Acidizing & Other Chemical Treatments

Introduction to Acidizing
Introduction
Acidizing is one of the oldest techniques in well stimulation processes still being used today, though
its use only began toward the end of the last century. Table 1 (below) lists the major events in the
early history of acidizing.
Acidizing is a chemical process which dissolves an unwanted substance in the formation, pipe,
surface equipment, or flow-lines. In the case of treating formation damage, acid removes flowrestricting particles, scale deposits, and minerals in the reservoir or in the immediate wellbore
vicinity. The acid mixture holds the dissolved substance in solution until it is either removed from the
well system or overflushed a safe distance into the formation; then, the well can produce at its
natural potential. Little, if any, increase in productivity will result unless formation damage actually
exists.
When a fracture is created during an acidizing operation in carbonate reservoirs, increased flow
capacity can result from acid etching of the fracture faces. Here, large increases in productivity are
possible by creating a highly conductive flow path through the formation.

Year

Event

1894

Acid was used to stimulate oil production in limestone formations in Lima, Ohio.

1896

First patent related to acid treatments of wells was issued to Herman Frasch.

1928

Acid was used in Glen Pool, Oklahoma by Gypsy Oil Company, a subsidiary of Gulf Oil
Company.

1929

Subsidiary of Gulf Oil Corporation injected uninhibited hydrochloric acid under pressure into
a well in Lee County, Kentucky.

1930

Acidizing experiments were discontinued.

1932

Dow Chemical Company and Pure Oil Company used an acid treatment of 15%
hydrochloric acid plus arsenic as an inhibitor on a well in the Greendale Pool of Midland
County, Michigan.

1932

Dow Chemical Company and Pure Oil Company used an acid treatment of 15%
hydrochloric acid plus arsenic as an inhibitor on a well in the Greendale Pool of Midland
County, Michigan.
Patents were issued to Grebe and Sanford of Dow Chemical Company for treatments of oil
wells with chemicals containing a corrosion inhibitor.
R.H. Carr of the Pure Oil Company was issued a patent on the technique of chemically
treating an oil well by the balanced fluid column method.
Dowel I Chemical Company formed Dowel I Inc. (now Dowell-Schlumberger from its Well
Service Group whose original main responsibility was stimulation of Dow's brine wells.
Carey K. West formed the Chemical Process Company, a predecessor to Byron Jackson,
Inc. (now BJ-Hughes).

1933

J.R. Wilson with Standard Oil Company filed a patent on a technique for treating sandstone
formations with hydrofluoric acid.

1935

Halliburton Oil Well Cementing Company (now Halliburton Services) began acidizing oil
wells.

1940

Dowell (now Dowell-Schlumberger) began the first commercial use of mixtures of

hydrochloric and hydrofluoric acid.

Table 1: Early History of Acidizing

Acid Treating Solutions

Acid Treating Solutions
Whatever their specific formulation, all acids have hydrogen ions that react with carbonate rock
(principally limestone and dolomite) to form water and carbon dioxide, and with siliceous minerals
(sandstone and clays) to form fluosilicic acid and water.

Mineral Acids
Hydrochloric Acid
Hydrochloric acid (HCl) is the workhorse of the stimulation business, finding extensive use in both
carbonate and sandstone acidizing. Chemically, hydrochloric acid is hydrogen chloride in aqueous
solution. Composed of hydrogen and chlorine gas, it is gaseous in the chemically combined state.
Hydrogen chloride gas is readily soluble in water. Concentration is described as percent by weight of
HCl gas dissolved in water. HCl acid is commercially available; its concentration has been
standardized at 20 Be, i.e., 31.45% acid, and it has a specific gravity of 1.160.
Many acidizing treatments employ HCl to some extent. Usually, it is used as a 15% solution when
treating carbonate formations. This concentration, commonly referred to as regular acid, was
originally chosen because of inadequacies in early inhibitors and difficulty of preventing corrosion of
well tubulars by more concentrated solutions.
Fifteen-percent HCl is used most frequently because it:

costs less per unit volume than stronger acids and is less costly to inhibit;
is less hazardous to handle than stronger acids;
retains larger quantities of dissolved salts in solution after spending.

Although acid concentrations higher than 15% may also be used in carbonate formations, lower strengths are more
suitable where acid dissolving power is not the sole consideration. In sandstone acidizing, for example, 5 to 7.5%
HCl is often used ahead of hydrochloric-hydrofluoric acid mixtures to prevent precipitation of formation-plugging
reaction products.
The principal disadvantage of HCl is its corrosive action on wellbore tubular goods.
HCl reacts with limestone (CaCO3) to form calcium chloride (CaCl2), water (H2O) and carbon dioxide
(CO2):
As shown, 2 moles of hydrochloric acid reacts with 1 mole of CaCO3 to produce 1 mole each of
calcium chloride, water and carbon dioxide. The molecular weights of these compounds are as
follows:

Compound

Molecular Weight

Hcl

36.47

CaCO3

100.09

CaCl2

110.99

H2O

18.02

CO2

44.01

Thus, to dissolve one pound of limestone, we would need

[(1 lb CaCO3)

(mole/100.09 lb)]

[(2 mole HCl/ mole CaCO3)

(36.47 lb/mole)]

= 0.729 lb HCl
On a volumetric basis, for the case of a 15 percent HCl solution (specific gravity = 1.076 at 60F;
density = 8.96 lb/gal), one gallon of acid will dissolve (8.96 0.15)/(0.729) = 1.84 lb CaCO3.
The reaction of HCl on dolomite is very similar to its reaction on limestone, except for the presence of
magnesium. The chemical reaction of HCl and dolomite CaMg (CO3)2 is:

4HCl + CaMg(CO3)sub>2 => CaCl2 + MgCl2+ 2H2O + 2CO2

(2)
Hydrofluoric Acid
Hydrofluoric acid is the primary dissolving chemical used in sandstone acidizing. In these
applications, HF is usually mixed as a dilute solution with HCl, or an organic acid. Its principal use is
to dissolve siliceous minerals.
Within the chemical industry hydrofluoric acid (HF) is available commercially as a relatively pure
material in anhydrous form (where it is fuming and corrosive) or as a concentrated (40 to 70%)
aqueous solution. Anhydrous HF is not used in the field because its low boiling point of 66.9 F is
often exceeded by ambient temperatures. HF reacts with silica and silicates, such as glass and
concrete. It also attacks natural rubber, leather, cast iron, and many organic materials.
HF is the only acid that reacts either siliceous minerals such as sand and clays. The reaction of HF on
quartz (SiO2), a primary component of sand, is:
4HF + SiO2 SiF4 + 2H2O
SiF4 + 2HF H2SiF6

(3)

Here, the end reaction product, fluosilicic acid (H2SiF6), is soluble in water, but its potassium and
sodium salts are insoluble. HF contact with formation water containing CaCl2, MgCl2, NaCl or KCl thus
must be avoided near the wellbore. The only salt solution compatible with HF is ammonium chloride.
The reaction of HF on bentonite clay (Al2(Si4O10)(OH)2) is:
36HF + Al2(Si4O10)(OH)2 4H2SiF6 + 2H3AlF6 + 12 H2O

(4)

Hydrofluoric acid also reacts with carbonates; its reaction with limestone is:

2HF + CaCO3 CaF2 + H2O +CO2

(5)

HF will react with calcium ions from any source to form the insoluble precipitate calcium fluoride
(CaF2), which can cause sever plugging problems in the formation. The portion of the reaction that
creates calcium fluoride is:
Ca++ + 2F- CaF2

(6)

CaF2 formation can be avoided through the proper use and optimal placement of HCl in the acid
treatment.
Hydrochloric-Hydrofluoric Acid Mixtures
Hydrochloric-hydrofluoric acid mixtures are the chief solutions used in matrix acidizing of sandstone.
These acids are very often used as mixtures because HCl ties up and displaces anions, which in turn
prevents reaction of these anions (e.g., Ca++, Mg ++, etc.) with HF. Although HF is the only acid
effective on siliceous minerals, it is ineffective as a stimulation agent on carbonates because its
reaction forms insoluble CaF2.
The usual HF solution used in the field contains 3% HF and 12% HCl. This solution is commonly
called regular mud acid. However, concentrations of HF in HCl solutions range from 0.5 to 9%, and
some operators prefer 1-1/2% HF and 6% HCl.
These mixtures may be formed from the dilution of concentrated solutions of HF or, more frequently,
from the reaction of ammonium bifluoride (NH4HF2) or ammonium fluoride (NH4F) with HCl. Usually,
15% HCl is used, and enough NH4HF2 or NH4F is added to create a solution containing 3% HF.
Consumption of hydrogen chloride by these reactions leaves 12% HCl remaining in solution.
Similarly, 1.5% HF can be prepared from 7-1/2% HCl solutions where the final HCl concentration is
6%.
Corrosion characteristics of HCl-HF mixtures are comparable to those of HCl alone, and similar
corrosion inhibitors are required. Both HCl and HCl-HF acid mixtures are stronger and more reactive
than organic acids.

Organic Acids
Organic acids offer the benefit of relatively low corrosivity and easy inhibition at elevated
temperature. They are particularly applicable, therefore, to high-temperature well applications.
Acetic (HC2H3O2) and formic (HCHO2) acids are the two principal organic acids used in acidizing. These
acids are weaker than mineral acids; they react more slowly and are also less damaging. Acetic, for
example, is the only acid available that will not damage chrome plating or aluminum and magnesium
surfaces. In some cases, organic acids are mixed with HCl or HF to provide deeper acid penetration
into the formation.
Acetic Acid
Acetic acid was the first organic acid to be used in appreciable volumes in acidizing. It is easy to
inhibit against corrosion and commonly used as a 10% by weight solution of acetic acid in water. At
this concentration, the reaction products are generally soluble in spent acid. Acetic acid functions well
as a perforating fluid or low-corrosivity acid when in contact with metals that corrode easily.
Commercially available "pure" acetic acid is approximately 99% acetic acid. It is called glacial acetic
acid because icelike crystals form at temperatures around 60 F and it solidifies near 48 F. When

glacial acetic acid is mixed with water, a contraction occurs. For this reason, the amounts of acetic
acid and water normally total more than the required volume when making dilute solutions.
Acetic acid reacts with limestone to form calcium acetate (Ca(C 2H3O2)2), water and carbon dioxide:
2HC2H3O2 + CaCO3 > Ca(C2H3O2)2 + H2O + CO2

(8)

As shown, 2 moles of acetic acid reacts either 1 mole of CaCO3 to produce 1 mole each of calcium
acetate, water and carbon dioxide. The molecular weights of these compounds are as follows:

Compound

Molecular
Weight

HC2H3O2

60

CaCO3

100.09

CaCl2

110.99

H2O

18.02

CO2

44.01

Thus, to dissolve one pound of limestone would require:

[(1 lb. CaCO3) x (mole/100.09 lb.)] x
[(2 mole HC2H3O2/mole CaCO3) x (60 lb./mole)]
= 1.2 lb.HC2H3O2
On a volumetric basis, for the case of a 15 percent HC2H3O2 solution (specific gravity = 1.037 at
60oF; density 8.64 lb./gal.), one gallon of acid dissolves (8.64 x 0.15)/(1.2) = 1.08 lb. of limestone.
An identical concentration of HCl dissolves 1.84 lb. of limestone. (see Table 1).
Formic Acid
Formic acid is the simplest of the organic acids. It is stronger than acetic, yet weaker than HCl, and
is most frequently used in combination with HCl as a retarded acid system for high-temperature
wells. Formic acid can be easily inhibited, but not as effectively as acetic acid at high temperatures
and long contact times. The percentage of formic acid generally used is 8% to 10% by weight.
A 10% solution of formic acid will dissolve as much limestone as an 8% solution of HCl. The chemical
reaction of formic acid and limestone is:
2HCHO2 + CaCO3 > Ca(CHO2)2 + H2O + CO2

(9)

Acid
type

Concentration
%

CaCO3
dissolved
per gal.
acid- lb.

CO2
formed
per gal.
acid cu.
Ft.

CaCl2
formed
per gal.
acid- lb.

HCl*

15*

1.84

6.99

2.04

Acetic*

Formic*

20

2.50

9.47

2.75

25

3.22

12.20

3.57

15*

1.08

4.09

1.71

20

1.43

5.41

2.25

25

1.80

6.82

2.84

15*

1,42

5.38

1.84

20

1.90

7.20

2.47

25

2.40

9.09

3.12

* The most commonly used strength for HCl is 15% and 10% for acetic and formic acids. In this
table, however, the HCl reaction rate on limestone is compared to the equivalent strength rates for
acetic and formic acid rather than to the latter's commonly used strengths.
Table 1: Reaction of three acids on limestone at various concentrations.
Formic acid is frequently used in reservoirs with extreme temperatures or low injection rates. At high
temperatures, organic inhibitors work more effectively on formic acid with HCl than on HCl alone.
This property minimizes the danger of hydrogen embrittlement of steel associated with HCl
treatment in high-temperature formations.
Organic acids have less dissolving capability than HCl and must be used in greater volumes for
comparable results, making such treatments more expensive.
The dissolving power of various concentrations of HCl, acetic, and formic acids is shown in Table 1.
The cost of acetic acid per unit based on dissolving power is more expensive than either HCl or
formic acid. With the exception of fracturing acidizing treatments, dissolving power is not often the
primary consideration in acid selection.
The most commonly used strength for HCl is 15% and 10% for acetic and formic acids. In Table 1,
however, the HCl reaction rate on limestone is compared to the equivalent strength rates for acetic
and formic acid rather than to the latter's commonly used strengths.
Hydrofluoric-Organic Acid Mixtures
Acid mixtures of HF and either acetic or formic acid are used to slow the reaction of the acid on sand
and clay, and to reduce corrosiveness. These acid mixtures can be effectively inhibited for up to 16
hours at 400 F. Mixing HF with organic acids can provide deeper penetration and, therefore,
effective removal of deep formation damage. Organic HF mixtures are recommended at temperatures
of 200 F and above; below 200 F they can cause the formation of undesirable reaction products.

Specialty Acids
Specialty acids are designed to deal with specific formation conditions, such as deep clay damage,
paraffin blockage in the reservoir, and situations requiring a retarded acid.
Powdered Acid

Powdered acids (sulfamic and chloroacetic) are used in applications where logistics are of primary
concern - for example, in remote locations where bulk transport of liquids is impractical or very
expensive. These crystaline powders are readily soluble in water.
Sulfamic acid (HSO3NH2) is a nonvolatile, nonhydroscopic, white crystalline or granular solid. Its
reaction products with carbonates are water soluble, and it is highly ionized in water. Sulfamic acid is
less corrosive than HCl, yet its strength is about the same. At 77 F a saturated solution of sulfamic
contains about 18% hydrochloric acid equivalent.
Sulfamic acid reacts with limestone to form calcium sulfamate (Ca (SO3NH2)2), water and carbon
dioxide
2HSO3NH2 + CaCO3 > Ca(SO3NH2)2 + H2O + CO2

(10)

One advantage of sulfamic acid is its solid physical state. Solid sulfamic acid can be transported and
stored without special equipment or tanks, and mixed with water at or near the wellsite as needed.
Sometimes it is cast into "acid sticks" for easy introduction into the wellbore.
The disadvantages of sulfamic acid include its decomposition at around 180 F, making it
inappropriate for applications where formation temperatures are above 160 F. Moreover, HCl offers
more dissolving power and comparable reactions at lower cost.
Chloroacetic acid is generally preferred to sulfamic acid when use of a powdered acid is appropriate,
because it is stronger and more stable.
Retarded Acids
Retarded HF acid can penetrate deeper into a formation than conventional HF to remove siliceous
solids. Retardation of HF achieves deeper penetration of unspent acid, can aid more complete
formation damage removal, and further increase production.
A number of retarded HF acid systems are commercially available several of which are:
SGMA (self-generating mud acid): The first retarded sandstone-acidizing system to be used extensively
was developed by Shell Oil Company. It involves pumping ammonium fluoride and an organic ester, methyl
formate, into the formation. (Methyl formate has a very low flash point and should be pumped with
caution.)In time, ester hydrolysis produces formic acid. This acid reacts with ammonium fluoride to form HF,
which then dissolves clays or any siliceous minerals it contacts.
Claysol retarded HF (Halliburton): A retarded clay-dissolving system which utilizes ion-exchange
properties of clay minerals to generate HF on clay in situ. Since HF is formed on clay surfaces, little sand is
dissolved by this process. HF is created by sequentially injecting a volume of 3% ammonium fluoride
followed by an equal volume of 5% HCl. This process dissolves clay in the formation as deep as a set of
sequences can be pumped without completely mixing together.
Clay acid (Dowell-Schlumberger): A retarded acidizing fluid using fluoboric acid (HBF 4) for matrix acidizing
of sandstone formations. HBF4 is usually applied as an afterflush to an HF treatment. Upon entering the
formation, HBF4 slowly hydrolizes to generate HF. Deep acid penetration to remove fines is possible
because of the slow generation of HF. Unlike clay-control agents, HBF 4 also produces a chemical fusion of
both fines and clay platelets, which provides fines/clay stabilization.
RHF acid solution (Nowsco): A retarded HF system for treating sandstone formations suffering deep
damage caused by migration and/or swelling of siliceous minerals. This single-stage treatment does not
require sequencing or "shut-in" time for hydrolysis reactions. Addition of aluminum chloride (AlCl 3) to an HF
acid solution forms aluminum fluoride complexes, similar to those formed in spent regular mud acid, which
retards the reaction rate of HF with siliceous materials.

Retarded Hydrochloric Acid

The HCl reaction rate on carbonate formations can be retarded by gelled acid, oil-wetting formation
solids, or emulsifying acid with hydrocarbon.

