the overall reaction:
slows the attack of acid corrosion on drillpipe, tubing Fe + 2H+ → Fe2+ + H2
or any other metal that the acid contacts during treat- metallic iron ionic hydrogen ionic iron hydrogen
ment. Brief explanations of corrosion mechanisms,
The unit of measurement used to determine the
corrosion inhibition and techniques for evaluating
amount of corrosion is lbm/ft2. Acceptable corrosion
inhibitor performance are presented in this section.
limits for low-alloy steel are shown in Table 15-2.
The acceptable range is from 0.02 to 0.09 lbm/ft2
15-2.1. Corrosion of metals of metal surface, depending on the temperature and
exposure time. Acids corrode more evenly, with less
Any metal surface is a composite of electrodes elec- pitting, at higher temperatures. At elevated tempera-
trically short-circuited through the body of the metal tures, more corrosion may occur, but the chance of
itself (Fig. 15-2). As long as the metal remains dry, forming a hole in the drillpipe or tubing string is
local currents and corrosion are not observed. How- actually less.
ever, on exposure of the metal to aqueous salt, alkali The effectiveness of a given corrosion inhibitor
or acid solutions, local action cells are able to func- depends on the metal. McDougall (1969) reported
tion, leading to chemical conversion of the metal to tests of five different commercial corrosion inhibitors
corrosion products. on N80, J55 and P105 tubulars. These results clearly

Table 15-2. Corrosion limits for low-alloy steel.

15-2.2. Acid corrosion on steel
Temperature Corrosion Limit (lbm/ft2)
All uninhibited acid solutions corrode steel. The
200°F [95°C] 0.02
attack of acid on steel occurs through the dissociated
hydrogen ions in the acid solution. This results in the 200° to 275°F [95° to 135°C] 0.05
oxidation and dissolution of iron at the anodic sites 275° to 350°F [135° to 175°C] 0.09

15-2 Additives in Acidizing Fluids

show the necessity of matching the inhibitor to the relative to the surrounding steel structure and thus
steel, because a wide range of responses was promote acid attack.
obtained for a given inhibitor. Smith et al. (1978)
pointed out that American Petroleum Institute (API)
designations for steels are inadequate to distinguish 15-2.4. Hydrogen embrittlement
corrosion rates because they identify yield strength,
whereas corrosion characteristics are determined pri- Hydrogen embrittlement results from the cathodic
marily by chemical composition. Because yield reaction described previously in which hydrogen
strength may be achieved either by physical or ions are reduced to elemental hydrogen. Elemental
chemical modifications in manufacturing, it is essen- hydrogen results from acidizing operations. Ele-
tial that the metal coupons tested are representative mental hydrogen adsorbed by a metal can lower
of the tubulars to be protected. ductility to the point that the metal becomes brittle.
Figure 15-3 shows the effect of hydrogen content
and tensile strength on the loss of ductility of steel.
15-2.3. Pitting types of acid corrosion The N80, P110 and Q125 grades of tubing and cas-
ing are prone to embrittlement as a result of acidiz-
In uninhibited acid solutions, the corrosion of steel is
ing. Consequently, inhibitor selection must take this
usually uniform. The constant shifting of anodic and
into account.
cathodic areas spreads corrosion fairly evenly over
the entire surface of the metal. In inhibited acids, pit-
ting of the surface occurs in some situations as a 60

result of inhibitor breakdown, insufficient inhibitor Tensile ductility (% reduction in area)

50 Utimate tensile
or metal impurities. strength = 130 ksi
40 156
• Inhibitor breakdown
Pitting-type corrosion is not uncommon on steel 30

containing an inferior corrosion inhibitor that is 20

exposed to acid solutions. All corrosion inhibitors
eventually break down after some period of time, 10
270 240 196
depending on various factors including tempera- 0
ture, acid strength and metal type. When this point 0 0.5 1.0 1.5 2.0 2.5
is reached, an inferior inhibitor may actually pro- Hydrogen content (ppm)
mote pitting by desorbing from the metal surface
in localized areas. Figure 15-3. Reduction in ductility with increasing hydro-
gen content and strength (Tetelman, 1973). 1 ksi = 100
• Insufficient inhibitor lbf/in.2.

Regardless of the quality of the corrosion inhibi-

tor, pitting may also occur if there is an insuf-
ficient amount of inhibitor to effectively coat the 15-2.5. Corrosion by different acid types
steel surfaces. Unprotected steel surfaces are The degree of dissociation of hydrogen ions from the
rapidly attacked by the acid solution and pitting acid molecule, along with the acid concentration,
occurs. determines the hydrogen ion activity, which is di-
• Metal impurities rectly proportional to its corrosivity on steel. The
Another condition that promotes pitting is the relative degree of dissociation for some common
presence of impurities or inclusions within the acids is hydrochloric > formic > acetic. Therefore,
steel. For example, small pieces of slag may hydrochloric acid (HCl) is more corrosive on steel
become trapped during the forming of the steel, than formic acid, which is more corrosive than acetic
or improper heat treating or quenching of the steel acid. Quite logically, the more aggressive an acid is
may produce discontinuities in its grain structure. in its attack on steel, the more difficult it is to inhibit.
These imperfections may, in turn, become anodic However, the mechanism of attack is the same for all
acid types.

Reservoir Stimulation 15-3

15-2.6. Inhibitor types – can be used in the presence of H2S without the
precipitation of salts such as arsenic sulfide
Inhibitors function by interfering with the chemical (which can plug the wellbore)
reactions that occur at the anode or cathode of the
corrosion cell. The two basic types of corrosion – do not poison refinery catalysts
inhibitors are inorganic and organic. There are also – work effectively in all acid concentrations.
inhibitor aids. Disadvantages of organic inhibitors are that they
• Inorganic corrosion inhibitors – chemically degrade with time in the presence of
This class of inhibitors includes the salts of zinc, acid and thus do not readily provide long-term
nickel, copper, arsenic, antimony and various other protection at temperatures above 200°F [95°C]
metals. Of these, the most widely used are the (Table 15-3)
arsenic compounds. When these arsenic com- – cost more than the inorganic corrosion inhib-
pounds are added to an acid solution, they “plate itors.
out” at cathodic sites of exposed steel surfaces.
• Inhibitor aids
The plating decreases the rate of hydrogen ion
exchange, because the iron sulfide that forms Although these additives do not function as inhib-
between the steel and the acid acts as a barrier. It itors, they increase the effectiveness of organic
is a dynamic process in which the acid reacts with inhibitors. The common inhibitor aids are potas-
iron sulfide, rather than the metal. sium iodide, cuprous iodide, cuprous chloride and
Some advantages of inorganic inhibitors are that formic acid. The addition of these materials to
they existing organic inhibitor formulations greatly
extends the range of their effectiveness, particularly
– work effectively at high temperatures for long
in higher temperature applications.
contact times
– cost less than organic inhibitors.
Table 15-3. Effectiveness of corrosion inhibitors at
Disadvantages of inorganic inhibitors are that high temperatures in 15% HCl.
they
Inhibitor Inhibitor Temperature Protection
– tend to lose their effectiveness in acid solutions Concentration (°F) Time†
stronger than about 17% HCl (%) (hr)