Gelled Acid Systems: Gelled acids are used to retard acid reaction rate during fracture acidizing.
Retardation occurs because increased fluid viscosity reduces the rate of acid contact with the fracture
face.
Other related advantages include:
reduced leak-off rate
deeper penetration
better cleanup of fines or solids transport
Viscosifying agents normally associated with gel led acid systems consist of natural polymers, synthetic polymers,
cross-linking agents, and surfactant gelling chemicals.
Chemically Retarded Acids: When it is desirable to extend the spending time of an acid system, a
chemical retarding agent may be used. Most chemical retarders are anionic surfactants (such as
sulfonates or sulfates). These oil-wetting surfactants adsorb onto a carbonate to create a physical
barrier to acid contact with the rock surface. The adsorption mechanism on a calcium crystal may
look like the illustration in Figure 1 (absorption mechanism ).

Figure 1

Emulsified Acids: Emulsified acids, obtained by emulsifying acid and a hydrocarbon, are effective
over a wide range of bottomhole temperatures. The system may be either oil or acid external, but
the most common form is an oil-external emulsion.

Oil-external emulsion is composed of hydrocarbon-base fluid (refined or crude) as the continuous phase
and HCl as the internal phase. This acid system retards the reaction of acid with the formation by
decreasing the amount of acid in contact with the rock. As the acid spends, the emulsifier reacts with the
resulting CaCl2 solution, releasing its emulsifying properties and therefore causing the emulsion to break.
Acid-external emulsion is composed of acid as the external phase, where selection of acid depends on the
well conditions involved. The acid phase may account for 80 to 90% of its total volume. Ordinarily,
aromatics, such as toluene or xylene, are used as the hydrocarbon or internal phase. This acid system is
used primarily to remove hydrocarbon materials like paraffin, congealed oil, and other deposits so acid can
contact acid-soluble materials.

Foamed Acid
Foamed acid has widespread application for effective fracture acidizing in carbonate reservoirs. Both
oil and gas wells have responded successfully to foamed acid stimulation treatments. Foamed acid is
particularly beneficial in low-pressure, low-permeability, liquid-sensitive formations because of the
following advantages:
High Viscosity: While often difficult to achieve with conventional gelling agents in acid, high apparent
viscosities are easily developed by foaming the acid. Higher viscosities may result in wider fractures, better
fluid-loss control, and better solids-carrying capabilities.
Reduced Fluid Loss: The high apparent viscosity of foamed acid results in reduced fluid loss, which allows
deeper acid penetration. In low-permeability reservoirs, foam bubbles may be sufficient to decrease leakoff
into the formation matrix.
Improved Solids Transport: In conventional acid treatments, large amounts of insoluble fines can be left in
the formation because of low-viscosity spent acid. These solids can reduce fracture conductivity. Foamed
acid and high viscosity suspend and remove more fines from the well during cleanup.
Better Cleanup: Foamed acid offers built-in gas assist. This means faster cleanup. It may even eliminate
the need to swab the well after acidizing.
Less Damage: Foamed acid has a low liquid content. Normally, the volumetric gas content (referred to as
foam quality) is 60 to 80 quality (i.e., 60% to 80% gas and 40% to 20% acid).
Experience with foamed acid has shown that increasing acid viscosity with conventional gelling agents before
foaming can help increase foam stability. The longer foamed acid, live or spent, is allowed to remain static, the
easier it is for acid to drain from the foam bubbles. This foam destabilization (liquid/gas separation) allows
suspended fines to settle out.
Nitrogen is the most common gas used to make foamed acid. Foam quality is generally between 60%
and 80%, although qualities as high as 95% have been used. The acid phase of the foam may
contain 0.5% to 1.0% surfactant and 0.2% to 2.0% corrosion inhibitor.
Turflo/Hydrofluoric Acid
As stated earlier, HCl-HF mixtures react with both siliceous and carbonate materials. In most
sandstone formations carbonate content is small, and an HCl preflush removes all carbonate
material. HCl may not, however, do the job effectively in formations with high limestone or dolomite
content. These carbonates can reduce the effectiveness of a HCl-HF treatment by increasing the
chance of secondary reactions and by limiting the amount of clays removed.
Turflo/hydrofluoric acid, a phosphoric acid-HF combination, is specifically designed for formations
with high carbonate content. Tests with this system have shown its reaction rate is much slower than
that of normal 12% HCl-3% HF with limestone and nearly as fast with silicas.
Since Turflo/HF is slightly slower reacting than HF acid, deeper penetration of HF is possible.
Turflo/HF is more expensive than conventional HF, but its limited reaction rate with carbonates allows
for improved formation damage removal in sandstone formations with high carbonate content..
However, caution should be exercised because precipitation problems may subsequently cause
severe permeability damage.

Exercises
1.. Which of the following is the strongest acid?
a. 10% formic
b. 5% HCl
c. 10% acetic
d. 6% HF
2How much limestone does 1000 gal of 15% HCl dissolve?
a. 100 lb
b. 1200 lb
c. 1800 lb
d. 2442 lb

3.. What is the usual quality of foamed acid?

a. 20 to 40%
b. 70%
c. 0.5 to 1.0%
d. 60 to 80%

4"Regular acid" refers to

a. 15% HCl
b. 12% HCl-3% HF
c. Hydrochloric acid at any strength
d. 10% acetic

5.Which of the following acids is most corrosive?

a. 10% acetic
b. 10% formic
c. 10% HCl
d. 10% HF

6.. What are the reaction products of HF on clay?

a. CaCl2 + H2O

b. H2SiF6 + H2O
c. CaF2 + H2O + CO2
d. H2SiF6 + H3AlF6 + H2O

7Which acid is used in sandstone acidizing?

a. Hydrochloric-hydrofluoric acid mixtures
b. HCL
c. Retarded HF
d. All of the above

8.. Foamed acid is most often used in

a. Sandstone reservoirs
b. Hydraulic fracturing applications
c. Fracture acidizing
d. Matrix acidizing in low-pressure carbonates

9.. Which acid is likely to be the best choice to remove clay damage in deep, hot sandstone reservoirs?
a. 6% formic - 1 1/2% HF
b. Regular mud acid
c. 7 1/2% HCl - 1 1/2% HF
d. 10% acetic

Additives in Acidizing Fluids

Corrosion Inhibitors
The principal additives to acidizing fluids are corrosion inhibitors. A corrosion inhibitor is a chemical
that slows acid corrosion on drill pipe, tubing, or any other metal that the acid contacts during
treatment. Brief explanations follow of the acid corrosion mechanism, types of acid corrosion, and
corrosion by different acid types.
Acid Corrosion on Steel: All uninhibited acid solutions corrode steel. The attack of acid on steel
occurs through the dissociated hydrogen ion of the acid solution. This results in the oxidation and
dissolution of iron at the anodic sites on the metal surface along with the reduction of hydrogen ions
and formation of hydrogen at the cathodic sites:
Anodic Reaction (Oxidation)

Metallic iron
Fe

Ionic iron
=>

Fe++

Electrons
+

2e-

(14)
Cathodic Reaction (Reduction)

Ionic
hydrogen
2H+

Electrons
+

2e-

Hydrogen
>

H2
(15)

These two reactions can be summarized by the following overall reaction:

Metallic iron

Ionic hydrogen

Ionic
iron

Hydrogen

Fe

+ 2H+

Fe++

H2
(16)

This electrochemical corrosion process is shown in Figure 1 (electrochemical corrosion ).

Figure 1

The units of measurement used to determine the amount of corrosion are lb./sq. ft. To illustrate, one
sq. ft of steel 0.001 in. thick weighs 0.041 lb.; 1.92 ft of 2-3/8 in. tubing has an inside surface area
of one sq. ft. If corrosion weight loss of this 2-3/8 in. tubing is 0.041 lb./sq. ft, then every foot of the
string has lost 0.021 lb. and is thinner by 0.001 in.
Acceptable corrosion limits are demonstrated in Table 1 (below). The range is from 0.02 to 0.09
lb./sq. ft of metal surface, depending on temperature. Keep in mind, however, that acids corrode
more evenly, with less pitting, at higher temperatures. At elevated temperatures, then, more
corrosion may be permitted with less chance of forming a hole in the drill pipe or tubing string. A
corrosion limit of 0.10 lb./sq. ft may be acceptable with a low pitting index representing 1% metal
loss. Furthermore, there is less risk in an initial completion acidizing treatment than on tubing
subjected to repeated acidizing.

Temp. -OF

Corrosion
Limit lb./sq. ft.

200

0.02

200-275

0.05

275-350

0.09

Table 1: Acceptable corrosion limits

Since acid corrosion is strongly influenced by the chemical composition of the steel, metal chemistry
is an important factor in corrosion studies on oilfield tubular goods. API specifications, however, are
based on physical properties of the metal (i.e., tensile strength) rather than chemical composition.
Marked differences in chemical composition may exist in the same grade of tubing or casing from
different manufacturers, or from lot to lot from the same manufacturer.
A general rule to follow when comparing the degree of corrosivity of two types of tubular goods is
that the higher the hardness of the metal, the more prone it is to acid attack. This rule is illustrated
in Figure 2 (Effect of HCl on different types of steel ).

Figure 2

Remember, however, that there are exceptions to every rule.

Types of Acid Corrosion: In uninhibited acid solutions, the corrosion of steel is usually uniform. The
constant shifting of anodic and cathodic areas spreads corrosion more or less evenly over the entire
surface of the metal. Pitting of the steel surfaces occurs in some situations due to inhibitor
breakdown, insufficient inhibitor, and metal impurities.
Inhibitor Breakdown: On steel exposed to acid solutions containing an inferior corrosion inhibitor, a
pitting type of corrosion is not uncommon. All corrosion inhibitors eventually break down after some
period of time, depending on, among other factors, temperature, acid strength, and metal type.
When this point is reached, an inferior inhibitor may actually tend to promote pitting by desorbing
from the metal surface in localized areas.
Insufficient Inhibitor: Regardless of the quality of corrosion inhibitor, pitting may also occur if there is
an insufficient amount of inhibitor to effectively coat steel surfaces under certain conditions.
Unprotected steel surface areas are rapidly attacked by the acid solution, and pitting occurs.
Metal Impurities: Another condition that promotes pitting is the presence of impurities or inclusions
within the steel itself. For example, small pieces of slag may become trapped during the forming of
the steel, or improper heat treating or quenching of the steel may produce discontinuities in its grain
structure. These imperfections may, in turn, become anodic to the rest of the surrounding steel
structure, and thus promote acid attack.
Hydrogen Embrittlement: This is one of the most insidious forms of corrosive attack. Because
oxidation and dissolution of iron occur at the anodic sites on the metal surface when steel is corroded
by acid, the reduction of hydrogen ions and formation of hydrogen takes place at the cathodic sites.
The cathodic reaction can be expressed as

Hydrogen
ion

Electron

H+

+ e-

Atomic
hydrogen
H

Atomic
hydrogen
=>

Atomic
hydrogen
+

(17)

Molecular
hydrogen
=>

H2

(18)

Because atomic hydrogen is very small, it can penetrate the metal and become lodged in void spaces
along metal grain boundaries. Molecular hydrogen is too large to penetrate and lodge in these
spaces, and is not a problem at well temperatures.
When atomic hydrogen that has penetrated the metal structure comes in contact with another atomic
hydrogen atom, the two combine to form molecular hydrogen within the steel structure. When the
larger molecule very slowly migrates out, extremely high pressures develop in the void spaces that
literally split the metal open. This process is called hydrogen embrittlement.
If hydrogen sulfide (H2S) is involved, the splitting phenomenon is known as hydrogen sulfide
cracking. H2S tends to slow down the transformation of atomic hydrogen into molecular hydrogen on
the metal surface at the cathode. It thus allows greater penetration into the metal which, in turn,
increases the probability of high-strength steel cracking. Figure 3 , is a photomicrograph of a crack in
stressed Pl05 pipe exposed to 15% HCl saturated with H2S.

Figure 3

This cracking can occur when very little physical corrosion is taking place. Most commercially
available corrosion inhibitors are ineffective in controlling cracking of high-strength steels in acid
saturated with H2S. As a general rule, steels with a Rockwell "C" hardness of 22 or less are not as
likely to experience H2S cracking as steels with greater hardness.
Corrosion by Different Acid Types The most common types of acid solutions used in the oil field are
HCl, formic, and acetic.
The degree of ionization of hydrogen from the acid molecule determines the acid strength, which is
directly proportional to its corrosivity on steel. The degree of ionization for these acids is HCl >
formic > acetic. HCl, then, is more corrosive on steel than formic, which is more corrosive than
acetic. Quite logically, the more aggressive an acid is in its attack on steel, the more difficult it is to
inhibit. The mechanism of attack, however, is the same for all three types, as shown below.

HCl
(inorganic)
acid
2HCl

Iron

Fe

Iron
chloride
=>

FeCl2

Hydrogen

H2
(19)

Formic (organic)
acid
2HCHO2

Iron
+

Fe

Iron
formate
=>

Fe(CHO2)2

Hydrogen
+

H2
(20)

Acetic (organic)
acid
2HC2H3O2

Iron
+

Fe

Iron formate
=>

Fe(C2H3O2)2

Hydrogen
+

H2
(21)

Inhibitor Types
There are two basic types of corrosion inhibitors: inorganic and organic.
Inorganic Corrosion Inhibitors: This class of inhibitor includes salts of zinc, nickel, copper, arsenic,
antimony, and various other metals. Of these, the most widely used are arsenic compounds.

When these arsenic compounds are added to an acid solution, they "plate out," or form iron sulfide
at cathodic sites of exposed steel surfaces. These plates decrease the rate of hydrogen ion exchange,
because iron sulfide acts as a barrier between metal and acid. It is a continuing process in which acid
reacts with iron sulfide, rather than metal.
Some advantages of inorganic inhibitors are that they:
work very effectively at high temperatures for long contact times;
cost less than organic inhibitors.
Disadvantages of inorganic inhibitors are that they:
tend to lose their effectiveness in 17 to 20% HCl and stronger acid solutions;
react with H2S (via FeS ions) to form an insoluble precipitate called arsenic sulfide. (In the
reservoir this precipitate exists in a gaseous state, but when it enters the wellbore and cools,
a plugging solid forms.);
poison refinery catalysts, such as platinum;
liberate occasionally toxic arsine gas as a by-product of corrosion;
resist mixing and safe handling.
Organic Corrosion Inhibitors: These inhibitors are composed of polar organic compounds capable of adsorbing onto
the metal surface, thereby establishing a protective film that acts as a barrier between the metal and the acid
solution. They usually serve as a cathodic polarizer by limiting the hydrogen ion mobility at cathodic sites. Organic
inhibitors are composed of rather complex hydrocarbon units with one or more polar groups made of sulfur, oxygen,
or nitrogen.
Some advantages of organic inhibitors are that they:
can be used in the presence of H2S without precipitation of arsenic sulfide, which can plug the wellbore.
do not poison refinery catalysts.
work effectively in all acid concentrations.
Some disadvantages of organic inhibitors are that they:
tend toward in-situ degradation that is, they chemically degrade with time in the presence of an acid
solution, and thus do not readily provide long-term protection at temperatures above 220 F.
cost more than the inorganic corrosion inhibitors.
Table 2 (below) demonstrates effectiveness of organic and inorganic corrosion inhibitors at high temperatures in
15% HCl. The protective time reflects time required for the HCl to remove 0.05 lb./sq. ft of exposed metal area.
Do not make the mistake of assuming that twice as much inhibitor provides twice as much
protection: the concentration limit varies from one inhibitor to another. The general rule is that a 2%
concentration is maximum. Beyond this point, no practical benefit is gained.
Remember that the purpose of a corrosion inhibitor is to slow the acid reaction rate on steel.
Inhibitors in and of themselves do not prevent corrosion.

Listed in Table 3 are some examples of corrosion protection times available at the more common
temperatures found in acidizing treatments.

Table 3

Intensifiers
Although these additives cannot be considered inhibitors when used alone, their effectiveness is
increased when they are used in conjunction with an organic inhibitor. The commonest intensifiers
are potassium iodide, cuprous iodide, and formamide. The addition of these synergistic chemicals to
existing organic inhibitor formulations greatly extends the range of their effectiveness, particularly in
higher-temperature applications.

Type Inhibitor

Inhibitor
Concentration%

Temperature
F

Protection Time- hr.*

Organic

0.6

200

24

1.0

250

10

2.0

300

0.4

200

24

1.2

250

24

2.0

300

12

Inorganic

*Time required for 15% HCl to remove 0.05 lb./sq. ft exposed metal area.
Table 2: Effectiveness of corrosion inhibitors at high temperatures in 15% HCl.

Surfactants

Surfactants, or surface-active agents, lower surface tension by adsorbing at the interface between
liquid and gas. Surfactants can also lower interfacial tension by adsorbing at interfaces between two
immiscible liquids and changing contact angles by adsorbing at an interface between a liquid and
solid. They are commonly used in acidizing (and other completion and workover operations) to
demulsify spent acid and oil, reduce interfacial tension, speed cleanup and prevent sludge formation.
Surfactants should not be added to treatment fluids without first having a full understanding of their
effects on the reservoir oil at downhole conditions. Without this understanding, it is better not to use
surfactants at all in the formulation, particularly when the objective is to break or prevent emulsion
(Schecter, 1992).
Surface tension is a property of liquids that distinguishes them from gases. Liquid molecules exert a
mutual attractive force on each other. When this force a combination of van der Waals' forces and
electrostatic forces is not balanced, a tension perpendicular to the surface develops. The greater
the attractive force of these molecules for one another, the greater the surface tension of the liquid,
and the greater the amount of work per unit area required to rupture the liquid surface. This amount
of work (surface tension) is specific for each liquid at a definite temperature and is expressed in
dynes/cm.
Interfacial tension is the force in the interface, or boundary layer, between two unlike liquids. This
tension results from unbalanced intermolecular forces in the boundary region, is a factor in the
formation or breaking of emulsions in the recovery of treating fluids from matrix permeability.
In general, surfactants can be divided into four main groups: cationic, anionic, nonionic, and
amphoteric.
Cationic surfactants are organic chemicals with molecules that ionize upon contacting water. The
water-soluble group is positively charged. The positively charged particle, consisting of oil-soluble
and water-soluble ends, contains the surface-active portion of the molecule. The active part orients
itself at the liquid/air, acid/oil, or liquid/liquid interface. Most cationic surfactants are amine
compounds, such as quaternary ammonium chloride:

where R represents an oil-soluble group.

Anionic surfactants are organic chemicals with molecules that also ionize upon contacting water. But
here the negatively charged particle of each ion, consisting of a water-soluble end and an oil-soluble
end, is surface active. The anionic surfactant is negatively charged; it is this part that is active in
orienting itself at the surface of the liquid, or at the interface between the water and oil. The
positively charged particle goes off into solution and has little to do with surface tension.
Some examples of anionic surfactants are:

sulfates

R-OSO3-

sulfonates

R-SO3-

phosphates

R-OPO3-2

phosphonates

R-PO3-2

where R represents an oil-soluble group.

Of these, the most common anionic surfactants are sulfates and sulfonates. Anionic surfactants are
primarily used as nonemulsifying agents, retarding agents, and cleaning agents.
Surfactants are organic molecules that do not ionize and therefore remain uncharged. Most nonionic
surfactants contain water groups that are polymers of either ethylene oxide or propylene oxide.
Some examples of nonionic surfactants are:

polyethylene oxide

RO(CH2CH2O)xH

polypropylene oxide

Nonionic surfactants are primarily used as foaming agents and nonemulsifiers.

Amphoteric surfactants are organic molecules with water-soluble groups which can be positively
charged, negatively charged, or uncharged. The specific charge depends on system pH level. If the
pH is acidic, the amphoteric surfactant takes on cationic properties, or a positive charge. If the pH is
in the neutral range, then it takes on nonionic properties, or remains uncharged. If the pH level is
basic, the amphoteric takes on anionic negative charge properties.
Two examples of amphoteric surfactants are:

amine sulfonate

RNH(CH2)ySO3H

amine phosphate

RNH(CH2)zOPO3H

Some amphoteric surfactants are used as corrosion inhibitors, foamers, and silt-suspending agents.
Properties Affected by Surfactants The main fluid properties affected by surfactants are surface and
interfacial tensions, emulsification tendency, wettability, and dispersibility.
Surface Tension

: Figure 1 illustrates how surfactants lower surface tension.

Figure 1

Since the water-soluble group exceeds the water solubility of the oil-soluble group, surfactant molecules
orient themselves at the air/water interface (surface). The water-soluble group is in water, and the oilsoluble group in the air. This changes the nature of the air/water interface, making it a combination of air,
water, and oil. Because oil has a much lower surface tension than water, surface tension of the water
surfactant mixture is lower than the surface tension of pure water.
Surface tensions of some common liquids are listed in Table 1 (below).

Liquid

Surface Tension - dynes/cm

Water

72.0

15% HCL

72.0

Spent 15% HCl

76.9

Octane

21.8

Table 1: Surface tension of common liquids.

Some surfactants can reduce surface tension of water to about 27 dynes/cm when used in relatively low
concentrations. One class of surfactants, called fluoro-surfactants, can lower surface tension below 15
dynes/cm.
Interfacial Tension: Interfacial tension describes the surface energy between two immiscible
fluids, such as water and oil. This interface acts like an invisible membrane that prevents the
liquids from mixing. The force required to break this molecular film is called interfacial
tension.

The interfacial tension between kerosene and water is about 49 dynes/cm. By the addition of
a surfactant, it can be lowered to near zero. Figure 2 (surfactants lower interfacial tension)
shows the surfactant being adsorbed at the oil-water interface.

Figure 2

Again, the water-soluble group adheres to the water, and the oil-soluble group is in the oil
phase. The interfacial surface between the two fluids is now a mixture of oil and water, with
the interfacial tension being greatly reduced. Even though the surfactant is water soluble,
some of it migrates through the interface and enters the oil phase.
When interfacial tension is lowered in an acidizing treatment, the water may break up into
smaller droplets that pass through the oil and flow out of the well without forming unwanted
emulsions. In the case of oil, interfacial tension can be reduced to enable the oil to pass
through rock pore spaces with greater ease.
Emulsification Tendency: An emulsion is a mixture of two fluids in which fine droplets of one
fluid remain suspended in the other. Emulsions may be oil-external or water-external. In the
first instance, oil is the external phase with the water droplets dispersed throughout. This is
the most common emulsion found in wellbores connected to oil reservoirs. Water-external
emulsion has an aqueous external phase with oil droplets distributed throughout.
Many crudes contain naturally occurring surfactants that reduce surface tension between oil
and formation water and thus promote the development of emulsions. Treatment of the
formation with certain surfactants can also lead to the development of emulsions. However,
certain surfactants can be used to treat wells with emulsions problems.

Wettability: Oil and water are immiscible liquids that compete for a place on the formation
surface. The questions of which liquid preferentially wets the rock surface is an important
factor in acidizing. When the formation surface is completely covered by a film of oil, the
formation is termed oil-wet. Conversely, when covered by water, the formation is water-wet.
The electrochemical approach usually explains the ability of a surfactant to adsorb at
interfaces between liquids and solids and alter the wettability of solids. Most formations are
mixtures of sand, clay, limestone, and dolomite. We next consider each of these components.
Sand usually has a negative surface charge. When a cationic surfactant is used, the positive
water-soluble group is adsorbed by the negative silica particle. This leaves the oil-soluble
group to influence wettability. As a result, cationic surfactants generally oil-wet sand. When
anionic surfactants are used, the sand and silicate minerals are generally left in their natural
water-wet state. Wettability characteristics exhibited by anionic and cat ionic surfactants on a
silicate particle are shown in Figure 3 and Figure 4 .

Figure 4

Figure 3

Limestone and dolomite usually have a positive surface charge. Since anionic surfactants have
a negative charge, the oil-soluble group is usually left to influence wettability. Hence, anionic
surfactants tend to oil-wet lime-stone and dolomite formations.
Because carbonates do not usually adsorb cationic surfactants, most cationic surfactants leave
limestone and dolomite in a natural water-wet condition. Wettability characteristics exhibited
by anionic and cationic surfactants on a carbonate particle are illustrated in Figure 5 and Figure
6.

Figure 6

Figure 5

In the case of nonionic surfactants, the wettability of silicates and carbonates depends
primarily on the solubility of the material. If the nonionic is oil-soluble, it will tend to oil-wet
the silicates. This is because silicates are attracted by hydrogen bonding.
Contact angles are used to study wetting of surfactants. Figure 7 and Figure 8 shows how a
wetting and nonwetting drop looks on a solid surface.

Figure 7

By using the proper surfactant, formation wettability can be changed from oil-wet to waterwet, and vice versa. Since oil flows more easily through water-wet formations, selection of the
proper surfactant can be an important factor in increasing oil production.

Figure 8

Figure 9 shows the results of oil flow through oil-wet and water-wet sands.

Figure 9

As discussed earlier, certain surfactants are used to alter wetting properties of a producing
formation. These curves show that oil exhibits better flow rates through water-wet
formations. Care should be taken to have the formation in a water-wet condition following an
acidizing treatment, which is often not a simple task. In many instances a surfactant may
have been added as an emulsion breaker, and it inadvertently acts as an oil wetter.
Dispersibility: Surfactants have been developed to inhibit the swelling, migration, and
flocculation of clays, even in high ionic strength solutions, such as acids. This is done by using
an anionic surfactant which effectively disperses clay particles in acid mud removal solutions
and minimizes the formation of aggregates. Since the smaller particles are easier to suspend,
the clay is removed more efficiently.
Another system for removing drilling mud is an aqueous solution of surfactants and other
chemicals that reduces mud viscosity and disperses solids.

Retarding Agents
These surfactants are designed to slow the reaction time of acid on carbonate formations. Reaction
time is the amount of time it takes for acid to spend from its original concentration to a concentration
of about 3.2% at conditions of bottomhole temperature and pressure. During matrix or fracture
acidizing, or the pumping of large volumes of acid into a carbonate formation, it is sometimes
desirable to control the reaction time of the acid.
The principal surfactants used as retarding agents are anionic oil-wetting surfactants, usually
sulfonates or sulfates. These function by adsorbing onto the carbonate formation and making part of

it oil-wet. Where the surfactant adsorbs most, the acid reacts least. Consequently, an uneven surface
is etched into the fracture faces. These uneven surfaces prop the fracture upon completion, resulting
in an improved fracture permeability and increased oil and gas production. Cores etched under
simulated reservoir conditions: Figure 10 (regular 15% HCl )

Figure 10

and Figure 11 (acid retarded with anionic surfactant ) shows this uneven etching of the acid retarded
with an anionic surfactant.

Figure 11

Unfortunately, these additives have proven only marginally beneficial in retarding acid reaction rates
in the field, and there use is not generally recommended.
Emulsifying Surfactants
These types of surfactants form with acid either an oil-external emulsion or an acid-external
emulsion. The acid-external emulsion is commonly used with a mixture of an aromatic and acid to
form a dispersion. The solvent phase in this blend dissolves organic residues, while the acid reacts
with scale to remove deposits on the formation to increase permeability.
The high-viscosity oil-external emulsions are more commonly used in fracture acidizing. As the acid
spends itself on the formation, the emulsion breaks. The emulsion retards the acid formation reaction
by physically preventing acid contact.
Suspending Agents
All calcareous formations less than 100% carbonate. Thus many insoluble fines are released during
acidizing. When the spent acid is removed from the formation, these fines can be left behind to
reduce permeability.
Two basic types of suspending agents are used in this application. One is a surfactant that adsorbs
onto these fines and keeps them in suspension by electrostatic repulsion. The other is a polymer that
creates a molecular bridging effect and, by trapping the fines between polymers, keeps fines
suspended. Suspending agents are effective when acidizing a carbonate formation that contains HClinsoluble materials, such as feldspar, quartz, and clays.

Antisludging Agents
When acid contacts some crude oils, a sludge can form at the acid/oil interface. This usually happens
when the crude contains a high percentage of asphaltenes, and is most severe with high-strength
acid systems (20% or higher). Once formed, the sludge is very difficult to dissolve into oil again. As a
result, it accumulates in the formation and decreases permeability.
To combat formation sludge, surfactants, both cationic and anionic, are used to adsorb and provide a
continuous layer of protection at the acid/oil interface. Sludge development can also be prevented by
lowering acid strength and controlling return rates after an acid treatment. Figure 12 (acid droplet in
sludge-forming oil- a skin like precipitate forms around the acid droplet )

Figure 12

and Figure 13 (acid droplet containing anti-sludge forming oil- no precipitate forms around the acid
droplet ) illustrate the effectiveness of an antisludging agent.

Figure 13

Selection of a particular agent is based on tests of the acid mixture with a reservoir oil sample.
Penetrating Agents
These surfactants are commonly used in acidizing tight gas reservoirs and in scale-removal
treatments. Their main function is to lower surface and interfacial tensions of the acid. This allows
the acid to more easily wet the formation rock and oil-wet scales, resulting in a more uniform
reaction.
Another benefit of lowering the surface tension of the treating fluid is to decrease the fluid's
likelihood to form water blocks in the formation, resulting in a faster and more efficient cleanup after
acidizing.
Most penetrating agents are nonionic surfactants which water-wet both silicates and carbonates.
These surfactants effectively lower the surface tension of acid from 72 dynes/cm to about 27
dynes/cm when used in a concentration of 0.1%.
Nonemulsifiers
One major problem encountered in acidizing is emulsification of crude oil and acid, or of crude oil and
spent acid. This phenomenon may or may not occur in the formation but does occur in the wellbore.
There are two fundamental types of emulsion: oil-external and water-external.
Oil-external emulsion is commonly encountered in oil wells. It is usually a thick, viscous fluid mixture
which can reduce the flow rate of the well by plugging the formation. Addition of proper surfactants
to the acid before pumping can prevent formation of an emulsion during the acid treatment.
Obviously, the selected surfactant must be compatible with acid, formation fluids, and all other
additives in the treatment design.
Alcohol
Alcohols are ordinarily used in acidizing fluids to remove water blocks, enhance fluid recovery, retard
acid reactivity, and decrease water content. Their effectiveness is limited. The most common alcohols
used in acidizing are isopropanol and methanol. Their physical and chemical properties are listed in
Table 2.

Properties

Isopropanol

Methanol

Specific Gravity at 68 F

0.785

0.792

Flash Point (closed cup) F

53.6

53.6

Solubility in Water

Completely

Completely

Table 2: Physical and chemical properties of isopropanol and methanol.

Isopropanol is normally used at a maximum of 20% by volume. Methanol is used at various
concentrations, commonly 30% by volume. In some cases, methanol alone is used to dilute
concentrated acid to various acid-treating solutions.
Alcohols are used in acidizing fluids for the following reasons:

Removal of Water Blocks: One problem which can severely decrease production in producing wells is
blockage of the pore spaces by water commonly known as a water block. Water blocks may form where
high capillary forces are present in porous rocks. The most severe water-block problems occur in
formations with gas permeabilities less than 120 md. The alcohol in the treating fluid reduces the capillary
forces within the reservoir, thus permitting easier removal of the liquid phases.
Enhancement of Fluid Recovery: Another problem encountered in treating oil or gas wells is
the recovery of treating fluids, especially in gas reservoirs. The high surface tension of water
or acid solution hinders their penetration and recovery. Conventional surfactants help
somewhat, although they surfactants lose much of their surface activity by adsorption. The
addition of alcohol to acid solutions reduces their surface tension. The concentration of alcohol
normally used for this purpose is of sufficient quantity that adsorption is not a problem.
Alcohol used in acidizing fluids also increases the vaporization rate of the fluid. This, in turn,
lowers vapor pressure, allowing for a more rapid desaturation of water from a gas reservoir.
Retardation of Acid Reactivity: Alcohol has a retarding effect on acid reactivity. The
retardation rate is proportional to the type and percentage of alcohol added.
Decrease of Water in Acid: Some formations contain a large amount of water-sensitive clays.
To minimize the amount of water contained in acidizing solutions, alcohols are used in place of
part or all of the dilution water.
The major disadvantages of using alcohol in acidizing fluids are:
Effective Concentration: It takes a large amount of alcohol, 20% or more, to provide beneficial effects.
Cost: Replacing water with alcohol in the acidizing solution makes the treatment more
expensive.
Low Flash Point: Both isopropanol and methanol, and even acid solutions containing 20% or
more by volume of either, have low flash points.
Increase in Corrosiveness: Corrosion tests have shown that alcohol-acid mixtures require a
higher concentration of inhibitor than equivalent nonalcohol-acid mixtures.
Adverse Reactions: Formation brines with a high concentration of dissolved salt solids can
"salt out" in the presence of alcohols. To help prevent the occurrence of this salt precipitation,
do not exceed 20% by volume of isopropanol or 50% by volume of methanol in treating
solutions.
Incompatibility: Some crude oils are incompatible with both methanol and isopropanol.
Conduct compatibility tests before acidizing a well with a fluid containing alcohol. Some
formation types may be extremely sensitive to aqueous solutions that contain high
concentrations of alcohols.
In some cases, formations should not be acidized with alcohol-acid solutions. The formation of undesirable methyl
chloride is possible with HCl solutions that contain 30% or more methanol at bottomhole temperatures above 200
F.
Mutual Solvents
A mutual solvent is a material that is soluble in both hydrocarbon and aqueous solutions. It can help
to solubilize an aqueous solution into a hydrocarbon solution or vice versa. Common mutual solvents
include ethylene glycol monobutyl ether (EGMBE), diethylene glycol monobutyl ether (DEGMBE),
modified glycol ethers (MGE), and also alcohol.

The use of mutual solvents, particularly EGMBE and MGE, in acid stimulation of a sandstone reservoir
is a common practice. Mutual solvents have been used in postflushes because they help to:
reduce water saturation from around the wellbore by lowering the surface tension of the water, thus
preventing water blocks
solubilize a portion of the water into the hydrocarbon phase, thus reducing the amount of
irreducible water saturation
provide a water-wet formation, thus maintaining the best relative permeability for oil
production
prevent insoluble fines from becoming oil-wet
stabilize emulsions
maintain the needed concentration of surfactants and inhibitors in solution by helping to
prevent adsorption of these materials onto the formation
Mutual solvents have also been found to reduce the formation damage that can result from using corrosion
inhibitors in acid treatments. The normal treating concentration of mutual solvents varies from 2 to 50% by volume,
depending on the application. Most sandstone acidizing applications use 10% or less.

Iron Sequestering Agents

Iron occurs naturally in formation water, and in formation minerals such as siderite, hematite and
pyrite. A primary source of iron, of course, is donwhole tubular goods. In solution, iron can exist in
two forms: ferrous iron (Fe2+) and ferric iron (Fe3+). Fe3+ is or primary concern in acidizing, because it
precipitates as gelatinous iron hydroxide (Fe(OH)3) at a pH of 2.5 to 3.5. This precipitation can lead
top formation damage.
When Fe3+ is present in the near-wellbore region, an iron sequestrant, or chelating agent, may be
added to the treating solution. Table 1 (below) provides information about various sequestering
agents, of which EDTA is the most commonly used.
Because these agents can themselves damage the formation, they should be used only when pr-job
evaluation and testing indicate a tendency for iron hydroxide precipitation during acidizing.
Other methods for keeping iron in solution include pH control and the use of oxygen scavengers. pH
control is achieved by using a weak acid, such as acetic, which reacts much more slowly than HCl on
limestone and other acid-soluble materials. Thus, some of the acid remains in solution, keeping the
pH low and inhibiting iron Hydroxide formation.