– react with hydrogen sulfide (H2S) through the Organic 0.6 200 24
iron sulfide that may be present to form an insol- 1.0 250 10
uble precipitate such as arsenic sulfide 2.0 300 2
– poison refinery catalysts (such as platinum) Inorganic 0.4 200 24
– may liberate toxic arsine gas as a corrosion by- 1.2 250 24
product 2.0 300 12
– are difficult to mix and unsafe to handle. † Time required for 15% HCl to remove 0.05 lbm/ft2 of exposed metal area
• Organic corrosion inhibitors
Organic corrosion inhibitors are composed of polar
organic compounds capable of adsorbing onto the 15-2.7. Compatibility with other additives
metal surface, thereby establishing a protective film
that acts as a barrier between the metal and the acid Any additive that alters the tendency of the corrosion
solution. They usually serve as a cathodic polarizer inhibitor to adsorb will also change its effectiveness.
by limiting hydrogen ion mobility at cathodic sites. For example, surfactants added to acid for various
Organic inhibitors are composed of rather complex purposes may form micelles that solubilize the
compounds, with one or more polar groups made inhibitor, thereby decreasing the tendency for the
of sulfur, oxygen or nitrogen. inhibitor to adsorb on the metal surface. Inorganic
Some advantages of organic inhibitors are that salts and mutual solvents can also interfere with
they inhibitor adsorption. If possible, additives that reduce

15-4 Additives in Acidizing Fluids

the effectiveness of inhibitors should be included in a ment if no pitting occurs. For some cases an amount
preflush or overflush rather than in the acid solution. as high as 0.095 lbm/ft2 is allowable. If these metal
losses cannot be sustained without adverse effects,
a more effective inhibitor must be found.
15-2.8. Laboratory evaluation of inhibitors If inhibitor cost becomes prohibitive, it may
The laboratory evaluation of a corrosion inhibitor be possible to reduce the cost by careful treatment
involves subjecting a coupon of the metal to be pro- design. Precooling the tubing by injecting a large
tected to the acid to be used. The coupon is normally water preflush will be helpful. Using formic acid
inserted into a mixture of the acid and corrosion rather than HCl helps reduce the corrosion problem.
inhibitor to be evaluated and placed in a heated pres- Also, minimizing the contact time reduces inhibitor
sure vessel. The replication of downhole conditions requirements.
is important. The amount of corrosion is determined The most important aspect is the proper testing of
by weighing the coupon before and after the test. representative metal samples using the precise acid
Inhibitor effectiveness is expressed in terms of metal formulation to be applied at the most adverse condi-
loss per unit area of metal exposed per unit of time. tions of temperature and pressure. The test should be
The typical unit is lbm/ft2/day. conducted in an oxygen-free environment. Only
Also to be noted is pitting, which is a localized under these conditions can a decision about the ade-
attack. If appreciable attack is confined to a rela- quacy of the corrosion inhibitor be made.
tively small area of the metal acting as an anode,
then the resultant pits may be deep. A pitting factor,
defined as the ratio of the deepest metal penetration 15-3. Surfactants
to the average penetration, as determined by the Surfactants, or surface-active agents, are used in
weight loss of the specimen, is sometimes reported. acidizing to break undesirable emulsions, reduce
A pitting factor of unity represents uniform attack. surface and/or interfacial tension, alter wettability,
Many factors influence the corrosion rate measured speed cleanup, disperse additives and prevent sludge
in such tests. Of major importance are formation. The use of surfactants requires careful
• degree of agitation selection of an appropriate molecule. Remarkably,
in the design of most well treatments, surfactants are
• metal type selected with little or no laboratory data to support
• exposure time the choice and sometimes without full knowledge of
their properties at the conditions in which they will
• temperature
be applied. Improper surfactant selection can lead to
• acid type and concentration results contrary to those intended and may be detri-
mental to the success of the treatment.
• inhibitor type and concentration
Surfactants owe their properties to their “dipolar”
• metal-to-acid volume ratio composition (Fig. 15-4). The surfactant molecule
• gas composition (if an interface is present) consists of a water-soluble (hydrophilic) group and

• pressure
• presence of other additives such as surfactants.

15-2.9. Suggestions for inhibitor selection

Some metal loss from wellbore tubular goods must
be expected when acidizing, and the primary issue Lipophilic group
Hydrophilic group
is what level can be tolerated. Most service company (water soluble) (oil soluble)
information is based on the assumption that a metal
loss of 0.02 lbm/ft2 can be tolerated during the treat- Figure 15-4. Dipolar surfactant composition.

Reservoir Stimulation 15-5

an oil-soluble (lipophilic) group, which are separated 15-3.2. Cationic surfactants
from each other although linked by a strong covalent
chemical bond. The molecules are classified into five Cationic surfactants carry a positive charge when
groups according to the ionic charge carried by the they ionize in aqueous solutions. There are two gen-
water-soluble group: eral categories of cationic surfactants. The first cate-
gory consists of long-chain primary, secondary and
• anionic tertiary amines. These are soluble only in acidic
• cationic solutions, where they ionize to form a long-chain
cation and simple anion salt. Figure 15-5 shows vari-
• nonionic ous molecular cationic structures.
• amphoteric The second important category of cationic surfac-
tants is the quaternary ammonium compounds. These
• fluorocarbons. ionize to form long-chain cations over a wide range
The hydrophilic-lipophilic balance (HLB) depends of solution pH. Cationic surfactants experience the
on the composition of the organic chain, which can same sensitivity to multivalent ions or increased con-
be 100% oleophilic (e.g., an alkane chain) or contain centrations of dissolved solids as anionic surfactants;
some oxygen atoms (e.g., an ethylene oxide chain) therefore, the same care must be exercised in their
and become more hydrophilic. The HLB value of a application as with anionic surfactants.
surfactant indicates how much its chains can oil wet Cationic and anionic surfactants are generally
a mineral. incompatible. When mixed, they tend to precipitate
in aqueous solutions.

15-3.1. Anionic surfactants

Primary amine R — NH+3
Anionic surfactants are commonly added to well
treatment fluids. These surfactants carry a negative R2
charge when they ionize in an aqueous solution.
Because most reservoir minerals are also negatively Tertiary amine R1 — NH+
charged at nearly neutral and higher pH values, ani- R3
onic surfactants exhibit minimal adsorption. Some
examples of anionic surfactants are +
R2
Sulfates R—O—SO3–
Quaternary amine R1 —N — R3
Sulfonates R—SO3–
R4
Phosphates R—O—PO3–
Phosphonates R—PO3–
Figure 15-5. Various types of cationic surfactants.
where R is an oil-soluble organic group.
Of these, the most common anionic surfactants are
sulfates and sulfonates. Anionic surfactants are sen- 15-3.3. Nonionic surfactants
sitive to multivalent ions such as Ca2+ and Mg2+. Nonionic surfactants have no charge at all in the
These tend to precipitate anionic surfactants, hydrophilic group and a long-chain organic (R) for
although this tendency can be overcome to some the lipophilic group. The water-soluble group is a
extent by increasing the surfactant concentration. polymer made from either ethylene oxide or propy-
Anionic surfactants are used primarily as nonemulsi- lene oxide. Other types include alkanol amine con-
fying agents, retarding agents and cleaning agents. densates and amine oxides. The general formulas for
these products are as follows:

15-6 Additives in Acidizing Fluids

Ethylene oxide polymer R—O—(CH2CH2O)xH to a greater extent than hydrocarbon surfactants.
Surface tensions as low as 30 dynes/cm can be
Propylene oxide polymer R—O—(CHCH2O)yH
obtained using surfactants with a hydrocarbon tail.

Values as low as 17 dynes/cm have been reported
CH3
using fluorocarbon surfactants. Fluorocarbons are
Alkanol amine commercially available in anionic, cationic and non-
condensate R—C—N—(CH2CH2OH)2 ionic forms.

O
15-3.6. Properties affected by surfactants
Amine oxides CH2CH2OH
 The main properties of a fluid or a mineral affected
COCO—N—O by surfactants are the surface and interfacial ten-
 sions, emulsification tendency, wettability, micelle
CH2CH2OH formation and dispersibility.