Compound

Maximum Solubility
in 1000 gal 15%

Amount of Fe +2 Chelated - ppn

EDTA (Ethylene Diamine

Tetraacetic Acid)

67

1,450

Sodium EDTA

~250

~5,000

NTA (Nitrilo Triacetic Acid)

420

13,790

Citric Acid

1,796*

57,292

*The solubility of citric acid is considerably higher than 1,796 lb. Theoretically, ferric iron in 15% HCl
spent on millscale can be chelated with 1,796 lb of citric acid. However, if the acid was only partially
spent on magnetite and the remainder spent on a carbonate rock, calcium citrate could precipitate.
Table 1: Solubility and iron chelating capability of various chelating agents.
Oxygen Scavengers: An oxygen scavenger can be used to economically control concentrations of iron
up to approximately 5,000 mpl. It functions by two different mechanisms. First, it removes free
oxygen from the fluid, and then helps prevent the oxidization of ferrous iron (F 3+2) to ferric iron
(Fe+3). Then, it acts as a reducing agent and reduces any dissolved ferric iron present to ferrous
iron. This helps maintain iron in solution and helps prevent the precipitation of ferric iron. This helps
maintain iron in solution and helps prevent the precipitation of ferric iron in solution. The amount of
iron that can be reduced with an oxygen scavenger depends upon the quantity of chemical added,
but it can be used up if the fluid is aerated before it is pumped.
A comparison of the amount of ferric iron that can be retained by the various methods and additives
is illustrated in Figure 1 (iron cotnrol acid systems).

Figure 1

The safest way to help prevent damage to the reservoir from precipitated iron hydroxide is to clean
or "pickle" the pipe with acid before acidizing the formation. This acid should contain large quantities
of iron-control additives and should be circulated out of the well, not pumped into the formation. In
conduction with this treatment, xylene or hydrocarbon phase should be incorporated or used as a

preflush to remove pipe dope and varnish that could plug perforations. ( In most instances, pipe
dope is not soluble in xylene or normal hydrocarbons.)

Fluid Loss Control Additives

In fracture acidizing, fluid loss control helps to extend fractures by minimizing leakoff of the treating
fluid through the fracture face. Fluid loss control is difficult to obtain with acid solutions on carbonate
formations because the acid is reacting on the surface where the fluid loss additive is being
deposited.
Fluid loss additives often are composed of two agents: an inert, solid particle that bridges at the
fracture surface and a gelatinous material that plugs the pores in the solid granular material.
Commonly used fluid loss additives are listed in Table 1 .

Fluid Type

Solid Additives

Gelatinous Additives

Aqueous pad

Silica flour

Guar

Calcium carbonate

Cellulose

Organic polymer

Polyacrylamide

Inert solid coated with

guar type material
Hydrocarbon pad

Inert solid coated with

organic sulfonate

Acid

Acid swellable solid

Guar

Organic resin

Karaya

Silica flour

Cellulose

Organic polymers

Polyacrylamide
Polyvinyl alcohol

Table 1 : Commonly used fluid loss additives.

In aqueous pad fluids, a combination of solid additive and polymer is usually selected. When water
without a polymer additive is used, an inert solid coated with guar-type material may be chosen. Acid
additives include acid-soluble organic polymers that swell and become soft when contacted by acid,
thereby giving both solid and gelatinous characteristics. Other additives are similar to those chosen
for use in water-base pad fluids.
We now focus on matrix fluid loss, fluid loss in natural fractures, fluid loss in wormholes, and
viscosity effects.
Matrix Fluid Loss: Many carbonates contain little permeability within the matrix of the rock. Because
acid is a reactive substance, however, it creates more surface area as it travels during leakoff. It is
very important, therefore, to confine the acid to the fracture. Fluid loss additives are usually
sufficient to control matrix leakoff. Ideally, they should be either degradable or slowly soluble in the
acidizing solution or in produced fluids.

Fluid Loss in Natural Fractures: Some limestone formations have unusually high permeability in the
form of natural fractures or vugular flow channels. Fluid loss control in this type of formation cannot
be achieved with ordinary fluid loss additives. A larger diverting material is usually required to control
the fluid lost to natural fractures.
Fluid Loss in Wormholes: Fluid lost to the matrix will react and, if lost in a highly reactive part of the
formation, may cause wormholes. These are large, highly conductive channels which usually start
when a large pore or vug grows at a rate substantially higher than that of smaller pores and receives
an increasingly larger amount of the acid as new surface area is created. From a fluid-loss
standpoint, wormholes are similar to natural fractures since they require larger particles for control.
If little fluid leakoff occurs to the matrix, few wormholes are likely to occur. For a more detailed
discussion of wormhole formation and growth, see Economides et al. (1995).
Viscosity Effects: The rate of leakoff is directly related to viscosity. A thicker fluid results in less fluid
lost to the formation and, therefore, improved fluid efficiency. If efficiency increases, more live acid
can be pumped deeper into the formation, thus increasing fracture flow capacity. Viscosifying the
acid can be one of the most important steps in providing fluid-loss control in fracture acidizing
treatments.
Friction Reducers
Friction reducers suppress turbulence and reduce friction pressure in fluids flowing through tubular
goods. This can either reduce horsepower requirements or increase treating rates. Most friction
reducers are long-chain natural or synthetic polymers, but not all of them work effectively in
acidizing solutions. Acid breaks down some of these polymers at a very fast rate, thus leaving little, if
any, friction-reducing properties.
Many different additives are used as friction reducers. Generic classifications of additives for waterand oil-base pad fluids and for acids are listed in Table 1.
Fluid Type

Generic Classification of Additive

Water based pad

Guar and HP Guar

Polyacrylamide
Cellulose

Oil based pad

Polyisobutylene
Fatty acids
Crosslinked organic polymers

Acid

Guar
Gum karaya
Polyacrylamide
Cellulose

Table 1: Friction reducers.

Clay Stabilizers

Many clay-stabilizing materials have been developed in recent years to combat formation damage
caused by clay swelling and migration. These generally are used in conjunction with minimumsalinity fluids such as 2% KCl, 4% NaCl, and 3% NH4Cl.
Types of Clay
Some clays, like smectite-mixed layer, swell when they contact fresh water or water with low salt
concentrations. There are several ways in which water can enter and damage a productive zone.
Some of these are:
water filtrate from drilling fluid;
loss of water from completion or workover fluids;
encroachment into the reservoir by water coning;
any type of water-base treating fluid.
Productivity also decreases when the produced fluid carries the clay fines (colloidal-size clay particles) in
suspension to the wellbore. When any type of pore restriction is encountered, the fines bridge off in the pore,
thereby plugging the pore and restricting the flow. Radial flow volume of fines increases while the number of pore
channels decreases. Some clays with migrating tendencies are illite, kaolinite, and chlorite.
Smectite-Mixed Layer: Smectite-mixed layer, a three-layer clay, is composed of two silica tetrahedral
sheets with a central octahedral sheet ( Figure 1 , smectite -mixed layer).

Figure 1

In the stacking of their mineral sheets, the proximity of two oxygen layers makes for a weak
chemical bond that allows water and other polar organic minerals to enter between unit layers and
cause the clay to swell. Figure 2 (three layer clay ) illustrates the bonding of smectite-mixed layers.
The cation exchange sites attract such positive ions as sodium, potassium, calcium, or ammonium.

Figure 2

Illite: Illite is a clay composed of two silica tetrahedral sheets with a central alumina octahedral sheet
( Figure 3 ).

Figure 3

Its structure is similar to smectite, except that potassium and oxygen bind the sheets tightly. Hence,
this clay does not expand in the presence of water. However, the potassium ions are very susceptible
to the leaching action of slightly acidic water. In some cases, the potassium may be removed and
replaced by another cation. These altered minerals, called degraded illites, then allow entry of water
and will swell as a result.

Kaolinite: Kaolinite is composed of one silica tetrahedral sheet and one octahedral sheet ( Figure 4 ).
Their tight hydrogen bonding is not susceptible to water entry. Although kaolinite swells very little on
contact with fresh water, it is an important component of migrating fines.

Figure 4

Figure 5 (two layer clay ) schematically illustrates a two-layer clay.

Figure 5

Kaolinite is the principal member of this family of clays. There are few cation exchange sites: 10% of
the number for smectite-mixed layer too few to cause significant swelling.
The degree to which a clay will swell depends on the ions the clay has adsorbed, the degree of
degradation of the clay, and the amount of substitution in the clay lattice. The amount of swelling of
several salts of smectite is shown for various concentrations in Table 1 (below). These data show
that certain ions, especially sodium, allow swelling of clays, resulting in formation damage. In Figure
6 (salinity effects on clays), solutions of sodium chloride (NaCl) were flowed through columns of
quartz sand containing 4% by weight of various clays.

Figure 6

These curves show that the higher salinity solutions of NaCl did less damage to the permeability of
the columns than the lower salinity and fresh water systems.

Salt Concentration

Sodium
Smectite

Potassiu
m
Smectite*

Calcium
Smectite

Distilled Water

33

27

0.4% Chloride
Solution

14

2.0% Chloride
Solution

8.5% Chloride
Solution

10.0% Chloride
Solution

3 to 4

*Ammonium chloride will perform essentially the same as potassium chloride.

Table 1: Effect of salt concentration on the swelling of smectite.
The data in Table 1 and Figure 6 show good agreement. Both indicate that low concentrations of salt
swell the smectite more severely than do higher salt concentrations. Figure 6 also indicates that the
sensitivity of the clays to water swelling is

kaolinite < illite < smectite

with kaolinite showing the least damage and smectite the most.
Clay damage may be caused by both swelling and migration. When these conditions occur in a
formation, the damage must be removed to improve production. This is commonly accomplished by
acidizing the formation with HCl-HF mixtures.
Clay Control
Formation damage due to clays must be prevented rather than cured. When clay particles in
sandstone reservoirs are rearranged or disturbed in any manner, it is usually impossible to restore
the original permeability.
X-ray diffraction analysis can easily determine the type and amount of clay in a particular sandstone.
These tests indicate which formations warrant a particular minimum-salinity fluid, clay stabilizer, or
special completion technique to avoid formation damage.
The position of clays in the rock can be quickly determined by the use of dyes that exhibit
characteristic colors when absorbed by different types of clays. Where detailed studies are
warranted, the scanning electron microscope (SEM) permits direct observation of certain actions on
clays.
In a virgin formation, the swelling of a clay particle is in equilibrium with the type and concentration
of salts in the connate water. Thus, filtered formation water used in workover operations should not
disturb this balance. If clean formation water is not available, it is necessary to synthesize an
economical substitute.
Cat ionic polymers have been developed that can plate out of fresh water, brine, or acid to stabilize
clays and minimize damage. These cationic materials do not oil-wet because the exposed polymer
prefers water over oil. The cationic ends of the clay stabilizers bind to the clay minerals in the same
manner as the sodium Na+, potassium K+, or calcium Ca++ ions bind. This leaves the water-soluble
end of the molecule to form a film over the clay minerals to prevent their swelling and migrating. The
principal cationic polymers currently available for use in sandstone acidizing include polyquaternary
amines (PQA) and polyamines (PA).
Polyquaternary Amines (PQA): PQA is a cationic organic polymer used as a clay-stabilizing additive in
sandstone acidizing applications and other treatments. It is a clay-stabilizing chemical that can be
universally placed out of aqueous solutions and strong acids.

Since PQA does not require a shut-in period, it allows faster well cleanup and prevents damage
resulting from swelling and/or migration of clay particles and other silicate fines. The chemical action
between PQA and clays results in longer stabilized production before migrating and/or swelling
silicates begin to redamage the formation.
Figure 7 illustrates relative permeability in a Bandera sandstone core without any clay stabilization

treatment.

Figure 7

Notice that after the core was calibrated with 2% KCl and then exposed to fresh water, permeability
decreased about 85%.
Figure 8 demonstrates relative permeability in a Bandera sandstone core after a clay-stabilization

treatment with PQA (polyquaternary amine).

Figure 8

Following 2% KCl calibration and clay-stabilization treatment, fresh water had only minimal effect on
the permeability, decreasing it slightly.
Although the PWA concentration needed depends on permeability, the usual maximum is 3% by
volume.
All fluids containing PQA should be overflushed with a sufficient volume of fluid containing PQA to
ensure that they are displaced to a distance of at least two feet from the wellbore. This results in
more fines stabilizing for a given PQA concentration.
Polyamines: These are cat ionic polyelectrolytes which stabilize water-sensitive clays against the
swelling and migration problems that might occur on contact with aqueous fluids. PA can be used in
aqueous preflush and overflush fluids and acids.

Bacteria Control Agents

Types of Bacteria
Bacteria can cause problems in oil-field operations. Even though these bacteria are extremely small
(1 to 3 microns), their sheer numbers can cause plugging problems in injection wells.
Generally, the worst problems result from the by-products or chemical processes of certain
organisms. Some of these problematic bacteria are sulfate-reducing bacteria, slime-forming bacteria,
and iron bacteria.
Sulfate-reducing Bacteria The bacterium causing the greatest concern to oil producers is the sulfatereducing organism. This bacterium, an anaerobic organism, needs an oxygen-free atmosphere in

order to spread. Under anaerobic conditions, it can produce H2S. This gas can then corrode downhole
tubulars, producing iron sulfide (FeS), which is insoluble in water and acts as a plugging agent.
Slime-forming Bacteria Other troublesome bacteria are the slime-forming types. Under aerobic
conditions, they may produce large slime masses that cause severe plugging problems. These
bacteria are usually found where fresh or surface water comes in contact with produced water.
Iron Bacteria A very common bacterium that can cause problems is the iron bacterium. This aerobic
bacterium has the ability to oxidize water-soluble ferrous ion to a water-insoluble ferric ion in its
metabolic processes. Iron bacteria can cause plugging of source well, filters, and surface lines.
Bactericides
Many chemicals can be used to control the growth of microorganisms. The most common term for
chemical agents designed to kill and inhibit the growth of bacteria is bactericide or biocide. Use of a
bactericide can reduce or eliminate the severe problem associated with bacteria.
Many bactericides, both cationic and nonionic materials, can be used in acidizing solutions. These
chemicals are effective at killing bacteria in concentrations from 1 to 2 gal/1000 gal.

Matrix Acidizing
Matrix Acidizing
This type of acidizing treatment is designed to remove skin damage that extends beyond the
immediate surface of the perforations or the face of the producing zone. Acid enters the pore space
of the formation below fracturing pressure and dissolves both the surface of the rock and the flow
restricting contaminants within the matrix.
A matrix acidizing treatment may be effective penetrating into the formation only a few inches or up
to several feet from the wellbore, depending on formation permeability. In wells that have suffered
from skin damage, production can increase many-fold. However, if a well had little or no skin
damage, an acidizing treatment stimulates natural production little more than one to two times,
depending on its design. Figure 1 (stimulation of natural production ) illustrates this phenomenon.

Figure 1

Matrix acidizing regains permeability by removing formation damage from the perforation tunnels
and existing flow channels around the wellbore to a depth of only a few inches. The amount of lost
production is directly related to the extend and depth of formation damage, as shown in Figure 2
(effect of damage on well productivity ).

Figure 2

The greatest productivity loss occurs in wells with severely damaged permeability within the first few
inches from the wellbore. According to Schecter (1992), three of the primary mechanisms that
contribute to an acidized well's productivity include "erosion of the pore structure as the acid flows
through these pores, consumption of the acid and, selective dissolution of certain minerals. Erosion
of the pore structure leads to both increase porosity and permeability...

Matrix Acidizing of Sandstone

Matrix acidizing in sandstone achieves the natural true permeability of the formation by removing
clay damage. The stimulation fluids are pumped into the porosity (pore spaces) of the rock below
fracturing pressure.
Since the acid is exposed to and reacts on such a large area of the formation, unreacted acid can be
effective only for a short distance into the reservoir. Thus, this type of treatment is primarily
designed to treat shallow damage in the immediate vicinity of the wellbore. Retarded hydrofluoric
acid systems can penetrate farther. Of course, the effective penetration is also a function of the
dissolving power and reaction rate, which depends on the properties of the acid and the mineral in
the formation.
Reasons for Treatment
Sandstone formations usually have clays that swell or migrate, plugging pore spaces and decreasing
permeability. Sandstone acidizing restores natural permeability and increases productivity by
removing clay damage and controlling fines migration.

Figure 1 (effects of damage zone-permeability decrease ) demonstrates damage ratio at various

depths of damage for varying degrees of permeability decrease. Obviously, the greatest damage
occurs near the wellbore.

Figure 1

Usually, acidizing an undamaged sandstone formation is not desirable. Theoretical production

increases obtained from these treatments are rarely above 1.3 not enough to justify the acidizing
cost. In some instances, however, a highly productive undamaged well can be stimulated enough by
acidizing to show an economic advantage: a production increase results from pore enlargement in
the zone adjacent to the wellbore. Figure 2 shows the effect on production of an improved
permeability zone.

Figure 2

Treating Acids
Acids used in stimulating sandstone reservoirs generally contain some form of the highly reactive
fluoride ion ( F- ). This ion is the only one that reacts significantly with sand and clay. Treating acids
containing the fluoride ion include HCl-HF and HF-organic acid mixtures.
HCl-HF Mixtures This acid blend can be prepared by one of three methods: dilution of concentrated
HF or, as is more frequently done, by mixing Hcl with ammonium bifluoride (NH4HF2).
HF-Organic Acid Mixtures: Blends of HF-organic acids, are used occasionally to retard the reaction of
acid on sand and clay, and to reduce corrosiveness. These can provide deeper penetration of unspent
HF and, consequently, effective removal of deep damage. Either HF-formic or HF-acetic can be
prepared from liquid HF, solid ammonium bifluoride (NH4F2), or ammonium fluoride (NH4F), and the
corresponding organic acid.
All acid solutions should be prepared with fresh water. Sea water or brines should never be used in
preparing acidizing fluid for HF-type treatments. Since these waters may contain sodium or
potassium ions, they can cause formation-damaging precipitants.
HF reacts with SiO2 to give fluosilicic acid (H2SiF6) and water. This is one of the more important
reactions of HF.
Rate of the reaction is primarily dependent on the following variables:

type of mineral present

size of sand grains
temperature
volume and/or strength of HF
concentration of HCl contained in the blend
Decreasing sand-grain size increases surface area for a given weight of sand. The larger the surface area, the
faster the acid reacts. The effect of temperature on the reaction rate is shown in Table 1(below).
Temperature

Reaction Rate Constant (cm/min)

75 F

3.89 x 10-5

100 F

5.59 x 10-5

150 F

11.27 x 10-5

200 F

20.05 x 10-5

300 F

51.46 x 10-5

Table 1: Effect of temperature on reaction of HF acid on sand.

This data show that increasing temperature significantly increases HF reaction rate on sand. Reaction
rate is about 13 times faster at 300 F than at 75 F. The primary control on reaction rate, however,
is the rate of acid movement and whether the acid contacts a fast or slow-reacting material. HF acid,
for example, reacts relatively slowly with quartz, but much more quickly with feldspar or kaolinite.
Increasing the acid volume and/or strength increases the distance unspent HF can be pumped into
the formation.
Varying the concentration of HCl in the acid blends also affects the HF reaction rate on sand ( Figure 3
., influence of HCl on HF-sand reaction ). Increasing HCl concentration in HCl-HF mixtures increases
the amount of sand that can be dissolved by equivalent concentrations of HF. Blends with greater HCl
strengths react longer.

Figure 3

Fluosilicic and fluoaluminic acids, reaction products between HF on clay or sand, can react with
sodium ions (Na+) or potassium ions (K+) to form precipitates.
The reaction of the sodium ion is:
H2SiF6 + 2Na+ > Na2SiF6

+ 2H+

H2AlF6 + 3Na+ > Na3AlF6

(22)

+ 3H+

(23)

The reaction products, sodium fluosilicate and fluoaluminate, are white, gelatinous solids which can partially plug
permeability. These potentially damaging precipitants can be prevented by proper acid placement techniques. On
the other hand, ammonium fluosilicate and ammonium fluoaluminate, reaction products with the ammonium ion, are
completely soluble.
Reaction of HF on limestone (CaCO3) produces a very fine white precipitant: calcium fluoride
(CaF2),along with water and carbon dioxide. Calcium fluoride can cause formation damage, but this
problem is avoided by proper placement of HCl.
Treatment Technique
The three key stages of fluid placement during an HF treatment are preflush, HF acid, and overflush
or afterflush. Although various fluids may be pumped ahead of the preflush or behind the overflush,
no change should be made in these three basic stages. This treatment technique is designed to be
compatible with natural formation fluids. Figure 4 illustrates the basic HF acid treatment design.

Figure 4

Preflush: A preflush fluid should always be pumped ahead of a fluoride-containing solution (e.g., HF
acid). It forms a vital barrier between the acid and the formation fluids which prevents the formation
of insoluble precipitants, such as sodium and potassium fluosilicates and fluoaluminates, and calcium
fluoride (a reaction product of HF with limestone). If HCl is used as a preflush, it dissolves the
limestone or dolomite, thereby reducing the possibility of the formation of insoluble precipitants. The
preflush fluid must be compatible with both the formation fluid and the HF treatment.
A solution of 5 to 15% HCl or acetic acid is popular for displacing formation brines to prevent them
from mixing with reacted HF. The solution is also useful in the removal of small amounts of
calcareous cementing material. Both conditions can result in the development of insoluble
precipitants.
Ammonium chloride (NH4Cl) is useful as a preflush if calcium chloride (CaCl2) has been used as a
workover fluid. The calcium chloride should be either circulated out with a 3% NH4Cl solution or
isolated behind a packer. Any calcium chloride left in the wellbore should be preflushed away into the
formation with HCl or NH4Cl solution.
Diesel oil, kerosene, and certain crude oils may also be used as preflushes. However, their use is
dependent on total compatibility with the formation fluids, the HF acid treatment, and all surfactants
included in the treatment sequence.
HF Acid: After the preflush, HF acid is pumped into the formation. The treatment fluid should be of
an adequate volume and have proper concentration. A 12% HCl-3% HF solution is the usual
concentration for damage removal in a high-quartz, low-clay formation. A 13.5% HCl-l.5% HF
solution may be used in a high-feldspar formation, and a 6.5% HCl-l.0% solution where high clay
content is a factor. In extremely "tight" formations (i.e., those with less than 1 md permeability), a
3% to 7% HCl-0.5% HF solution may be used. Table 2 (below) provides more detailed acid-use

guidelines for sandstone acidizing.

Situation

Acid Type

HCl Solubility > 20%

HCl only

High Permeability (100 + md)

High Quartz 80%, Low Clay <5%

12% HCl - 3% HF1

High Feldspar >20%

13.5% HCl - 1.5%

HF1

High Clay >10%

6.5% HCl - 1.0% HF2

High Iron Chlorite Clay

3% HCl - 0.5% HF2

Low Permeability (20- md)

Low Clay <5%

6% HCl - 1.5% HF3

High Chlorite

3% HCl - 0.5% HF4

Preflush with 15% HCl

Preflush with Sequestered 5% HCL

Preflush with 7.5% HCl or 10% Acetic

Preflush with 5% Acetic

Table 2: Acid use guidelines for sandstone acidizing (From McLeod, H. O.: "Matrix Acidizing", Journal
of Petroleum Technology, Dec. 1984, pp. 20552069).
As mentioned earlier, when HF is pumped into a formation, a decrease in permeability occurs, with a
possible corresponding increase in pump pressure. This condition is due to the initial rapid reaction of
the clay, precipitation of hydrous silica, and the dislodging and migration of fines. The 3% and 6% HF
concentrations demonstrate this initial reduction in permeability, followed by overall permeability
increase. Occasionally, as demonstrated by the 9% HF concentration, the damage is complete, with
the wellbore totally plugged ( Figure 5 , change in permeability observed during acidizing with various
strength HF acid systems).

Figure 5

No more acid can be injected at this point without fracturing the rock. To maintain permeability, 3%
HF is used for most treatments; in high clay content formations, even lower-strength HF should be
used. Lower-strength HF acid concentrations generally present fewer problems than higher
concentrations.
Overflush: The overflush, or afterflush, is designed to minimize the precipitation of Si(OH)4 , which
can limit the success of acid treatments. The overflush is also used to:
displace unreacted HF into the formation, thus reducing corrosion, leaving more acid to react in the
formation, and allowing for a shut-in period, should one be required (e.g., ahead of a gravel pack)
displace HF reaction products away from the wellbore
remove the oil-wet relative permeability problems caused by cationic surfactants, such as
corrosion inhibitors
stabilize clays and fines
reestablish oil or gas saturation near the wellbore
Typical overflushes for HF treatments are 3% NH 4Cl, 3% to 7% HCl, organic acid, diesel oil, kerosene, crude oil,
and nitrogen (commingled with any of the above fluids, or by itself). Aqueous ofterflushes are the most effective in
displaying spent acid from the near wellbore region.
The most common is 3% NH4Cl, because it is one of the few salts that will not precipitate insolubles
with active or spent HF. Diesel is another frequently used overflush in oil-producing wells. Often, a
mutual solvent is added to the overflush to improve saturation and relative permeability
characteristics.

HF reacts very rapidly on clays. Consequently, a long shut-in time is not required. A slow return of
the treatment load should begin as soon as practically possible. This minimizes fines movement;
those that do move are more likely to come back to the wellbore without bridging. Allowing the
reacted acid system to remain in the formation for extended periods of time increases the chance of
fluid intermixing. Also, energy used to place all treating fluids may be dissipated.
Use of Additives
During acid treatment of sandstone formations, fluids pumped into the rock pores contact a large
surface area, where capillary pressures begin to govern flow rates and fluid recovery.
Thus, selecting the proper additives ensures that
treated fluids are used throughout the acidizing sequence
the additives are not adsorbed onto rock surfaces to leave virtually untreated acid solutions
to penetrate the deeper portions of the formation
Figure 4 (HF acid treatment design), shows the preflush fluid in direct contact with formation fluids. To prevent
emulsion problems and sludge deposits, the preflush fluids must be adequately treated to maintain compatibility
with formation crude oil.
If the additives have a tendency to adsorb on the rock, steps must be taken to minimize their
adsorption enough to allow adequate penetration. Surfactants can reduce the acid's surface tension,
and thus reduce capillary pressure and aid in cleaning up the reacted acid solutions.
Treatment Design
Before designing a sandstone treatment, the engineer should gather as much information as possible
about the composition and properties of the formation. Although well data, cores, and formation
materials are not usually available, the engineer needs to obtain or estimate information about the
following:
formation permeability
fracturing pressure
condition of the tubing
wellbore geometry
Formation Permeability: Formation permeability must be estimated to calculate the injection rate possible during
treatment stages. Generally, a minimum injection rate of 1/4 BPM should be achieved during final HF placement
and overflush. Sometimes early injection rates may be very low, making it necessary to use the hesitation-squeeze
technique of acid placement. However, if a proper analysis has been made of the wellbore condition by previous
well testing or other estimates, the injection rate can be estimate before HF reaches the formation. Then, if the
calculated treatment time is too long, a mini HF treatment can be run to open up more injectivity before the main
acidizing volume.
Fracturing Pressure: Fracturing pressure must also be estimated to determine the allowable injection
rate into a formation. Fracture gradients of new wells are usually available, but these values decline
as the formation is depleted. A useful technique is available to estimate the effect of reservoir
pressure decline on the fractured gradient.
Condition of the Tubing: Any rathole requires isolation or cleanout prior to acid placement. Tubing
should be run to bottom, and the well circulated with a formation-compatible fluid to clean the

wellbore of all debris and sludge. Otherwise, during the treatment the more dense acid will displace
the rat-hole fluid and allow this debris and sludge to enter the perforations, potentially causing
severe plugging.
Wells that periodically scale up can be treated for calcium scale by circulating acetic acid down the
annulus and up the tubing. This action removes cumulative calcium carbonate scale from the
downhole pump and around perforations. Should iron scale exist in the tubing, acid can be pumped
down the tubing through coil tubing to bypass the inner pipe wall. Coil tubing is especially useful in
injection wells, where it allows acid to bypass (and thus protect) the injection tubing string.
Injection water often contains sufficient oxygen to cause oxidation corrosion. Acid removes the iron
oxide from tubing walls coated with iron hydroxide. This reaction removes some protection from
water with dissolved oxygen. However, ferric chloride created by the acid and iron oxide reaction
causes more corrosion; this type of corrosion cannot be prevented by acid corrosion inhibitors. Bare
metal can be protected from HCl by inhibitors, but inhibitors do not prevent the oxidation-reduction
process between ferric iron and pure tubing iron.
Tubing in the well if it is known to be clean, or it can be cleaned in place can be used to inject
acid. If the tubing has considerable scale buildup or if paraffin and/or asphaltenes have accumulated
inside, the tubing should be bypassed with a concentric string or replaced with a special treating
string. If a treatment string is used, however, pipe dope application to the threads should be closely
supervised. Excessive pipe dope can cause perforation plugging and less than desirable acidizing
results. The use of plastic-coated tubing eliminates the need to clean or "pickle" the tubing with acid
prior to acid placement.
Wellbore Geometry: The mechanical aspects of acid placement must be selected according to well
conditions and wellbore geometry.
In wells with long multiple-producing intervals, zone coverage control is needed. The most effective
treatment is with an opposed cup packer (wash tool). It can distribute the HCl preflush over every
foot of zone, followed by a similar run with the HF acid stage and then the overflush. This technique
ensures that every part of the perforated interval is treated.
Another way to acidize the productive zone effectively is with a retrievable bridge plug and squeeze
packer positioned, respectively, below and above selected perforations.
Moreover, successful use of these techniques requires an excellent cement job. A cement bond log
(CBL) run after primary cementing can help to show whether zone isolation has truly been achieved.
If there is some question about cement job integrity in the vicinity of the intended perforations,
diverting materials should be considered.
Tubular Cleanup Fluid: If new tubing is in the well, the safest way to help prevent formation damage
is to pickle the pipe with acid containing large quantities of iron-retention additives, and to circulate
the acid out of the well. Xylene or hydrocarbon phase should be used as a preflush for the removal of
pipe dope and varnish, which can plug perforations. A suggested tubular cleanup procedure includes
15% HCl to remove the mill scale which is in most new tubular goods. Sequestering additives
maintain the dissolved iron in solution and the penetrating, nonionic surfactant helps the acid contact
the pipe and scale after the xylene. This cleaning and pickling process helps prevent the deposition of
debris into the formation during the stimulation treatment.
Selecting Stage Volumes: The engineer can better select sandstone acidizing stages and stage
volumes by analyzing the well.
Formation Injection: A hydrocarbon preflush should be placed in the formation ahead of the HCl preflush if
crude oil/acid incompatibility exists. Should a problem crude and calcium coexist in the reservoir, an
aromatic acid dispersion should be squeezed into the formation to remove both calcium carbonate and
paraffin/asphaltenes.

Preflush: The volume of preflush fluid should be large enough to accomplish two goals: (1)
dissolve the calcium carbonate contained in the zone contacted by unreacted HF and (2)
provide sufficient fluid at least 2 ft from the wellbore to serve as an adequate barrier between
the reacted HF and formation brine.
Therefore, the volume and strength of the preflush is somewhat contingent on the calcium
carbonate content of the formation. HF reaction products (H2SiF6, etc.) are somewhat
compatible and soluble in the presence of calcium carbonate; hence, it is only necessary to
remove the calcium carbonate from the zone contacted by HF to prevent precipitation of
calcium fluoride.
HF Acid: The HF stage should be designed for at least two hours (preferably four hours) of
contact time around the wellbore.
Over flush: The overflush should be designed to displace the HF to a radius of 3 to 5 ft
around the wellbore, or the overflush volume should at least equal the HF stage. This pushes
hydrous silica and other insolubles out to a safe distance, minimizing the damaging effects
from these solids during subsequent production.
Stage volumes for the acid treatment are determined by the allowable injection rate in 8 to 10 hours of daylight
acidizing time. First priority is the overflush, second is the 2 to 4 hours of HF contact time, and third is total acid
pumping time. Nitrogen or CO2 can be added to the various stages, depending on reservoir pressure and the
anticipated difficulty in recovering the treatment.

Matrix Acidizing of Carbonate

In matrix acidizing, HCl is injected into the formation below fracturing pressure. The objective of
such a treatment is to achieve radial acid penetration and increase permeability near the wellbore.
The main application for this technique is to remove near wellbore damage and restore productivity
in highly permeable zones.
A major problem in carbonate acidizing is that HCl usually reacts too fast. Generally, the main factors
that affect HCl reaction rate on limestone and dolomite are area/volume ratio and diffusion.
Area/Volume Ratio: HCl reaction time is indirectly proportional to the carbonate surface area in
contact with the acid. Extremely high area/volume ratios are the general rule in matrix acidizing.
Therefore, obtaining significant acid penetration before spending during a matrix treatment is almost
impossible. Figure 1 (effect of area-volume ratio on HCl-CaCO3 reactions) shows the comparative
effect of area/volume ratio on HCl spending time in a 6-in.

Figure 1

wellbore 0.1-in. fracture, and matrix of a limestone formation.

Diffusion: Diffusion is the time required for spent HCl on the formation surface to be replaced by live
acid in solution.
Well Candidates
Carbonate formations damaged during drilling or completion are generally the best candidates for
matrix acidizing treatments, because natural production can usually be restored. In some cases,
however, other types of treatment may be equally effective.
If the formation is homogeneous, such that an induced fracture will heal, hydraulic fracturing with
proppant may be a better stimulation choice. Nearby water zones would definitely be a factor in
considering a matrix treatment, but, again, a low-injection fracture acidizing treatment may yield
better results.
For example, consider a fracture acidizing treatment designed for significantly increasing production
and minimizing bottom water production. This design involved a well with a 60-ft perforated interval
in a carbonate formation 200 ft above an oil-water contact. There were two choices in attempting to
stay away from the water: (1) a true matrix acidizing treatment and (2) a controlled height fracture
acidizing treatment designed at a low injection rate. Matrix acidizing provides the best chance that
only the perforated interval is treated, but would require a whopping 180,000 gal of HCl to dissolve a
5-ft wellbore radius. In contrast, fracture acidizing at 12 BPM with a viscous preflush and 30,000 gal
of HCl would create an etched fracture length of approximately 200 ft. The created flow capacity is
more or less equivalent to a 100-ft effective wellbore radius.

Acidizing Considerations
Only a few special considerations need discussion in most cases of carbonate formation acidizing. To
maximize production, acid types and additives need to be carefully selected. From the standpoint of
reaction with formation minerals, however, there is little chance of doing more harm than good to
production. Table 1 provides some useful guidelines for acid selection.
When HCl is injected into a carbonate reservoir under matrix conditions, acid preferentially flows into
the areas of highest permeability. Acid reaction in the high-permeability regions causes the
development of large, highly conductive flow channels called wormholes ( Figure 2 , carbonate core
with large wormholes). High reaction rates, as observed between all concentrations of HCl and
carbonates, tend to favor wormhole creation.

Figure 2

Wormhole length normally is controlled by the fluid-loss rate from the wormhole to the formation
matrix. It can be substantially increased by reducing the fluid loss rate from the worm-hole to the
formation with fluid-loss additives. The careful selection of type and concentration of additive is
essential. For example, too high a concentration of fluid-loss additive can plug the formation, and too
little is not effective.
The most effective fluid-loss additives are solids or acidswellable polymers used in fracture acidizing.
Emulsified acids, because of their high viscosity, often give better results than plain HCl. On the other
hand, retarded acids usually work no better than HCl in a matrix treatment because they do not
control the rate of fluid loss from a wormhole.
Treatment Design
The design of a matrix acidizing treatment for a carbonate formation consists of specifying acid type
and volume, a maximum injection rate, and fluid pressure that will not fracture the formation. The

same calculation method used to determine maximum injection rate and pressure in matrix acidizing
of sandstone applies here. Selection of acid type and volume, however, are more arbitrary.

Situation

Acid Type

Perforating Fluid

5% Acetic

Damaged Perforations

10% Formic
10% Acetic
15% HCl

Deep Wellbore
Damage

15% HCl
28% HCl
Emulsified HCl

Table 1: Acid use guidelines for carbonate acidizing.

A good general recommendation is to inject 50 to 200 gal/ft of 15% or 28% HCl. Exact acid volume
and strength cannot be predicted without knowing specific near-wellbore conditions. A good general
rule would be to use larger acid volume in high-temperature wells (or where deep damage is
suspected), and high-strength HCl with an effective fluid-loss additive in zones where acid can be
injected at practical rates of 0.25 to 0.5 BPM.