Nonionic surfactants obtain their water solubility • Surface and interfacial tensions
by attaching the long hydrocarbon chain to a highly Rosen (1989) presented a good discussion of how
soluble molecule such as polyhydric alcohol or by surface and interfacial tensions are reduced by sur-
reacting it with ethylene oxide. Most of the com- factants. Figure 15-6 is a simplified diagram of the
pounds in this classification are esters, ethers and interface between two condensed phases. A mole-
ether-esters. The lipophilic group may be derived cule in the bulk of a liquid is surrounded by mole-
from natural oils and fats, petroleum oils or synthe- cules like itself and the forces are balanced. At the
sized hydrocarbons. The hydrophilic group is usually interface, however, the forces acting on the mole-
a polyhydric alcohol or an alkyd oxide polymer. cules in the two liquids are different from the
These surfactants are used as nonemulsifiers and forces acting on the molecules in the bulk liquids.
foaming agents. The terms Aaa and Abb in Fig. 15-6 represent the
interaction energy between molecules at the inter-
face and similar molecules in the bulk of the liquid
15-3.4. Amphoteric surfactants whereas Aab represents the interaction energy
Amphoteric surfactants have a hydrophilic group between dissimilar molecules at the interface.
that changes from cationic to nonionic to anionic The increase in potential energy of the mole-
with increasing pH. In other words, if the solution is cules at the interface compared with that of the
acidic, the amphoteric surfactant acts like a cationic molecules in the bulk liquid is simply Aaa – Aab
surfactant; if the solution is neutral, it acts like a and Abb – Aab. Therefore, the total increase in
nonionic surfactant; and if the solution is basic, it
acts like an anionic surfactant. These properties are Aaa Aab
derived from the two groups of opposite charge on
the surfactant head. The amphoterics are usually
either amine sulfonates or amine phosphates. The Liquid a
general formulas are as follows:
Amine sulfonates RNH—(CH2)xSO3H
Amine phosphates RNH—(CH2)yOPO3H Liquid b

15-3.5. Fluorocarbon surfactants Aab Abb

Fluorocarbons form surfaces of lower free energy
than hydrocarbon surfaces. Consequently, fluorocar- Figure 15-6. The interface between two liquids (Rosen,
bon surfactants lower the surface tension of solutions 1989).

Reservoir Stimulation 15-7

 potential energy at the interface becomes Aaa + Abb
– 2Aab. The interfacial free energy per unit of sur- Gas
face area, which is also known as the interfacial
tension γI, becomes
γI = γa + γb – 2γab , (15-1)
where γa and γb are the surface tensions of pure Liquid b
liquid a and liquid b, respectively, and γab is the
interaction energy per unit of surface area between
liquids a and b. Abb
The value of γab tends to be large when similar
liquids are in contact; this causes γI to be small. Figure 15-7. The interface between a liquid and a gas.
Conversely, if liquid a is quite different from liq-
uid b, then the interaction energy is small and the
interfacial tension between the two liquids is large. • Emulsification tendency
Surface tensions of some liquids are listed in
An emulsion is a mixture of two fluids in which
Table 15-4.
fine droplets of one fluid are suspended in the
other. Emulsions may be oil external or water
Table 15-4. Surface tension of some liquids.
external. In the first instance, oil is the continuous
Liquid Surface Tension phase with the water droplets dispersed through-
(dynes/cm) out. This is the most common emulsion found in
Water 72.0 wellbores. A water-external emulsion has an aque-
15% HCl 72.0 ous external phase with oil droplets distributed
Spent 15% HCl 76.9
throughout.
Many crudes contain naturally occurring surfac-
Octane 21.8
tants that reduce the surface tension between oil
and formation water and thus promote the devel-
Figure 15-7 illustrates the interaction between opment of emulsions. Treatment of the formation
a liquid and a gas. In this case the interface is the with certain surfactants can also lead to the devel-
surface of the liquid. The interaction between a opment of emulsions. However, appropriate sur-
gas molecule and other gas molecules is negligi- factants can be used to treat wells with emulsion
ble, as is the interaction between gas molecules problems. Laboratory testing is required to deter-
and the liquid. Therefore, γI = γb; in other words, mine the appropriate surfactant.
the interfacial tension is simply the surface tension
• Wettability
of the liquid.
A surfactant, when added to two immiscible Oil and water are immiscible liquids that compete
phases, adsorbs at the interface. If one of the liq- for space on the formation surface. Which liquid
uids is water and the other is a hydrocarbon, the preferentially wets the rock surface is an important
hydrophobic end of the surfactant will be oriented factor in acidizing. When the formation surface is
toward the hydrocarbon, and the hydrophilic group completely covered by a film of oil, the formation
will be oriented toward the water phase. This causes is termed oil-wet. Conversely, when covered by
a change in the interface. Now the interaction is water, the formation is water-wet.
between the hydrophilic group of the surfactant and An electrochemical approach helps to explain
the water phase and the hydrophobic group of the the ability of a surfactant to adsorb at interfaces
surfactant and the hydrocarbon phase. These inter- between liquids and solids and alter the wettability
actions are much stronger than the original interac- of solids. Sand usually has a negative surface
tion between the water and hydrocarbon, which charge. When a cationic surfactant is present and
effectively leads to an increase in γab and a con- the pH rises above the pzc, the positive water-sol-
comitant decrease in γI. uble group is adsorbed by the negative silica parti-
cle. This leaves the oil-soluble group to influence

15-8 Additives in Acidizing Fluids

 wettability. As a result, cationic surfactants gener-
ally create an oil-wet sand, although cationic sur-
factants can be chemically modified to yield a
water-wet sand. When anionic surfactants are
used, the sand and silicate minerals are generally Oil Water
left in their natural water-wet state. Wettability
characteristics exhibited by anionic and cationic
surfactants on a silicate particle are shown in
Fig. 15-8. Carbonates have a pzc at a pH of 9–10
and thus are normally oil-wet by cationic surfac- Hydrophilic Oleophilic
oleomicelle hydromicelle
tants above a pH of 9 whereas anionic surfactants
oil wet the rock below a pH of 9.

Silicate particle
Water
Oil-wet Water-wet

Lamellar micelle

Figure 15-9. Examples of surfactant micelles that can form

in liquids above a specific surfactant concentration (Hall,
1986).

Once the aggregate has been dispersed, a different

Cationic surfactant Anionic surfactant
surfactant may be required to prevent the dis-
Figure 15-8. Silicate particle wettability characteristics persed particles from rejoining.
(Hall, 1986).

• Micelle formation
15-3.7. Applications and types of surfactants
Surfactants can form micelles in liquids when pre- In recent years, the uses of surfactants have grown
sent above a specific concentration for each mole- quickly. This unique class of chemicals has found
cule, solvent and temperature. This concentration application in almost all phases of acidizing. A com-
is referred to as the critical micelle concentration prehensive review is beyond the scope of this chap-
(CMC). Below the CMC, many properties of the ter. However, a brief review follows.
system are concentration dependent. Some of these • De-emulsifiers
properties are surface tension, interfacial tension,
A de-emulsifier is used to break oil-water emul-
foam stability and emulsion tendencies. Figure
sions, which occur commonly. The action of a de-
15-9 shows examples of surfactant micelles.
emulsifier depends on how quickly it can concen-
• Dispersibility trate at the oil/water interface. The faster the con-
To separate a highly associated structure (e.g., centration at the interface, the more rapid will be
a sludge) into its particulate elements usually the rate of emulsion breaking. These surfactants
requires energy. If the dispersed phase is not in are usually oil-soluble chemicals that are blended
intimate contact with the continuous liquid phase, with other de-emulsifying surfactants to achieve a
then the energy transfer will not be very efficient. synergistic response.
A wetting surfactant that wets the dispersed phase • Nonemulsifiers
with the liquid phase greatly improves the dis-
These surfactants are added to well treating or
persibility. This is one aspect of aiding dispersion.
workover fluids to prevent emulsions. Chemical