Fracture Acidizing
Fracture Acidizing
Fracture acidizing is a process in which acid is injected at a high enough rate and pressure to fracture
the formation. It usually involves injecting a viscous pad fluid ahead of the acid to initiate the
fracture. Differential rock removal occurs as the acid reacts chemically with the formation faces. This
results in an uneven etching pattern which increases flow capacity to the wellbore and provides a
higher productivity ratio.
Fracture acidizing has application in carbonate reservoirs, both limestone and dolomite. There are
two main reasons for performing this type of stimulation treatment. First and foremost is low
permeability, where natural production is not economical; a conductive fracture provides much more
flow area for produced fluid or gas. The second reason is to overcome damage that extends deeper
than matrix acidizing can effectively reach.
Successful fracture acidizing depends on developing a fracture geometry with adequate surface area.
Ideally, the created fracture should cover the productive interval vertically, be as long as the well's
drainage radius, and be wide enough to aid acid penetration.
The ideal fracture geometry is seldom, if ever, obtained, because of geological considerations or
mechanical limitations. The vertical fracture height may exceed the productive interval and extend
into a barren interval or into unwanted production. The conductive fracture length is usually less than
the created fracture length because the fast surface-reaction rate generally spends the acid quickly.
The spent acid and the residual preflush then create additional unetched fracture area.

Fracture Geometry
In deciding whether to place a propped fracture or an acid fracture in a a carbonate formulation, we
must be guided by the treatment costs and their expected post-treatment performances. For both
types of treatments, there are optimal fracture lengths based on the Net Present Value (NPV) of the
fracture treatment (Economides et. al., 1994). In general, acid treatments results in shorter fractures
than propped treatments, and thus would more likely be appropriate for higher-permeability
formations.
Theoretically, a vertical fracture extends an equal distance from the wellbore in opposite directions (
Figure 1 , Fracture geometry).

Figure 1

Fracture geometry is defined as fracture length in one wing of the fracture times the height and
width of that wing. Factors that affect fracture geometry are:
volume of injected fluid
fluid loss
viscosity of injected fluids
injection rate
rock properties
formation fluid properties
The first four of these factors can be controlled. Volume is restricted only by economic factors; injection rate can be
in-creased by using friction reducers, more hydraulic horsepower, larger tubular goods, or a combination of these.
More information about these controllable variables follows.

Fluid Loss: It is much more difficult to control this critical factor with acid solutions than nonacid
solutions, because the acid reacts with the formation to continually enlarge pore sizes. Fluid loss not
only affects fracture geometry, it also influences acid penetration distance through fluid leakoff
velocity. Table 1 (below) presents data illustrating the importance of fluid loss control. In this
example, the formation had an average permeability of 1 md and 15% porosity. In each case, the
only variable was the fluid loss properties of the acidizing fluid.

Treating*
Fluid

Ceff
ft/min
1/2

W**

L ft.
BPM

Inj
Rate

% Fluid. eff.

No FLA

.005

75

.036

136

15

4.6

50 lb FLA /
1000 gal

.001

75

.082

501

15

38.4

100 lb FLA /
1000 gal

.0001

75

.120

811

15

91.0

* 10,000 gal 28% HCl

** Average Width
Table 1: Effect of fluid loss on fracture geometry.
Viscosity: Viscosity affects the reaction rate of acid on carbonate rock because it influences the
treatment fluid's capacity for turbulence, and thus the rate of contact between the hydrogen ions and
the rock surface. The higher the viscosity of the acid, the lower its capacity for turbulent flow, and
the lower the reaction rate.
Viscosity may also be the most important factor affecting the penetrating distance of live acid in
carbonate rock. High viscosity means low turbulence, which in turn means low acid-spending rate
and deeper penetration. This phenomenon is shown graphically in Figure 2 (Acid penetration distance
vs.

Figure 2

acid viscosity ). (The term used to describe viscosity in this figure is the "stoke," which is equivalent
to (centipoise/100) x density.) Doubling the viscosity provides a significant increase in the
penetration distance of live acid.
Another phenomenon not shown in this curve is the relation of increased viscosity to fracture width.
As viscosity increases, the fracture width at a given pump rate also increases ( Table 2 , below).
Although larger volumes of acid are regard for this purpose, even greater penetration distance can
be achieved.

Viscosity Fracture
Width in.

cp

0.038

10

0.068

100

0.120

1000

0.214

Injection Rate = 10 BPM

Fracture Length = 100 ft
Young's Modulus = 10 x 106psi
Table 2: Effect of viscosity on fracture width.

Injection Rate: Generally speaking, the higher the injection rate, the greater the fluid turbulence,
and the greater the rate of contact between the hydrogen ions and the rock surface in other
words, the greater the acid spending rate. Spending rate is governed by these factors in combination
with hydrogen ion concentration. Increased hydrogen ion concentration and turbulence work together
to increase acid spending rate and decrease penetration distance.
Increased injection rate can increase penetration distance under certain circumstances. All other
things remaining constant, the faster acid flows down a fracture, the farther it will travel before it
spends (unless it goes into turbulent flow). This is because contact time between the acid and the
formation is insufficient to allow complete reaction between the acid and the formation.
Figure 3 (Acid penetration distance vs.

Figure 3

pump rate) shows both phenomena occurring. The curve for limestone shows a decrease in
penetration distance as the acid goes into turbulence. Then an increase can be seen as the acid
travels farther in a given period of time. On the dolomite curve, the distance traveled is more
important than the mixing rate because the surface reaction rate is slower for dolomite than for
limestone.
Higher injection rates also increase the fracture width, provide greater cooling effects, and improve
fluid efficiency. These effects are not shown on this curve, but all tend to increase penetration
distance.
Formation Characteristics

Other important considerations in fracture acidizing are the following formation characteristics: rock
composition, permeability, and temperature.
Rock Composition: The physical and chemical composition of the rock influences the reaction of acid;
for example, dolomite is generally slower to react with HCl than limestone.
Carbonate formations are often mixtures of dolomite, limestone, and acid-insoluble materials. The
more insoluble material a formation contains, the slower its reaction with acid. If the acid-soluble
portion is lining fractures in an otherwise insoluble formation, excellent stimulation may be obtained
even though total solubility is low.
Although carbonates seldom contain large quantities of clays, occasionally they can contain enough
to deter the fracture acidizing treatment. If clays are present, potassium chloride can be added to
the preflush and afterflush solutions. If iron compounds are present, iron sequestering agents added
to the acid will inhibit the secondary precipitation of iron compounds when the acid spends.
Permeability: The matrix permeability dictates both the fluid properties and the amount of fracture
conductivity needed to obtain the desired production rate. High permeability decreases fluid
efficiency.
Temperature : Under normal conditions, acid reacts more quickly with carbonate materials as
temperature increases. At extremely high temperatures, however, fluid viscosity decreases, which
decreases fracture penetration significantly. Figure 1 contains data on the relationship between acid
penetration distance and temperature.

Figure 1

Treatment Materials and Procedures

Laboratory test data may also be important in the design of a fracture acidizing treatment. These
data may be gathered from fluid-loss tests, acid reaction rate measurement, and acid etching tests.
Fluid-Loss Tests: Fluid-loss tests should be run on cores to determine how much fluid-loss additive is
needed. The fluid-loss coefficients are necessary to calculate created fracture geometry in computer
designs.
Acid Reaction Rate Measurement: An acid's surface reaction rate can be determined on a formation
core with a rotating core disc in a reaction cell to determine the penetration distance of live acid in a
fracture. If no cores are available, generalized data obtained from typical limestone and dolomite
formations can be substituted.
Acid Etching Tests: These very important laboratory tests help determine if fracture conductivity can
be created by acid solutions, and which acids etch best. They also measure conductivity and the
injection time required to obtain adequate conductivity. To calculate the productivity increase
resulting from a treatment, first determine the fracture conductivity.
Types of Fracture Acidizing Treatments
There are several basic concepts to remember when considering types of acidizing treatments:
Any pumped fluid follows the easiest route.
A hole cannot be dissolved without leakoff. For example, 1000 gal of 15% HCl dissolves 10.8
cu ft (80 gal) of limestone but occupies 135 cu ft.
The higher the permeability and the solubility, the greater the leakoff.
Low-viscosity acids leak off more than high-viscosity acids.
If the leakoff is less than the injected amount, a fracture will be created.
Acid flows down a fracture easier than into the adjoining matrix.
Acid spends faster in a small hole than in a big hole, or faster in a narrow fracture than in a
wide fracture.
Low-viscosity acid spends faster than high-viscosity acid.
A 90% soluble rock is 10% insoluble, which will produce approximately 200 lb of fines/1000
gal 15% HCl.
A number of fracture acidizing treatments types are available, each with advantages and disadvantages. Some of
the common treatments are described below: conventional treatments, foamed acids, combination treatments, and
preflushes.
Conventional Treatments: Conventional treatments run with low-viscosity acid are easy to perform.
They tend to obtain high fracture flow capacity because of the narrow fracture and turbulent flow
that develop. These treatments require less acid than most others and the acid may be chemically
retarded.

These advantages are balanced by comparable disadvantages. The acid reacts rapidly in narrow
fractures, but spends so quickly that deep penetration of the live acid is difficult. Low-viscosity acid
does little to aid in fluid-loss control, and its fines-carrying capacity is limited.
Conventional fracture acidizing with high-viscosity acid overcomes most of the problems of lowviscosity acid, but has other disadvantages.
Advantages include easy mixing and pumping, good fluid-loss control, and better fines-carrying
capacity. High-viscosity fracture acidizing treatments may use either gelled or emulsified acids.
Gelled acids are more effective in friction reduction. A high-viscosity treatment is a retarded
fracturing fluid system which develops a wider fracture, helps establish laminar flow within the
fracture, and has a physical surface retarding effect.
Disadvantages of high-viscosity acid treatments are their high cost and possible problems of
emulsion and lower fracture flow.
Foamed Acid: In addition to emulsified or gelled acids, foamed acid may be used in fracture acidizing
treatments. Foamed acid has an erosive or scouring effect on the face of the fracture which helps
develop good fracture flow capacity close to the wellbore. The fluids are easy to recover, even in lowpressure wells. The foam is good for removing fines and controlling fluid loss when used in lowpermeability formations.
In spite of these advantages, foamed acid spends too fast to achieve deep penetration. More
pressure is required at the surface to pump it. Foamed acid has considerable fluid-loss control
capabilities, but it is more expensive than fluid-loss additives.
Combination Treatments: It is possible to run variations and combinations of the previously
described types of treatments. An alternating-phase method called the "alpha" technique uses
phases of acid (to improve fluid flow capacity) alternated with nonacid phases that contain fluid-loss
additives. These non-acid phases also act as acid extenders, thus reducing the volume of acid
required. The phases are normally alternated in 10- to 60-minute time frames, depending on specific
situations.
The density-controlled acidizing technique uses the overriding and underriding characteristics of
fluids with different densities, which are pumped in sequence into vertical fractures. This system uses
less acid than others, and keeps acid out of unwanted zones because of viscosity differences.
When standard fracture acidizing systems do not work, or cannot be run, systems called extended
matrix acidizing and closed-fracture acidizing may be employed. Although calculations cannot be
made regarding their acid penetration into wormholes or natural fractures, extended matrix acidizing
does allow the acid, at less than fracturing pressure, to enter natural fractures and the area of
highest permeability and solubility.
In closed-fracture acidizing, the "easy way out" routes for the acid are created fractures that have
been allowed to close, and previously etched fractures that are closed.
When matrix acidizing is used, the acid generally goes out the area of highest permeability because
there is less resistance to flow. It also goes out the areas of highest solubility because there are less
fines released to act as fluid-loss control additives. It goes out natural fractures which have high
solubility because they channel more readily.
Preflushes: Closed fracture acidizing can use a preflush to create a fracture rather than relying on a
natural fracture system. The procedure is to create the fracture system by pumping a high-rate
preflush, and then allow the fracture to close. Then, acid is pumped at below fracturing pressure
through perforations into the closed fracture.

A previously etched closed fracture treatment is identical to the above, except the initial fracture is
made with acid rather than with a preflush.
When preflushes are pumped before the treating phase, the treatment becomes more complex, more
acid is required, and the cost goes up. However, the returns from this type of treatment are better
fluid-loss control, and deeper penetration of live acid. An excellent acid-retarding system is
introduced. Also, uneven etching is achieved mechanically, and unetched areas are able to support
over-etched or acid-softened formation faces.
A preflush may be any fluid compatible with the treating phase that serves these intended purposes:
creating the main fracture system prior to the acid phase
controlling fluid loss ahead of the acid phase
cooling the fracture face for longer acid reaction
controlling density for optimum acid placement
A high-viscosity preflush can also
create a wider fracture, for an acid-retarding effect
allow the acid to channel, for a fingering effect
control natural fracture leakoff more effectively
Overflush fluids are those generally pumped after the treating phase. These can be any compatible fluid that
forces the acid out farther into the formation
carries an energized fluid, such as nitrogen or CO2, for easier fluid recovery
aids in the recovery of fines, if the fluid has sufficient viscosity

Treatment Design
The usual fracture acidizing design uses a computer to calculate the volumes of fluid necessary to
obtain precise fracture geometry and productivity increases. The following discussion, which relates
to fracture acidizing computer models, describes outputs, fracture conductivity, and inputs.
Outputs A fracture acidizing treatment creates conductivity by using acid to etch the walls of the
created fracture. Thus a treatment design program must keep track of acid spending-how the acid
reacts with the fracture walls by providing several pieces of data:
penetration distances
amount of viscous fingering
viscosity of stages
acid velocities
temperatures
acid concentrations

etched fracture length

Fracture Conductivity A fracture acidizing treatment must create a conductive fracture that increases well
production. Fracture conductivity results directly from the etching process. The conductivity at a given point in the
fracture is a function of the reactivity of the acid passing that point and the contact time between the acid and the
fracture at that point.
Intuitively, it would seem that the longer the acid has contacted a portion of the fracture, the more
material it will have removed and the greater the conductivity will be. If so, the greatest conductivity
should be next to the wellbore where acid has contacted the formation the longest. This may be far
from true, since fluid temperature is usually lowest as it enters the fracture and, if cool enough, the
acid reacts very slowly and does very little etching there. As it penetrates farther into the fracture
the acid becomes warm, increasing in effectiveness while it still has sufficient strength. The net result
may be low fracture conductivity next to the wellbore and near the etched length, with possibly much
higher conductivity somewhere in-between.
Any production increase calculations made in conjunction with a fracture acidizing program must
consider this great conductivity variation along the fracture length. A single steady-state productivity
index ratio cannot be effectively calculated.
Calculating production using a type curve simulator is difficult. Numerical simulators, however,
readily lend themselves to this type of calculation.
Inputs: Fracture acidizing design programs require the input of formation properties
fluid properties
an estimated fracture height
the pay zone location or height
They also require information about whether the treatment:
is conventional
uses the viscous fingering technique
uses foamed acid
uses any other special technique
Along with the treatment type, the acid type must also be selected and the acid concentration entered.
Acid type and concentration alone do not set the reaction kinetics. The other reaction component
must be considered: the rock. If laboratory-generated reaction-rate data are available for the specific
formation, these are usually entered into the computer program. If not, the program can empirically
calculate reaction rate constants from rock-composition (dolomite or limestone) data. The program
also requires data about
well configuration
injection rate
proposed treatment designs

Treating Techniques

After selecting the type of acid and additives and using a computer design to help choose the
quantity of preflush, viscous preflush, acid, and overflush, the number of stages must be determined.
An estimate must be made of the expected vertical fracture height, given the injection rate, viscosity,
rock properties, and changes in rock composition above and below the perforated interval.
Consider the apparent viscosity of the fluids in the treatment design. If the perforated interval
appreciably exceeds the expected vertical fracture height, then a multiple-stage treatment is
necessary. Of course, injection surveys, such as temperatures surveys and radioactive surveys, may
be useful in obtaining accurate fracture height information after a treatment. This data can then be
used for planning similar fracture acidizing treatments in the future. Mechanical diversion or use of
diverting materials may be required to obtain the most effective zonal coverage.

Diverting Materials in Acidizing

Diverting Materials In Acidizing
To obtain maximum stimulation from a matrix or fracturing acidizing treatment, it is necessary to
treat the total productive interval. When several zones are open to the wellbore, or when the section
to be treated is massive, it is often necessary to divide the treatment into stages. A technique that
forces each stage to go into a different zone ensures treatment of the total productive interval.
In the case of multiple intervals, the formations may differ from one another in reservoir pressure as
well as permeability.Flow often can be effectively diverted using downhole equipment such as
packers and bridge plugs, and sliding sleeves between packers. However, since use of a workover rig
to move downhole equipment can significantly increase total cost, techniques for separting the
treatment into stages without using packers are often preferred These techniques, which use a
diverting material, temporarily plug the interval just treated, thereby diverting the next acid stage to
an untreated zone.
Diverting can be achieved completions like openhole zones, gravel-packed zones, and perforations by
varying the diverting material size distribution.

Solid Type
The most widely used method of placing treating fluids employs diverting agents composed of solid
particles. The particles create a restriction in and across the formation sections that accept fluid most
readily, forcing the breakdown of other exposed intervals. Ideal solid-type diverting agent properties
have a wide particle-size distribution
coarse: 0.25 to 0.002 in.
fine: 0.02 to 0.0001 in.
are soluble in both water and oil
have a slow rate of solubility, so the agent remains solid during the entire stimulation
treatment
dissolve in a reasonable time, so the well can be returned to production or injection without
unnecessary delay
cause no damage to formation permeability
are suitable for use with both perforations and in openhole

block effectively across fractures and perforations at high differential pressures

remain stable at high bottomhole temperatures
are compatible with all well and treating fluids, including acid
More information about the physical and chemical properties of solid-type diverting materials follows.
Physical Properties: The melting point of the solids used in diverting should be sufficiently higher
than the formation temperature so that the solid does not melt or soften on the formation face
during the treatment. However, some solids depend on melting with reservoir temperature to be
removed. The most important property of the diverting solids is their particle-size distribution.
Diverting in all types of completions, except gravel-packed zones, requires a uniform particle-size
distribution from 40-mesh to smaller than 325-mesh. This distribution provides sufficient variation in
particle size to treat a wide range of varying permeabilities.
To divert through a gravel pack, the solid diverting material must be fine enough to penetrate the
gravel pack and filter out on the formation face. Effectiveness of acid distribution with and without
diverting agent is demonstrated by comparing Figure 1 (distribution of acid without diverting agent )
and Figure 2 (distribution of acid with diverting agent).