Reservoir Stimulation 15-9

 suppliers and service companies have many differ- This normally renders the particles oil-wet and
ent surfactants that are classified as nonemulsifiers. causes them to act more like droplets of oil than
The chemicals are usually mixtures of surfactants solid particles. As long as they remain oil-wet, they
and solvents that are blended to obtain a final tend to remain suspended in the spent acid.
composition with broader applications. Normally, Another force working to suspend the silt parti-
the surfactants are chosen so that they will water cles is electrostatic repulsion. Because all the par-
wet the formation. They should also mix easily ticles carry the same charge, the particles repel
with treating or workover fluids and prevent the each other and tend to not agglomerate. This com-
formation of emulsions with the reservoir fluids. bination of oil-wetting and electrostatic repulsion
makes an effective silt-suspending system.
• Emulsifiers
Specialized emulsions are often used as treating flu- • Antisludge agents
ids. Many solvent systems concurrently use aqueous When acid contacts some crude oils, a sludge can
and hydrocarbon phases. Such emulsions may ex- form at the acid/oil interface. This is most severe
hibit higher viscosity than either base fluid. Emul- with high-strength acid systems (20% or higher).
sions also have the ability to isolate the internal Once formed, the sludge is difficult to redissolve
phase so that it is not as reactive. A common exam- into the oil. As a result, the sludge accumulates in
ple of this technology is the use of emulsified acid. the formation and decreases permeability.
With these properties, emulsions are efficient To combat the formation of sludge, cationic and
scale removal systems. When an inorganic scale is anionic surfactants are used to adsorb and provide
deposited in combination with a hydrocarbon scale a continuous layer of protection at the acid/oil
(paraffin or asphaltene), an efficient scale removal interface. Sludge development can often be pre-
system can be formulated by emulsifying a solvent vented by lowering the acid strength.
for the inorganic scale—usually HCl—with the
• Surface tension reducers
hydrocarbon. Usually, the emulsion has a low vis-
cosity with a stability of up to several hours at bot- Surfactants are commonly used in treating tight
tomhole conditions. The stability of the emulsion is gas wells and in scale removal treatments. Their
low to minimize the potential for damaging the well main function is to lower the surface and inter-
with the emulsion during workover. The hydrocar- facial tensions of the treating fluid. This reduces
bon phase ranges from 10% to 30% by volume with the capillary pressure, which makes it easier to
a water-base fluid as the external phase. Most emul- recover fluid from the capillary pore channels and
sifiers used in this application are nonionic. to prevent oil-wetting films. Lowering the capil-
lary pressure aids in cleaning up the well because
• Silt-suspending agents less differential pressure is required to move the
Surfactants can also be used to remove acid-insol- fluid through the capillary channels. The maxi-
uble clay and silt during an acidizing treatment. A mum differential pressure available to clean up a
surfactant is added that adsorbs onto the clay or well is the reservoir pressure less the lowest draw-
silicate particles and keeps them suspended by down that can be achieved at the perforations. If
electrostatic repulsion. With this surfactant pre- this maximum differential pressure is not high
sent, damaging insoluble residues can be removed enough to move the liquid out of a pore channel,
with the spent acid. These particles, if not a block exists and its removal may require a sur-
removed, can stabilize emulsions or settle out and factant that provides a lower surface tension (i.e.,
block the pore throats of the producing formation. lower capillary pressure).
The mechanism for suspending silt with a surfac-
• Corrosion inhibitors
tant can also be best understood by an electrochem-
ical approach. Silt particles are minerals, such as Corrosion inhibitors function by adsorbing onto
quartz, feldspars and clays, that, assuming the the steel and providing a protective barrier
treating fluid has a pH above the pzc, carry a nega- between it and the acid. Surfactants that are effec-
tive surface charge. Silt-suspending surfactants are tive as corrosion inhibitors include certain quater-
cationic, and the positively charged end of the mol- nary amines and acetylenic nonionics. Generally,
ecule adsorbs onto the surface of these minerals. these materials contain some cationic species.

15-10 Additives in Acidizing Fluids

• Bactericides – nonionic—stable foam with acid or brine; be-
When treating a formation, it is usually desirable cause of cloud point problems, nonionics nor-
to leave it water-wet to aid the production of oil. mally cannot be used above 200° to 250°F
This is done with an appropriate surfactant. It is [95° to 120°C]
also desirable to leave the formation free of conta- – anionic—stable foam with brine; can be used up
minating bacteria that may have been inadver- to 300°F [150°C]
tently pumped into the well with the treating fluid. – cationic—stable foam with acid or brine; can be
Many cationic surfactants possess this biocidal used up to 300°F
property and are commonly used in conjunction
– amphoteric—stable foam with acid or brine; can
with other wetting surfactants.
be used up to 350°F [175°C].
• Clay treaters
Foam stability usually can be improved by
Drilling muds commonly contain the highly water gelling the liquid.
swelling clay smectite (bentonite). While a well is
being drilled and completed, some of the clay may
invade the producing zone and decrease formation
productivity. Several chemical solutions are used 15-4. Clay stabilizers
for the removal of this invading clay. Chemicals used to stabilize clays and fines function
The swelling properties of smectite may be by being adsorbed, usually by electrostatic attraction
changed by chemical reactions, because all clays or ion exchange, on the minerals to be stabilized.
are negatively charged at pH values above their Because silicates above their pzc values have a nega-
pzc values. Thus, positively charged cations (cal- tive charge, the most effective stabilizer has a posi-
cium, sodium, potassium and hydrogen) may be tive charge (cationic). Common clay stabilizers are
attracted to the clay and are known as exchange- highly charged cations, quaternary surfactants, poly-
able cations. The particular cation and the quantity amines, polyquaternary amines and organosilane.
present in a clay system govern the degree of
water swelling or clay expansion. For example,
hydrogen smectite swells less in water than 15-4.1. Highly charged cations
sodium smectite. By reacting sodium smectite
(bentonite) with acid, hydrogen ions will replace Two highly charged cations that were once widely
the sodium ions by the cation-exchange process. used as clay stabilizers are hydroxyaluminum
Because hydrogen clay retains less water than (Al6(OH)12(H2O)126+) and zirconium (Zr4+) added as
sodium clay, the treatment of drilling mud with zirconium oxychloride (ZrOCl2). Solutions contain-
acid can shrink smectite and clean up mud filter ing either stabilizer are usually pumped after various
cake. However, acid may also cause clay particles preflushes. The stabilizer solution is then overflushed
to flocculate. This flocculation results in larger with a compatible fluid to remove excess clay stabi-
clay particles that may be more difficult to remove lizer from the near-wellbore region, and the well is
from the well. shut in. These systems do not appreciably affect for-
Surfactants have been developed to inhibit the mation wettability.
flocculation of clays, even in solutions of high The primary advantages of these systems are
ionic strength. This is accomplished by using a • inexpensive
surfactant that effectively disperses clay particles • treat for both migration and swelling damage
and minimizes the formation of aggregates. In
• can treat a large area of rock.
addition, smaller particles are easier to suspend,
resulting in more efficient removal from the well. The disadvantages are
• Foaming agents • hydroxyaluminum is not acid resistant
Surfactants are used to generate a stable foam. The • require shut-in to polymerize
following guidelines are usually applicable for sur- • can cause plugging
factant application:

Reservoir Stimulation 15-11

• difficult to use in fracturing the polymers also promote water-wetting of the sili-
• require proper preflushes and overflushes. cate. In addition, polymers of sufficient length can
promote polymeric bridging between silicate particles.
Systems such as hydroxyaluminum can also be If a treated silicate is contacted by brines, the
used in treating water injection and disposal wells polyamine can lose its positive charge and be
to stabilize silicates and minimize future plugging washed off the silicate. When this occurs, that sili-
from colloidal fines in the injection water. cate is no longer stabilized.
The disadvantages of polyamines are that
15-4.2. Quaternary surfactants • treatment may not be permanent
Quaternary surfactants have been used as clay stabi- • they are expensive.
lizers for dry gas wells. At conditions above the pzc,
these surfactants are readily adsorbed by silicates
owing to electrostatic attraction between the posi- 15-4.4. Polyquaternary amines
tively charged surfactant and negatively charged
Polyquaternary amines can be used in any water-
clay. The resulting charge neutralization reduces the
base fluid, including acids and bases. The chemical
ion-exchange capacity of the clay. Therefore, the
structure of the two polyquaternary amines that have
clay is not as susceptible to swelling resulting from
been widely used is as follows:
the adsorption of hydrated cations.
Quaternary surfactants promote oil-wetting of the CH3 Condensation
silicate, which tends to minimize the adsorption of  products of
water by the silicate. However, if any liquid hydro- —CH2—CHOH—CH2—N(+)— dimethylamine
carbons are present, the silicate can readily become  and
oil-wet. This, of course, reduces the relative perme- CH3 epichlorohydrin
ability of the rock to hydrocarbons. Also, clays swell
by imbibing fluids into their lattice structure. —CH2—CH—CH2—CH— Dimethyl diallyl
  ammonium chloride
CH2 CH2
15-4.3. Polyamines
Polyamines are organic polymers that contain more N(+)
than one amine group. For the purpose of this dis-
cussion, only primary, secondary and tertiary amines CH3 CH3
are considered polyamines. Polyamines are posi-
tively charged in acidic fluids. The general structure Clays and fines are stabilized by charge neutraliza-
of a polyamine is as follows: tion, water-wetting and polymeric bridging. Silica
fines have a lower charge density than clays. There-
R´
fore, polyquaternary amines preferentially adsorb on

clays as opposed to silica. When acidizing a water-
CH3—[R—N—R]n—CH3
sensitive formation with hydrofluoric acid (HF), clay

stabilizer should be used if possible. If it is not pos-
H
sible to put clay stabilizer in all fluids, it should be
where R is a repeating hydrocarbon unit, R´ can be used in the overflush, which should be overdisplaced
either a hydrocarbon unit or a hydrogen, and n is the with fluid that contains no clay stabilizer to ensure
number of amine units in the polymer. that no unadsorbed clay stabilizer is left at the well-
Because the polymer has many amine units, it can bore. A normal concentration of polyquaternary amine
adsorb strongly on the silicate with many points of for applications in HF treatments is 5 gal/1000 gal of
attachment. The polymers can effectively neutralize active polymer in all fluids or 71⁄2 gal/1000 gal of clay
the negative charge of the silicate. By carefully con- stabilizer in 200 gal of overflush.
trolling the carbon:nitrogen ratio, usually 8:1 or less,

15-12 Additives in Acidizing Fluids

 There has been concern regarding the distinction polysiloxane coating stabilizes fines by blocking ion-
between fines migration and clay migration. Fines exchange sites and increasing interparticle attractive
consist predominantly of silt-sized particles of quartz forces. Interparticle attractive forces can include van
and feldspars. Laboratory data indicate that the der Waal forces and hydrogen bonding. These forces,
polyquaternary amines are not as effective in con- in addition to the electrostatic forces, help maintain
trolling fines migration as compared with clays the fines in their aggregated state along the pore
(Hall, 1986; Ayorinde et al., 1992). wall. By blocking the ion-exchange sites, the poly-
siloxane coating decreases the magnitude of double-
layer repulsion.
15-4.5. Organosilane The polysiloxane formed can bind to minerals that
Kalfayan and Watkins (1990) proposed that an have low-cation-exchange capacities (quartz), as
organosilane compound can be used as an additive well as to clays that have high-cation-exchange
to HCl-HF mixtures to prevent poststimulation fines capacities. Therefore, the organosilane additive is
migration. Organosilane has the following general well suited for formations that contain nonclay fines
structure: as well as clay fines.

OR
 15-5. Mutual solvents
RO—Si—OR
 Mutual solvents, as the name implies, are chemicals
R´NH2 that are mutually soluble in both hydrocarbons and
water. The most efficient mutual solvents are glycol
where R and R´ are hydrolyzable organic groups. ethers, a reaction product of alcohols and ethylene
As an additive to acid, organosilane hydrolyzes oxide. These chemicals are relatively safe and easy to
to form silanols, which have the following structure: use in the field. The preferred glycol ethers contain at
OH least a butyl or higher molecular weight group.
 The use of mutual solvents in the acid stimulation
HO—Si—OH of a sandstone reservoir is a common practice.
 Mutual solvents are used in acid solutions and over-
R´NH2 flushes to
The silanols react with each other and with silanol • aid in reducing water saturation around the well-
(Si–OH) sites present on siliceous mineral surfaces to bore by lowering the surface tension of the water
form covalent siloxane (Si–O–Si) bonds by a conden- to prevent water blocks
sation/polymerization reaction mechanism. The reac- • solubilize a portion of the water into a hydrocar-
tion of the silanols with one another and with the bon phase to reduce the water saturation
silanol sites on siliceous mineral surfaces forms a non- • aid in providing a water-wet formation to maintain
oil-wetting polysiloxane coating on siliceous mineral the best relative permeability to oil
surfaces. The length of the polysiloxane chain formed
by the hydrolysis of the organosilane, and the subse- • help to prevent insoluble fines from becoming oil-
quent condensation/polymerization of silanols, is not wet and stabilizing emulsions
known but is believed to be short. Acid, which cat- • help to maintain the required concentration of sur-
alyzes the initial hydrolysis of the organosilane, also factants and inhibitors in solution by reducing
retards the growth of polymer chains. adsorption of these materials
The mechanism by which the polysiloxane coating • help to dissolve both the adsorbed inhibitor and
stabilizes fines is different from the ion-exchange acid-insoluble residue (certain acid corrosion
mechanism by which other clay stabilizers work. inhibitors contain acid-insoluble residues that can
However, it is similar to the coating process pro- cause formation plugging and inhibitor adsorption
posed for fluoboric acid (Boyer and Wu, 1983). The on formation minerals and change the wettability)
polysiloxane coating binds clay and other siliceous • dissolve any oil on the formation pore surface
fines in place through covalent siloxane bonds. The