Figure 1

Figure 2

If the diverter is not fine enough to penetrate the gravel pack, the material will bridge on the gravel.
This diverts the fluids to a different portion of the gravel pack. However, fluid can then move
vertically in the gravel pack so that all the acid is still flowing into the same highest-permeability
zones. The low-permeability zones may remain untreated.
Chemical Properties: The diverting solids should have limited solubility in acid solutions. To aid in
their removal after the acidizing treatment, however, the solids should be soluble in natural formation
fluids, such as oil, gas, and connate water.
A material with limited solubility in water is useful for diverting acid in water wells or injection wells.
In these situations, a sufficiently high volume of water flows through the diverted zone to eventually
remove all the solid diverting material. These solid diverting agents should be compatible with
surfactants, corrosion inhibitors, and mutual solvent additives in the acidizing fluids.

Gel Type
Gel-type diverting agents are available in both temporary and permanent forms.
Temporary Gels: Temporary gels are used during acidizing or fracturing treatments that call for
diverting or blocking action. They are commonly used in previously acidized or fractured wells, with
side permeability differences, that benefit more from multiple than single extended fractures or flow
channels.

Temporary gels are either oil- or water-base mixtures. They are usually pumped into the formation
as relatively thin fluids which set up quickly to form a semi-solid or thick gel that prevents additional
fluid from entering the zone. After a predetermined time the gel breaks, reverting to a water-thin
liquid that is easily produced from the well.
Diversion of a pregravel-pack acid treatment can be accomplished with 5 bbl batches of gel led 3%
NH4Cl plus 100 lb. of correctly sized gravel-pack sand. The combination of viscosity and particles
diverts treating fluid to other perforations.
Permanent Gels: Permanent blocking gels are especially useful for blocking within the formation. On
the surface they are thin, true solutions of low viscosity that can penetrate any water-permeable
formation. Once in place within the formation, they solidify into a rigid, permanent gel that does not
break.
Permanent gels are designed to
alter the injection profile of water-injection wells
shut off water zone encountered in air drilled wells
plug lost circulation zones

Ball Sealers
Ball sealers are used to temporarily seal perforations during acidizing treatments. When seating
against perforations, ball sealers direct treating fluid selectively so that each portion of the perforated
interval is treated. Two types of currently available ball sealers are the standard weighted ball sealer
and the buoyant ball sealer.
Standard Weighted Ball Sealer This type of ball sealer is put into the treating fluid stream at regular
or predetermined intervals, or is dropped in batches. Generally, at least one ball preferably more
is injected for every perforation.
Ball diameters vary from 5/8 to 1-1/4 in., and specific gravities range from 0.9 to 1.8. Its size is
proportional to that of the perforation to be sealed. Obviously, during fracture acidizing, balls are not
added until the formation has been broken down and is accepting fluid.
When fluid injection is stopped, or upon completion of the treatment, the balls are no longer held
against the perforations and they fall to bottom. Fluid velocity and differential pressure hold the ball
sealer in position during the treatment. If the perforation density is too great or the balls are oddly
shaped, or if communication exists behind the pipe, this type of ball sealer falls to bottom. Figure 1
demonstrates the seating efficiency of ball sealers in a test case.

Figure 1

Characteristics of ball sealers are shown in Table 1(below). The type to use in a specific application
is determined by the carrying fluid, bottomhole temperature, and maximum perforation diameter. To
ensure a total "ball-off," use 200% excess over the number of perforations.

OD Sizein.

Specific
Gravity

Core
Diameterin.

Core Material

Maximum Perforation Diameter-in.

5/8

1.2

None

Solid Rubber

0.38

5/8

1.3

1/2

Nylon

0.38

3/4

1.3

5/8

Nylon

0.52

7/8

0.9

3/4

Phenolic

0.52

7/8

1.1

3/4

Nylon

0.52

7/8

1.3

3/4

Nylon

0.52

7/8

1.4

3/4

Phenolic

0.52

7/8

1.8-2.0

3/4

Aluminum

0.52

15/16

1.2

None

Solid Rubber

0.52

1.1

7/8

Nylon

0.63

1.3

7/8

Nylon

0.63

1-1/4

1.2

1.06

Nylon

0.87

1-1/4

1.3

1.06

Nylon

0.87

Table 1: Standard weighted ball sealers with rubber exterior

Buoyant Ball Sealer: This type of ball sealer, developed by Exxon Production Research, improves the
reliability of diverting techniques by properly controlling the density between the ball sealer and the
treating fluid.
Balls having a density less than the treating fluid can achieve 100% seating efficiency on perforations
that are accepting fluid, provided that they are transported to the perforated interval. This efficiency
can be maintained at very low injection rates through individual perforations.
Buoyant ball sealers dramatically improve the ability to divert well-treating fluids, not only in
fracturing-type treatments but in matrix rate treatments as well. Using buoyant ball sealer concepts,
wells having over 1000 perforations through 250 ft of interval have been stimulated effectively
throughout their entire area. Matrix treatments have been successfully diverted where conventional
ball sealer practices would not have been attempted.
Buoyant ball sealers are characterized by having a syntactic foam core (containing hollow spheres
bound together with resin) and a polyurethane cover. They are generally available in the same sizes
as standard weighted ball sealers. Buoyant ball sealers have more uniform density and higher
compressibility. A 50% excess over the number of perforations is recommended.

Selection of Diverting Materials

Diverting materials are available for use in varied well conditions and over a wide temperature range.
Selection of the best agent and concentration is based on the formation fluids contacted, interval
length, formation temperature, physical properties of the formation, type of well completion, and
placement. Guidelines for the use of the more common temporary diverting agents are listed as
follows:
1. Graded Rock Salt

-Melting

Point: 1,472 oF

- Soluble in: water or dilute acid

-Specific Gravity: 2.164
-Type Well: Oil, Gas, Injection, Disposal
-Type Diversion: On perforations
On slots
In perforations
On formation

Concentrations to Divert:
-On Perforations (3/8" perforations) 16 lb at 1
lb/gal, 9 lb at 1 1/2 lb/gal
-In Perforations (per perf.): 1/2 to 2 lb
-Open Hole (lb/ft2 of Formation): 5 lb
2. Oil Soluble Resin

-Melting

Point - 328 oF

- Soluble in: oil or distillate

-Specific Gravity: 1.062
-Type Well: Oil, Gasb
-Type Diversion: On slots
In perforations
On formation
Concentrations to Divert:
-On Perforations (3/8" perforations):2 lb at
2 lb/galf
-In Perforations (per perf.): 1/8 to 1lb
-Open Hole (lb/ft2 of Formation): 2.5 lb
3. Oil Soluble Resin in Salt Solution

-Melting

Point - 328 oF

- Soluble in: oil or distillate

-Specific Gravity: 1.062
-Type Well: Oil, Gasb
-Type Diversion: Through gravel pack
On formation
In perforations
Concentrations to Divert:
-In Perforations (per perf.): 1/2 to 2.5 gal

fluid containing 0.5%

-Open Hole (lb/ft2 of Formation): 5 to 20
lb./1000 gal fluid
4. Karaya gum

-Melting

Point -

None

- Soluble in: water

-Specific Gravity: 1.062
-Type Well: Injection, Disposal
-Type Diversion: On formation
In perforations
Concentrations to Divert:
-In Perforations (per perf.): 1/4 to 1 lb
-Open Hole (lb/ft2 of Formation): 50 to 200
lb/1000 gal fluid
5. Graded Benzoic Acid

-Melting

Point - 252oF

- Soluble in: Oil, water, acid ,gas

-Specific Gravity: 1.316
-Type Well: Oil, Gasi, Injection, Disposal
-Type Diversion: On perforations
On Slots
In perforations
On formation
Concentrations to Divert:
-On Perforations (3/8" perforations)
9 lb at 1/2 lb/gal, and 2 lb at 1 lb/gal f
-In Perforations (per perf.): 1/4 to 1 lb
-Open Hole (lb/ft2 of Formation): 2.5 lb

6. Benzoic Acid in Alcohol Solution

-Melting

Point - 252oF

- Soluble in: Oil, water, gas , acid

-Specific Gravity: 1.316
-Type Well: Oil, Gas, Injection, Disposal
-Type Diversion: Through gravel pack
On formationd
In perforations
Concentrations to Divert:
-In Perforations (per perf.): 4%7
-Open Hole (lb/ft2 of Formation): 4%7

7. Unibead* OS-160 Buttons-OS160 Wide Range

-Melting

Point - 192 oF

- Soluble in:Oil
-Specific Gravity: 0.92
-Type Well: Oil, Gasc
-Type Diversion: On perforations
On slotse
Concentrations to Divert:
-In Perforations (per perf.): 1/4 to 1
lb
-Open Hole (lb/ft2 of Formation): 2.5
lb

8. Graded Napthalene
-Melting

Point - 176oF

- Soluble in: Oil or gas

-Specific Gravity: 1.145

-Type Well: Oil, Gasi
-Type Diversion: On perforations
On slots
In perforations
On formation
Concentrations to Divert:
-On Perforations (3/8" perforations)
8 lb at 1/2 lb/gal or 2 lb at 2 lb/gal f
-In Perforations (per perf.): 1/4 to 1
lb
-Open Hole (lb/ft2 of Formation): 2.5
lb

9. Unibead* OS-130 Buttons-OS130 Wide Range

-Melting

Point - 155 oF

- Soluble in: water or dilute acid

-Specific Gravity: 0.92
-Type Well: Oil, Gasc
-Type Diversion: On perforations
On slotse
In perforations
On formation
Concentrations to Divert:
-In Perforations (per perf.): 1/4 to 1lb
-Open Hole (lb/ft2 of Formation): 2.5
lb

10. Unibead* OS-90 Buttons- OS90 Wide Range

-Melting

Point - 138 oF

- Soluble in: oil

-Specific Gravity: 0.92
-Type Well: Oil, Gasc
-Type Diversion: On perforationse
On slots
In perforations
On formation
Concentrations to Divert:
-In Perforations (per perf.): 1/4 to 1
lb
-Open Hole (lb/ft2 of Formation): 2.5
lb
* wax polymer
a. If oil or gas is not making any water, a cleanup operation with dilute acid or brine may be required.
b. If gas well is not making distillate, oil soluble resins should not be used.
c. Unibead materials may be used in gas wells if temperature of zone exceeds the melting
point of Unibead material, but zone must be cooled by preflush or the first stage of treating
fluid to a temperature lower than the melting point. When the zone regains its original
temperature, Unibead material melts and is removed.
d. Oil soluble resin in salt solution and benzoic acid in alcohol solution will pass through a
sand pack and bridges on the formation. They will also bridge in perforation.
e. Unibead material will bridge on a 3/8 in. perforation, but the bridge will be weak.
f. The lb represents the amount of diverting agent required to bridge on a perforation (open
behind perforation) when used at the concentration listed (lb agent/gal of carrier fluid).
g. Each perforation or sq. ft. of formation will take approximately 25 gallons of treating fluid
containing 4% graded benzoid acid in alcohol solution before flow will be decreased to a
minimum. The treating fluid must contain enough additional material to saturate it at bottom
hole treating temperature.
h. Material should not be considered for HF acidizing operations. Other bridging agents are
compatible.
i. Subliming materials. Should receive special consideration for gas well applications.

Wellbore Cleanout and Scale Removal

Wellbore Cleanout

Wellbore cleanout is generally a soaking and agitation treatment designed to open up ferforations
and formation damage occurring in perforations or in the immediate wellbore vicinity. This technique
allows the treating solution to dissolve sludge and acid-soluble precipitants (scale) and recover mud
filtrate, formation fines, and other materials that might restrict production. Removing these
contaminants permits the well to produce at its natural potential.
Special attention is required for wellbore cleanouton the increasingly rare occasions when oil-external
emulsion muds and true oil-base muds are used. Emulsions used for drilling are usually fairly lowsolids, oil-external, oil-wet, clay-stabilized emulsions. Oil-base muds are usually prepared by gelling
a viscous, highly asphaltic oil and adding to it blown asphalt, fine calcium carbonate, and other
materials that impart additional fluid-loss properties. An approach used to successfully remove
formation damage caused by oil-base muds is discussed later.
A well is cleaned out prior to production testing (or before it is placed on initial production) or
whenever a producing interval begins to "clog up." This type treatment is designed only to remove
near-wellbore contaminants. The treating solution is not intended to penetrate the formation beyond
the immediate surface of the perforations or face of the productive interval.
Treating Solutions
Prior to the selection of a treating solution, formation fluid samples should be taken to determine the
presence of chlorides, sulfides, sulfates, and pH. If a sample of scale and/or sludge can also be
obtained, a more thorough laboratory analysis can be performed.
Many types of treating solutions may be used for wellbore cleanout. The constituents are based on
type of damage, formation type, general formation conditions, and the treating technique.
Pure Solvents: Xylene or toluene alone is most effective in removing paraffinic and asphaltic sludges
and oil-base mud. However, care must be taken in the selection of a hydrocarbon solvent when the
reservoir is dry gas. Solvents such as kerosene and diesel may cause relative permeability effects
which can seriously hinder production. For these applications, aromatic solvents, such as xylene and
toluene, are preferred. They are more easily removed from the formation than are straight-chain
solvents.
Mutual Solvent Systems In acidizing, mutual solvents are used in the postflush to:
reduce surface and interfacial tensions to promote cleanup and fluid load recovery
strip oil and sludge layers from acid-soluble materials
prevent emulsions from forming
break existing emulsions
assist in preventing or removing water blocks
Commonly available mutual solvents are
Amoco A-Sol: a blend of water-soluble and oil-soluble alcohols
EGMBE: ethylene glycol monobutyl ether
Amoco A-Sol A-28: a blend of alcohols
Amoco Super A-Sol: a blend of alcohols and xylene

 A variety of proprietary service company mutual solvents (e.g., MS-10, MS-12, MS15 (BJ
Services), MS-200 (Nowsco), Musol A (Halliburton), MAS (Serfco), and WSA-2, EZ-Sol and
MAS (Western)).
All these mutual solvent/acid systems can break through a thin sludge coating and allow acid to
contact the surface of the solid covered by sludge. However, mutual solvent/acid systems do not
disperse sludge.
To remove thick sludge, an aromatic solvent soak must usually precede a mutual solvent/acid
treatment. A two-hour xylene or toluene soak can soften sludge layers and allow mutual solvent/
acid penetration. Plain acid following an aromatic solvent soak generally has no positive effect.
Oil-base muds present a special problem in acid treatment. Many of these muds contain emulsifiers
that can develop very stable emulsions with acid or spent acid. In addition, mud solids and drill
cuttings provide the fines to stabilize the emulsions. An aromatic solvent soak followed by mutual
solvent and acid usually disperses it completely. The ideal mutual solvents for this operation are
Super A-Sol, A-Sol, or EGMBE, and the acid should be weak intensified acid (1/2% HF), if possible.
The treatment area is usually confined to the wellbore and open natural fractures, since the fines,
which are necessary for the emulsion, do not penetrate into the formation.
To avoid problems in completing a well drilled with an oil-base mud, circulate the well with solids-free
mud and then flush with xylene. The xylene dilutes the mud and causes any remaining solids to drop
out of suspension. These solids can be circulated out or removed by an appropriate mutual solvent
and acid.
Acid-External Emulsified Acid This acid system is usually composed of 10% xylene, with a surfactant
which disperses the aromatic solvent in the acid, and 90% acid phase that is usually 15% HCl. Acid
nonemulsifiers are not used because they may make the acid dispersion unstable. Moreover,
performance experience in the field shows that nonemulsifiers have little effect even when injected
into oil-producing intervals.
Stability of the acid-external emulsified acid is influenced by three factors: the degree of agitation
during preparation, concentration of the xylene phase, and strength of the acid phase. Increasing the
xy1ene or acid strength decreases stability. Should separation occur, the aromatic solvent can be
readily redispersed by circulating.
5 to 15% HCl This solution, with a high concentration of anionic surfactant (1 to 3% by volume), is
widely used for well-bore cleanout. The high surfactant concentration reduces surface tension and
makes the acid highly adaptable to both carbonate and sandstone formation as a first-stage wellbore
treatment for water-base mud removal. Even when diluted with 20 volumes of brine, surface tension
properties remain very low.
Another characteristic of this solution is that clay solids, which normally have a tendency to cluster
when contacted by acid, are effectively dispersed for easier removal. In addition to shrinking
hydrated mud by acid reaction, this mixture softens and allows the removal of harder and more
tenacious filter cakes.
Weak Intensified Acid (1/2% HF) Weak intensified acid, consisting of 1/2% HF, is useful in
unplugging perforations and establishing flow for HCl or HCl-HF acid mixtures. HF is especially useful
for dissolving clays and silica, making it a good choice for sandstone acidizing. In carbonates,
however, HF must be used in extremely low concentrations to avoid formation of insoluble
precipitants such as calcium fluoride.
Treating Procedure

The number of soaking and agitation applications depends on the amount of damage that has
occurred in perforations or in the immediate wellbore area. Treating solutions designed for
suspension, aromatic-solvent acid dispersions, or cleanup types are normally used in a soaking
action. The treating solution is placed, or spotted, across the perforations or producing interval, and
is allowed to set for a fixed period of time. The treatment load is then recovered.
Agitation can be accomplished by one of three methods. One technique is to spot the treating
solution across the perforation, allow a short soaking period, and then wash it back through the
annulus by reciprocating or rotating the work-string. Another method is to pressure-up, staying
below fracturing pressure, and then release the pressure very quickly. This action is sometimes
referred to as "backsurging the perforations." The third method is to spot the treating solutions
across the perforations, allow it to soak for awhile, and then swab back through either the casing or
the tubing, or jet the treatment back with nitrogen.
With any of these techniques, the treating solution may have to be applied several times before the
formation is opened for fluid entry. The use of several wellbore cleanout applications allows for a
matrix or fracturing acidizing treatment to be performed without fear of pushing unwanted plugging
material into natural formation permeability.