Reservoir Stimulation 15-13

• serve as a de-emulsifier 15-6. Iron control additives
• improve the cleanup of spent acid following
treatment. 15-6.1. Sources of iron
Commonly used mutual solvents and their normal When appreciable quantities of iron in the form of
concentrations are Fe3+ (ferric ions), rather than the usual Fe2+ (ferrous
• ethylene glycol monobutyl ether (EGMBE): 10% ions), are dissolved by the acid, iron precipitation
by volume and permeability reductions can occur after acidiz-
ing. The oxidation state of the iron governs precipi-
• ether/surfactant/alcohol blends: 5% by volume.
tation. Ferric iron precipitates at a pH of about 2,
whereas ferrous iron precipitates at a pH of about
7—the actual values depend on the concentrations of
15-5.1. Adsorption of mutual solvents the ferrous and ferric ions. Because spent acid solu-
King and Lee (1988) studied the adsorption proper- tions seldom rise to a pH above 6, precipitation of
ties of an alcohol-mixture mutual solvent, such as a ferrous iron is seldom a problem. Sources of iron
blend of isopropyl alcohol and isooctyl alcohol, and include
EGMBE. They found that adsorption of the mutual
• corrosion products found on the walls of the tubu-
solvent can be severe depending on the type of
lars
mutual solvent. For deep damage removal, products
that are lost during injection through the formation • mill scale
are not acceptable because the mutual solvent is • iron-bearing minerals.
removed from the leading edge of the acid. Although Iron occurs naturally in formation waters or in for-
there appears to be no direct damage caused by mation minerals (Table 15-5). However, the tubulars
adsorption of the mutual solvent, the acid is left after in the well are one of the most prominent sources of
the loss without any material to lower surface tension iron. Before the acid reaches the formation, it flows
or to break emulsions. Paktinat (1991) recommended for a relatively long time through the tubing. Tubing
the use of ethoxylated alcohol with EGMBE to mini- usually contains rust, which is dissolved by acid.
mize adsorption, thus resulting in deeper penetration Newly manufactured tubing has a crust of mill scale.
of the mutual solvent and reduced emulsion tenden- The thickness of the mill scale on oilfield tubulars
cies. varies considerably depending on the cooling rate
and how much the pipe was manipulated during the
straightening procedure. Mill scale is composed of
15-5.2. Chlorination of mutual solvents
two distinct layers—a hard, dense layer next to the
King and Lee (1988) presented data on the chlorina- pipe that is approximately 0.003 in. thick; on top of
tion of mutual solvents with 15% and 28% HCl at the dense mill scale is a layer of softer, flaky mill
temperatures from 70° to 250°F [20° to 120°C]. The scale that is approximately 0.007 in. thick. Most of
chlorination issue has long been of interest because the softer scale pops off the pipe during the straight-
chlorinated hydrocarbons poison refinery catalysts. ening procedure.
Their data show that the chlorination of mutual sol-
vents is a function of
Table 15-5. Oxidation state of iron
• type of mutual solvent in formation minerals.

• temperature Mineral Chemical Formula Oxidation State

• concentration of HCl (i.e., spending of HCl Hematite Fe2O3 Fe2+
reduces the possibility). Magnetite FeO–Fe2O3 Fe2+–Fe3+
At temperatures exceeding 200°F, especially with Pyrite FeS Fe2+
28% HCl, the chlorination of most mutual solvents Siderite FeCO3 Fe2+
was severe, if there were no carbonates with which the Chlorite clay – Fe2+
acid could react. The presence of carbonates resulted
Mixed-layer clay – Fe2+
in very low production of chlorinated hydrocarbons.

15-14 Additives in Acidizing Fluids

 The theoretical quantity of 15% HCl required to • Sequestering agents
remove 0.073 lbm of mill scale from 27⁄8-in. tubing is Sequestering agents bond to the iron and hold it
69 gal/1000 ft of tubing. If a 10,000-ft well is acidized in solution so that it cannot precipitate. Citric acid,
for damage removal, approximately 690 gal of 15% ethylenediaminetetraacetic acid (EDTA) and
HCl could be neutralized by the mill scale. Of course, nitrilotriacetic acid (NTA) are some of the more
the acid contact time and temperature control the commonly used sequestering agents.
quantity of mill scale removed. If acid is spent on mill
scale, it will contain 85,900 ppm of total iron. Of this, • Reducing agents
57,300 ppm will be ferric iron (Fe3+). Thus, the lead- Reducing agents convert ferric (Fe3+) to ferrous
ing edge of the treating fluid may be partially spent (Fe2+) iron. Secondary precipitation of ferric iron
acid that contains a high concentration of iron. The occurs at a pH of about 2.0. The secondary precip-
ferric iron can be precipitated as ferric hydroxide itation of ferrous iron hydroxides does not occur
(Fe(OH)3), a dark brown gelatinous precipitate that until the pH is above 7.0. Returned spent acids
can be damaging to the formation. never have a pH this high. Erythorbic acid and
It should be emphasized that acid dissolves iron sodium erythorbate are commonly used as reduc-
compounds regardless of the presence of any type ing agents. Erythorbic acid is preferred over
of inhibitor used to protect the elemental iron in the sodium erythorbate in sandstone acidizing because
steel. Iron control additives help prevent the precipi- the addition of sodium salts of either sequestering
tation of iron hydroxide. or reducing agents to mud acid can lead to the pre-
Concern is often expressed about the dissolution cipitation of insoluble hexafluosilicate. Hall and
of iron-containing minerals (siderite, hematite and Dill (1988) reported that erythorbic acid is unsta-
chlorite) from the formation and subsequent precipi- ble in hot HCl and decomposes to form an insolu-
tation of the dissolved iron. Previous studies indicate ble precipitate. Although this is true, the decompo-
that most of the iron contained in these minerals sition process is slow and the acid normally
occurs in the Fe2+ oxidation state (Table 15-5) and spends long before precipitation can occur
does not present a precipitation problem. However, (Crowe, 1985).
numerous exceptions to this rule exist. Streaks of Most reducing agents also act as oxygen scav-
pure hematite (Fe2O3) occur in some sandstones, engers that remove dissolved oxygen from the
whereas others contain Fe3+-type minerals uniformly fluid. The scavengers prevent the oxidization of
distributed within the matrix of rock. Where these ferrous iron to ferric iron. This maintains iron in
conditions are present, greater amounts of an iron solution by preventing the precipitation of ferric
control additive are required to control ferric hydrox- iron. The amount of iron that can be reduced
ide precipitation. depends on the quantity of chemical added.
Aeration of the solution can introduce additional
oxygen.
15-6.2. Methods of iron control Table 15-6 compares iron control additives,
The three methods currently used to help keep iron showing their advantages and disadvantages and
in solution are pH control, sequestering agents and the amount of each required in 1000 gal of 15%
reducing agents (also effective as oxygen scaven- HCl to sequester 5000 ppm of ferric iron at 150°F
gers). These may be used individually or in combi- [65°C] for a minimum of 2 days.
nation, depending on the source and amount of iron The safest way to prevent damage to the reservoir
dissolution expected. from precipitated iron hydroxide is to clean or
pickle the pipe with acid before acidizing the for-
• pH control mation. The acid should contain large quantities of
pH control is accomplished by the addition of a iron control additives and should be circulated out
weak acid that is very slow to react so that a low of the well, not pumped into the formation. In con-
pH is maintained after the HCl has spent. Acetic junction with this treatment, a dispersed hydrocar-
acid is typically used for this purpose. A low pH bon phase should be incorporated or used as a pre-
aids in preventing the secondary precipitation of flush to remove pipe dope that could plug the perfo-
iron. rations.

Reservoir Stimulation 15-15

 Table 15-6. Comparison of various iron control agents.

Control Agent Advantages Disadvantages Amount (lbm)

Citric acid Effective at temperatures up to Precipitates as calcium citrate if excess 175
400°F [205°C] uncomplexed quantities are used (more
than 10 lbm/1000 gal)

Citric acid–acetic acid Very effective at lower temperatures Even for the indicated amount, calcium Citric: 50
mixture citrate precipitates unless at least 2000-ppm Acetic: 87
Fe3+ is present in spent acid.

Efficiency decreases rapidly at temperatures

above 150°F [65°C]

Lactic acid Little chance of calcium lactate Not very effective at temperatures above 190
precipitation if excessive quantities 100°F [40°C] (at 75°F [25°C])
are used

Acetic acid No problem from possible precipitation Effective only at temperatures at about 150°F 435
as calcium acetate

Gluconic acid Little chance of calcium gluconate Effective only at temperatures up to 150°F 350
precipitation
Expensive on a cost-performance basis

Tetrasodium salt Large quantities may be used without More expensive to use than many other agents 296
of EDTA precipitation of calcium salt.

Effective at temperatures up to 400°F

Nitrilotriacetic acid Effective at temperatures up to 400°F 150

More soluble in acid than EDTA—

higher concentrations can be used

Less expensive than EDTA

Sodium erythorbate Smaller quantities required Increased corrosion inhibitor concentration 23

required for certain applications
Effective at temperatures up to 400°F
Should not be used in HF—use erythorbic acid

The treatment of sour wells presents an entirely 15-7. Alcohols

different type of precipitation problem. In addition to
free sulfur precipitation, by the reaction of Fe3+ with Alcohols are used in acidizing fluids to remove water
H2S, the dissolved Fe2+ also precipitates as ferrous blocks, enhance fluid recovery, retard acid reactivity
sulfide (FeS) on spending of the acid. FeS precipi- and decrease water content. The most common alco-
tates at a pH of about 2. Laboratory and field data hols used in acidizing are isopropanol and methanol.
presented by Hall and Dill (1988) show that a com- Their physical and chemical properties are listed in
bination of NTA, EGMBE and a sulfide modifier is Table 15-7.
an effective system for controlling the precipitation
of FeS and free sulfur when acidizing sour wells. Table 15-7. Physical and chemical properties of
Crowe (1985) previously proposed a two-component isopropanol and methanol.
system to address sour well problems. The system Property Isopropanol Methanol
incorporates erythorbic acid to reduce ferric iron to
Density at 68°F [20°C] 0.785 0.792
ferrous iron and EDTA to chelate ferrous iron and
Weight (lbm/1000 gal) 6.54 6.60
eliminate the precipitation of FeS.
Flash point (closed up, °F [°C]) 54 [12] 54
Solubility in water Complete Complete

15-16 Additives in Acidizing Fluids

 Isopropanol is normally used at a maximum of • Low flash point
20% by volume. Methanol is used at various concen- Both isopropanol and methanol, and even acid
trations, but a typical concentration may be 25% by solutions containing 20% or more by volume of
volume. Alcohol is used in acidizing fluids for the either, have low flash points.
following reasons.
• Increase in corrosiveness
• Removal of water blocks
Corrosion tests have shown that alcohol-acid mix-
One problem that can severely decrease produc- tures require a higher concentration of inhibitor
tion is blockage of the pore spaces by water; this than equivalent acid mixtures without alcohol.
is commonly known as a water block. Water
blocks may form where high capillary forces are • Adverse reactions
present in porous rocks. The most severe water Formation brines with a high concentration of dis-
block problems occur in formations with gas per- solved salts can “salt out” in the presence of alco-
meabilities less than 120 md. The alcohol in the hols. To help prevent the occurrence of salt precip-
treating fluid reduces the capillary forces within itation, treating solutions should not exceed 20%
the reservoir, thus enabling easier removal of the by volume of isopropanol or 40% by volume of
liquid phases. methanol.
• Enhancement of fluid recovery • Incompatibility
Another problem that occurs in treating oil or gas Some crude oils are incompatible with both
wells is the recovery of treating fluids, especially methanol and isopropanol. Compatibility tests
in gas reservoirs. The high surface tension of should be conducted before acidizing a well with
water or acid solutions hinders their penetration a fluid containing alcohol. Some formation types
and recovery. Conventional surfactants help, may even be extremely sensitive to aqueous solu-
although they lose much of their activity by tions that contain high concentrations of alcohols.
adsorption. The addition of alcohol to acid solu- • Side reactions
tions reduces their surface tension. The concentra-
tion of alcohol normally used for this purpose is There are undesirable side reactions when alcohols
sufficient so that loss by adsorption is not a prob- are used in acidizing. Even under moderate temper-
lem. ature conditions, alcohols react readily with acid.
In the case of organic acids (e.g., acetic or formic
• Retardation of acid reactivity acid), these reactions result in ester formation, with
Alcohol has a retarding effect on acid reactivity. the only resulting problem being a possible loss of
The retardation rate is related to the type and per- available acid for the stimulation reaction. Even
centage of alcohol added. this may be of small consequence, because the
esterification reaction is reversible and regeneration
• Decrease of water in acids
of the organic acid for the desired stimulation reac-
Some formations contain a large amount of water- tion is possible (Keeney and Frost, 1975):
sensitive clays. To minimize the amount of water
contained in acidizing solutions, alcohols are used CH3COOH + CH3OH CH3COOCH3 + H2O
in place of the dilution water. acetic acid methanol methyl acetate

The major disadvantages of using alcohol in acid- However, in an alcoholic solution of HCl, a
izing fluids are as follows: reaction takes place that results in the formation
of the following organic chlorides:
• Effective concentration
CH3OH + HCl → CH3Cl + H2O
It takes a large amount of alcohol, 20% or more, to
methanol hydro- methyl
provide beneficial effects.
chloric acid chloride
• Cost
CH3CHOHCH3 + HCl → CH3CHClCH3 + H2O
Replacing water with alcohol in the acidizing solu- isopropanol hydro- isopropyl
tion makes the treatment more expensive. chloric chloride
acid

Reservoir Stimulation 15-17

 This poses a genuine problem in gas well stimula- Recent field trials by Shuchart and Ali (1992)
tion because the second and third of these reactions show that the use of 3% acetic acid in HF acidizing
are irreversible, and any HCl lost to this process can- sequences decreases the occurrence of scaling. The
not be regenerated, as is possible with organic acids use of acetic acid delays the precipitation of alumi-
in the first equation. Thus, these reactions reduce the nosilicate scale by two mechanisms—a buffering
HCl content. A second problem concerns the reac- effect and a chelating effect.
tion products themselves. Although the presence of
organic chlorides in natural gas might not present
any special problems, their presence in produced 15-9. Organic dispersants
crudes or distillates is considered serious contamin-
ation, because of the detrimental effect of chlorinated A relatively new method of removing organic
hydrocarbons on refinery catalysts. deposits is the use of a dispersant surfactant with
Figure 15-10 shows the effects of increasing tem- xylene. These surfactants can penetrate and loosen
perature on the reduction of acid strength for four organic deposits so that the xylene can effectively
concentrations of methanol. The data show that there dissolve or remove the deposit. Concentrations of
is no significant loss of acid strength with methanol 1% to 10% volume/volume are used depending on
concentrations up to 32% by volume until the tem- the deposit type, hardness and adhesion and the bot-
perature exceeds 175°F [80°C]. tomhole temperature. For matrix, wellbore and tub-
ing cleanup treatments, a soaking period of several
hours is recommended.
15

10 15-10. Organic solvents

HCl (%)

As Fig. 15-1 shows, organic solvents used alone or

5 16% MeOH
in combination with acid and other materials are use-
32% MeOH
48% MeOH
64% MeOH
ful for removing water blocks and solids. King
0 (1986) provided a good discussion of the uses of
0 50 100 150 200 250 300 these solvents alone and in combination with acid for
Temperature (˚F)
damage removal. Organic solvents include alcohols
in addition to more traditional solvents such as
Figure 15-10. Effect of various concentrations of methanol
on acid strength at increasing temperatures (courtesy of
xylene, toluene and diesel.
Halliburton Services). Organic solvents are particularly useful for the
removal of organic deposits. An organic solvent can
be combined with acid when the inorganic scales are
mixed with or coated by asphaltenes and paraffins.
An oil-external emulsion with the appropriate acid as
15-8. Acetic acid the internal phase is useful for treating mixed depos-
A common problem in HF acidizing is the precipita- its. The emulsion provides a further benefit of retard-
tion of reaction products. Many of the precipitation ing the acid, thus allowing the deeper penetration of
reactions occur almost immediately on spending the live acid.
acid solution. Most of these precipitation problems
can be overcome by the use of an adequate acid pre-
flush and ammonium chloride (NH4Cl) overflush. 15-11. Diversion
However, precipitation can also occur days, months
Diversion is often required to ensure that the treating
or even years after an HF acidizing treatment. This
fluid works effectively. Diverters function simply by
precipitation is often called aluminosilicate scaling.
equalizing the flow so that zones of differing perme-
Scales of this type are believed to form when the
abilities can be treated. Schechter (1992) provided a
spent HF mixes with formation fluid to slightly raise
good discussion of diversion principles. The empha-
the pH, thus causing precipitation.
sis in this section is on diversion through the use of

15-18 Additives in Acidizing Fluids

particulates added to the treating fluid and foams discharge regulations. On flowback, emulsion and
rather than the use of packers or ball sealers. oil/water separation problems that occur can poten-
Ideally the diverter should tially result in excess oil solubilized in the water by
the formation of microemulsions. Emulsion prob-
• be insoluble in the treating fluid
lems under such circumstances can result in thou-
• form an essentially impermeable layer on the for- sands of gallons of non-pipeline-quality oil and
mation face without penetrating deeply into the could shut down the separation unit and minimize
formation production from these wells. Dehydrated oil and
• be easily removed following the treatment. clean discharge water are required to maintain nor-
Generally all, or at least most, of these criteria can mal uninterrupted production.
be met using materials such as oil-soluble resins, Regulations for the disposal of produced water in
benzoic acid flakes and other particulates. Particulate offshore operations are becoming increasingly strin-
diverters may cause damage and can be difficult to gent. The U.S. National Pollutant Discharge
clean up as a result. Elimination System (NPDES) has established dis-
Foams may also provide effective diversion charge levels for oil and grease at a 29-mg/L
(Zerhboub et al., 1991). Foamed fluids have the monthly average with a grab sample maximum of
additional advantage of good cleanup with little or 42 mg/L. This is a reduction in the allowable levels
no potential for damaging the formation. The ratio from 48 to 29 mg/L. The penalty for noncompliance
of nitrogen to fluid depends on the bottomhole con- by the operator can be severe. These discharge levels
ditions during the treatment. Diversion and fluid are causing the reevaluation of acidizing treatments.
placement strategy are addressed in Chapter 19. During the flowback immediately following an
acid treatment, significantly higher levels of oil and
grease than those permitted for discharge have also
been recorded. During flowback, spikes in the basic
15-12. Additive compatibility sediment and water (BS&W) values occur immedi-
All additives should be tested in the laboratory. ately after an acid treatment. Microemulsions are sus-
Compatibility of additives with formation fluids pected of occurring during flowback. The produced
should be tested using a sandpack method developed oil is solubilized in the returned spent acid, and this
by Ali et al. (1994). This procedure is more repre- results in significantly higher levels of oil and grease.
sentative of downhole conditions and uses more sand The use of matrix additives is believed to contribute
than the test in API Recommended Practices for to the solubilization of the oil and additives. These
Laboratory Testing of Surface Active Agents for Well additives should be optimized to minimize emulsion
Stimulation (RP 42) (1977). The acid system with upsets and the levels of oil and grease.
additives is drawn through a pack of formation core Verification and optimization of the additives used
material or a mixture consisting of 10-wt% illite- in acid stimulation treatments have been requested
bentonite, 10-wt% silica flour and 80-wt% 100-mesh by operators. Obtaining an answer to treatment facil-
sand. There are no universal additives for all forma- ity upsets by additive optimization in matrix treat-
tion problems. Any potential incompatibilities ments can have a tremendous impact on acidizing
between additives and formation fluids must be iden- workover operations. Research by Bansal (1993)
tified and corrected before acidizing. determined the following maximum concentrations
of inhibitors, surfactants and mutual solvents that
may be present in the returned fluids to maintain oil
15-13. Facility upsets following and grease levels below 48 mg/L:
acid stimulation • inhibitors: 80 ppm
• surfactants: 10 ppm
15-13.1. Discharge requirements
• mutual solvents: 100 ppm.
The chemicals used in acidizing treatments have
The common denominator for each of these addi-
been linked with oil and water separation facility
tives is surface-active compounds (i.e., surfactants).
upsets, causing noncompliance with environmental

Reservoir Stimulation 15-19

The surfactants provide acceptable fluid perfor- et al. (1994) recommended an alternate procedure
mance, such as corrosion inhibition, dispersion and that better simulates downhole intermixing of the
wetting properties, as they were initially designed for stimulation fluids and the produced crude. The pro-
the acid treatment. However, if the additives are used cedure involves filtering formulated acid, containing
in excessive concentrations, they may exacerbate the inhibitor, surfactants, mutual solvents and nonemul-
emulsification tendencies of fluids during flowback. sifiers, through a sandpack containing 10-wt% silica
The difference in emulsion stability is attributed to flour, 10-wt% clays (such as montmorillonite) and
other, more dominant factors (e.g., stabilization by 80-wt% 100-mesh sand prior to completion of the
solids precipitation [organic and inorganic], ferric emulsion test. This procedure simulates the filtration
ion interaction with the crude oil and viscosity of the acid system within the rock matrix. Surfact-
increase at the interface). Results presented by ants, such as those used in nonemulsifiers, are
Coppel (1975) show that acids partially spent on for- adsorbed onto mineral surfaces. The adsorption
mations contain potentially precipitable materials in minimizes the availability of the surfactants in solu-
solution. As the pH of the produced acid increases tion to prevent emulsions.
during flowback and mixes with other produced flu- Durham et al. (1995) reported that oil and water
ids, precipitates form that can stabilize emulsions. emulsion upsets could be minimized by proper selec-
Dunlap and Houchin (1990) recommended polarized tion of the acidizing additives and surface treating
microscopy to evaluate return fluids to establish the chemicals. When acid flowbacks are introduced into
cause for a stabilized emulsion. Specific damage a production system, the control of emulsions by
mechanisms, such as emulsion stabilization by chemical treatment can significantly change in com-
organic deposits, solids and iron, could be detected parison with control during production of the well
and identified. prior to treatment. These authors completed exten-
sive emulsion breaker and water clarification tests
with the desired acid/additive systems and fresh
15-13.2. Prevention of facility upsets crude oil to duplicate the commingling of the acid
Preventing upsets requires optimizing the fluid design with the oil during flowback. The low pH of the
to minimize or eliminate the formation of precipitates water in the emulsion rendered the current treating
and using the optimum de-emulsifier. The potential program ineffective until the acid flowback was
for the formation of emulsions of acid and produced completed. Nonionic de-emulsifiers were found to be
crude oil while still providing the required downhole more effective than sulfonate-type additives for treat-
function optimization of the de-emulsifier treatment ing these emulsions. On-site testing is recommended
is evaluated currently by the procedures recommend- to select an effective chemical treatment.
ed in API RP 42 (1977). Vigorous mixing of acid Ali et al. (1997) reported the optimization of
with fresh crude oil in a glass container is observed acidizing additives to reduce production facility
under bottomhole temperatures (hot-water bath) to upsets. The authors combined additive treatment
determine the characteristics and time for emulsion optimization with a new absorption/filtration process.
breakout. Fine siliceous materials, ferric iron or both The optimized treatments involved the evaluation of
can be added to evaluate emulsion stability. surfactants and mutual solvents, which are consid-
These fluid interactions can simulate the downhole ered to be the additives primarily responsible for
emulsion problems encountered; however, these tests emulsion problems during acid flowback. Elimina-
fail to accurately predict the interaction of the treating tion of some additives, minimizing the concentra-
fluids with the acid-sensitive crudes during flowback. tions of other additives and using a dual-purpose
As a result, marginal treatment response is observed. mutual breakout solvent reduced facility upsets. All
Downhole emulsions and facility upsets may be recommendations were based on laboratory testing
attributed to inadequate prejob compatibility testing, using the sandpack method and on-site testing with a
because the additives employed in the acid system laboratory unit. The filtration process used a special-
may preferentially adsorb out onto the rock matrix or ized absorption medium to aid in lowering oil and
partition to the oil phase during production. grease levels. This combination of treatment opti-
Alternate testing procedures have been developed mization with filtration/absorption reduced facility
to more accurately simulate reservoir conditions. Ali upsets while not interfering with the efficacy of the
treatment.

15-20 Additives in Acidizing Fluids