Scale Removal
Prior to production, well fluids are in a natural undisturbed state. As production occurs, it creates a
chemical disturbance and physical imbalance within the formation. The environment changes as a
result of pressure drop, which allows dissolved gases to come out of solution.
These changes destroy the state of equilibrium, thereby creating the initial stages of scale
development as the salts reestablish equilibrium under new conditions. Scale can restrict or block
tubing, flowlines, surface equipment, downhole equipment, the wellbore, and perforations, and thus
completely choke off production.
Scale formation is usually a long and dynamic process with more than a single cause. One direct
cause of scale is the mixing of incompatible waters. Other causes include corrosion leading to iron
precipitation, and abrupt drops in pressure or temperature.

Types
Scale can be divided into three broad classes, based on their solubility in water, their reaction with
HCl, or their removability with HCl. The classifications are (1) watersoluble, (2) acid-soluble, and (3)
acid-insoluble. These classifications are simplified, because pure calcium sulfate or pure calcium
carbonate is rarely deposited. Although scale deposit is usually a mixture of one or more major
inorganic components plus corrosion products, congealed oil, formation fines, paraffin, and other
impurities, these classes are adequate for field analysis. Common scale deposits are listed in Table
1.

Scale Type

Chemical Formula

Mineral Name

Water Soluble

NaCl

Sodium Chloride (salt)

Calcium Carbonate

CaCO3

Calcite

Iron Carbonate

FeCO3

Siderite

Iron Sulfide

FeS

Trolite

Acid Soluble Deposits

Iron Oxides

Fe3O4

Magnetite

Fe2O3

Hematite

Mg(OH)2

Brucite

Calcium Sulfate

CaSO 2H2O

Gypsum

Calcium Sulfate

CaSO4

Anhydrite

Barium Sulfate

BaSO4

Barite

Strontium Sulfate

SrSO4

Celestite

Barium Strontium Sulfate

BaSr(SO4)2

Magnesium Hydroxide
Acid Insoluble Deposits

Table 1: Common scale deposits.

Identification of Scale: One of the most important factors in dealing with scale is accurate
identification of the material being deposited. There are two fundamental means of identifying scale:
laboratory testing and fluid identification.
Laboratory Testing: The primary means of identifying scale in the laboratory are
X-ray diffraction: This method is the fastest laboratory method available and requires the smallest sample.
chemical analysis: The scale sample is decomposed and dissolved in chemical solution, and
its various compounds are then analyzed by standard techniques of titration or precipitation.
Field Identification: The following three-step procedure can help make a preliminary field identification.
1. Add scale to water. If it dissolves, it is probably sodium chloride.
2. Add scale to 15% HCl.
a. If it bubbles vigorously and dissolves, it is probably calcium carbonate.
b. If it bubbles slowly and turns the acid yellow, it is probably iron
carbonate.
c. If it bubbles and smells like rotten eggs, it is iron sulfide.
d. If it dissolves slowly without bubbling and turns the acid yellow, it is
probably iron oxide.
e. If it dissolves slowly in acid with no bubbles and does not color the
acid, it may be magnesium hydroxide.

3. If it does not dissolve, it is one of the acid-insoluble scales. If it is gypsum, you can scrape it or
dent it; it also has the monoclinic characteristic of crystal structure. The crystals are usually fairly
large.
Anhydrite is harder than gypsum and the crystals are harder to see. They are both slowly soluble in hot acid. Barium
sulfate and strontium sulfate are very heavy, usually dark, with very fine crystals of almost any color.

Sand or silicates (formation) may often be identified by its grain structure but may look much like
the above. It is lighter in weight than barium or strontium sulfate.

Scale Removal
Acid-soluble scales include the following:
calcium carbonate
iron carbonate
iron sulfide
iron oxides
calcium hydroxide
These scales can be removed by one or more of the following solutions:
15% HCl with no surfactants HCl, containing only corrosion inhibitor to lower the corrosion rate, is
a basic acid (without surfactants). It is not normally used for scale removal.
15% HCl with 0.15% penetrating agent This acid solution contains 1.5 gal of a
penetrating agent per 1000 gal acid. Penetrating agents lower the surface tension of
the acid solution, increasing the ability of acid to wet and spread. This solution is very
effective on scales containing small amounts of iron. It can be used for all acid-soluble
scale when treating surface, gathering lines, or any other system where the solution
does not enter the formation.
15% HCl with sequestering agents This solution is used to prevent the precipitation
of iron hydroxide. It is effective in handling scale that contains iron (Fe+2 and Fe+3)
compounds. The HCl dissolves the iron scales. Sequestering agents (see Section 4.3)
prevent iron precipitation by forming a complex with the iron, thus keeping it in
solution and preventing secondary precipitation. With most iron scales, a stronger acid
strength may also be considered.
10% acetic acid The greatest asset of this acid in scale removal is that it does not
damage "chrome," or alloy steel, found in downhole pumps. Calcium carbonate scales
readily react with this acid, as do most other scales.
15% HCl -aroma tic dispersion This acid dispersion contains an aromatic solvent,
acid, and an emulsifying surfactant.
Acid-insoluble scales include
calcium sulfates
barium sulfate
strontium sulfate
barium strontium sulfate
Acid-insoluble calcium sulfate can be removed by chemical methods; barium sulfate and strontium sulfate cannot.
There are two removal techniques for calcium sulfate (gypsum); one employs carbonate and
hydroxide converter solutions, the other organic acid salts.

Carbonate and hydroxide converter solutions convert gypsum (CaSO4 2H2O) to calcium carbonate,
which is acid soluble. However, these converting properties are severely retarded when dense
laminated gypsum scale is encountered. Because of a lack of penetration, repeated application may
be necessary. In some cases, hydroxides form a sludge which can be pumped from the well; in
others, acid must be used to remove the reaction precipitant. Although hydroxides have proved fairly
effective in some wells, in others they tend to decrease in effectiveness with re-treatment. This is a
result of a buildup of calcium hydroxides sludge within the interstices of the gypsum and on the
surface, limiting solvent penetration.
With carbonate and hydroxide converter solutions, an acid stage is required to remove the reaction
precipitate. These jobs are usually conducted in four stages, requiring a considerable amount of time.
Organic acid salts react with gypsum to form a reaction precipitate which tends not to adhere to the
gypsum but to form a water-dispersible sludge. The reaction precipitant has a tendency to slough
away from the gypsum surface, thereby increasing solvent penetration. Also, since the reaction
product does not adhere tightly and is readily dispersible in water, an acid stage usually is not
needed to remove the sludge. However, should it become necessary to remove the sludge, it is
soluble to the extent of 1.2 lb/gal of 15% HCl.
When barium sulfate or strontium sulfate deposition has been diagnosed, the most practical solution
is to eliminate the cause. For instance, barium sulfate is most often formed by the mixing of native
formation water with injection or produced waters from another interval one of which is high in
barium while the other is high in sulfates and isolating these waters can prevent the problem. The
presence of barium sulfate usually indicates either a lack of zone isolation or faulty casing.
The removal of barium sulfate or strontium sulfate is an extremely difficult problem. Available
chemicals that remove small amounts of these sulfates are usually inefficient and expensive. These
deposits are best removed mechanically, by jetting or running a bit and scraper.

Scale Prevention
Several methods of preventing scale formation are available. The two most successful and widely
used methods are (1) the gradual placement of water-soluble polyphosphates (solid scale inhibitors)
into the formation and (2) the use of liquid scale inhibitors.
Solid Scale Inhibitors: Solid polyphosphates are placed into the formation during water-base
fracturing treatments. After placement, the polyphosphates dissolve very slowly in the water
produced by the well. The amount of phosphate dissolved per unit volume of water produced is small
but usually suffices to control scale formation. When placed properly, it can give long-term
protection.
One argument against the use of polyphosphates is the placement method itself, which is not only
relatively expensive but also not always possible. The material's reversion to inactive calcium
orthophosphate (calcium phosphate scale) in the presence of HCl also prohibits the use of acid
treating solutions before and after its placement.
Liquid Scale Inhibitors: These inhibitors, including organic phosphates and synthetic organic
polyelectrolytes, have also been widely used for scale control. Successful scale control depends on
the adsorption of the inhibitor on the rock matrix and slow desorption into the produced fluids. The
adsorption properties of inhibitors vary. Many scale inhibitors are effective in preventing scale but
have poor adsorption properties, which makes frequent re-treatment necessary.
Figure 1 shows a liquid organic scale inhibitor that effectively prevents scale deposition in formation

waters.

Figure 1

Its good adsorption properties provide long-lasting protection.

Placement of liquid scale inhibitors may be accomplished in three ways: (1) by the matrix squeeze
technique, (2) as an additive in stimulation treatments, and (3) by metering the liquid into water
injection systems.

Paraffins and Asphaltenes

Paraffin And Asphaltene
Paraffins are organic deposits caused by changing wellbore conditions that upset the chemical
equilibrium so that various materials in the crude oil precipitate out of solution. These materials
separate and deposit a waxy material called paraffin (in some cases asphaltene). Figure 1 illustrates
the development of paraffin in a flowing well.

Figure 1

Paraffin, usually deposited in the wellbore, extends to the top of the well and into flowlines from a
depth where the formation temperature is approximately the same as that at which the oil became
saturated with the separated wax.
Asphaltene deposits, usually hard and brittle, occur at the bottom of the wellbore adjacent to the
producing formation wall.
The buildup of paraffin or asphaltene can completely plug up the oil flow in a producing well if the
problem is ignored or left untreated.

Properties
Paraffins are either normal, branched, or cyclic alkanes with the chemical formula CnH2n+2. Paraffin
deposition is difficult to inhibit because these hydrocarbons are generally very inert and therefore
resistant to attack by acids, bases, and oxidizing agents.
Crude paraffin deposits are made up of individual alkanes ranging from a carbon chain length of 20
with a melting point of 98 F to a chain length of 60 with a melting point of about 215 F. Crude wax
or paraffin deposits consist of very small crystals that tend to agglomerate and form granular wax
particles about the size of ordinary table salt grains. Deposited paraffin may also contain gums,
resins, asphaltic material, crude oil, sand and silt, corrosion products, scale, and often water.
The primary cause of wax separating from crude oil is loss of solubility, often resulting from changing
environmental conditions that disturb solution equilibrium. Factors affecting this equilibrium include
temperature and pressure changes, evaporation, and loss of dissolved gases. Those paraffins having
the highest melting point and molecular weight are the first to separate from solution. The quantity
of lower melting point waxes with smaller molecular weights to separate from solution depends on
how much the oil's equilibrium changes prior to deposition that is, the solubility of different

paraffin waxes in specific crude oil at a given temperature decreases with an increase in melting
point and molecular weight.
Asphaltenes are black carbonaceous petroleum components characterized by relatively high
molecular weights and insolubility in light paraffinic hydrocarbon solvents, such as pentane and
petroleum ether. The asphaltene fraction of petroleum is made up of polycyclic, condensed aromatic
rings with few side chains. These compounds are considered polar materials due to the presence of
sulfur, nitrogen, oxygen, and complex metals.
Asphaltenes occur in many crude oils in the form of colloidally suspended solid particles. Asphaltene
precipitation takes place when crude oil loses its ability to disperse the particles. Asphaltene stability
is dependent on crude oil composition and the nature of reservoir rock surface. The balance that
holds them in a stable suspension is dependent on the same conditions that cause paraffin to
separate from crude.
Pour point and cloud point measurements refer to crude oil's ability to hold paraffin in solution. Cloud
point is the temperature at which paraffin begins to come out of solution. This point is visible in clear
solutions as a slight cloudiness. Since the cloud point of a dark crude oil is not visible, instrumental
methods may be used to obtain crude oil cloud points.
If crude oil is slowly cooled below the cloud point without agitation, small wax crystals gradually form
an interlocking network which inhibits flow. The pour point is reached when oil ceases to flow.

Factors Affecting Deposition

Temperature: When crude oil cools, it loses its solubility, and can no longer keep the particles in
suspension. Paraffin solidifies, its particles settle and accumulate into waxy deposits.
Pressure: Pressure holds dissolved gases and volatile constituents in solution and helps maintain the
fluid at formation temperature. Obviously, it is impossible to produce oil without having a
considerable pressure drop; two factors, then, work simultaneously. As pressure drops, the
temperature drops, because gases evolve and expand, and heavier components settle out, forming
paraffin.
Loss of Volatile Constituents: Loss of the lighter constituents of the crude definitely reduces the
quantity of paraffin the oil can hold in solution. The reduction in the volume of oil results in less
solvent available to dissolve the same amount of wax.
Suspended Particulate Material: Evidence shows that as paraffin begins to separate when
temperature drops, formation fines such as sand and silt speed this process.
Co-produced Water: Although water has no direct effect on wax solubility in oil, it may reduce acute
paraffin problems in wells that began producing it in appreciable amounts. One possible explanation
is that steel tubing will water-wet, thus reducing the tendency for paraffin to deposit.
Conditions Favoring Paraffin Deposition: Even though wax may separate from crude oil, the produced
paraffin does not necessarily deposit on the tubular goods and other equipment. It seems logical, in
fact, for the wax to remain suspended in the crude oil itself. This ideal situation often exists, and in
wells producing a very waxy crude, few paraffin problems occur. Some factors that cause paraffin
accumulation in a well are
alternate coating of the pipe and draining of the oil. When a surface is intermittently coated with oil, the
thin film left on the pipe surface is too thin and its movement too slow to carry away wax particles.
presence of only an oil film contact with the pipe while the well is flowing.

contact of the oil with an unusually cold surface, such as in oil production through aquifers;
this can cause paraffin crystals to grow directly on the pipe wall. (It is estimated that heat
loss by conduction from a pipe in contact with water is approximately eight times greater than
that which would occur in contact with air or dry earth.)
rough pipe surfaces, which often provide excellent sites for paraffin deposition.
electrical charges on various materials in the crude oil, which tend to promote migration of
the separated waxes to the pipe walls.

Removal and Control Techniques

There are basically three methods for removing and/or controlling paraffin deposition: mechanical,
thermal, and chemical.
Mechanical Methods: Several mechanical techniques remove paraffin deposition in tubing, flowlines,
and pipelines. These include
rod scrapers
wireline scrapers
flowline scrapers
balls, pigs, and/or soluble plugs
free-floating pistons
hollow rods for circulating hot fluids
The major advantage of using mechanical methods is that positive cleaning is assured. There are some
disadvantages, however. Application is rather limited because of the time, expense, personnel, and special
equipment involved. If tools are lost in the hole, a fishing job may be necessary.
One preventive mechanical method is the use of smooth-surface pipe. The internal surface of pipe
can be made smooth by plastic coating or removal of mill scale. Smooth pipe surfaces do not prevent
paraffin deposition, but in most cases they slow the process.
There are three widely used plastic coatings for pipe: phenol-formaldehyde, epoxy phenolic, and
polyurethane.
Phenol-formaldehyde has been in use longest, and is the most widely used coating in oilfield tubulars. It is
a highly crosslinked polymer, with excellent resistance to temperature, chemicals, and infusion by small
molecules (H2O, CH4, H2S). Its surface is extremely smooth and has a high gloss. It is a brittle plastic which
becomes extremely rough when abraded by sand.
Epoxy phenolic is the second most widely used material in oilfield tubulars. Less resistant to
temperature, chemicals, and infusion than phenol-formaldehyde, its surface is almost as
smooth, but it is less brittle and does not deform as badly when abraded by sand.
Polyurethane is a relative newcomer, and the least crosslinked of the three. It has lower
temperature, chemical, and infusion resistance than the other two, and its surface is not quite
as smooth as phenol-formaldehyde. Polyurethanes are quite flexible, and although (like the
other two materials) its film thickness is reduced by sand abrasion, the plastic is only slightly
deformed and maintains most of its smoothness.

Plastic-coated pipe either works extremely well or is a dismal failure. Numerous examples of both cases can be
found in oil-field operations. Given the descriptions above, it is apparent why particular plastics may perform well or
not, depending on their application and the experience of the particular oil operator. In areas where the oil stream
contains no sand or other abrasive solids, plastics effectively prevent paraffin buildup. When brittle plastics (such as
phenol-formaldehyde) are used in wells containing abrasive materials, the plastic deforms badly, leaving a rough,
abraded surface which only invites severe paraffin deposits.
There are three important factors regarding the use of plastic coatings in the prevention/reduction of
paraffin deposition:
Paraffinic plastics such as polytetrafluoroethylene, polyethylene, and polypropylene, no matter how
smooth, do not reduce paraffin buildup. In fact, because they are paraffins themselves, they cause paraffin
buildup by either hydrogen bonding or a phenomenon closely resembling cocrystallization.
Smooth, nonparaffinic plastics reduce paraffin deposits only as long as they remain smooth.
Wirelines, fishing tools, piano wire equipment, and other workover or measuring devices
destroy the effectiveness of the plastic coating by damaging the smooth surface.
All metal surfaces (nipples, valves, etc.) must be coated with plastic. One uncoated nipple
can effectively choke the well.
Thermal Methods: All thermal techniques use heat to remove the paraffin. Methods in current use include
bottomhole heaters
hot oil, a common method which melts the waxy accumulation; lease crude oil is run
through heat exchangers and pumped into the well at temperatures greater than 300 F
steam, which melts the paraffin so that it can be flowed with the oil from the well
heat-liberating chemicals (such as magnesium bars) followed by HCl; these produce
chemical reactions which release heat, thereby melting the paraffin
These approaches ensure paraffin removal. In order to prevent further deposition, the working temperature must be
maintained above the melting point of the wax.
Thermal techniques have some disadvantages. Bottomhole heaters require special equipment and
consume additional power. Hot fluids pose a danger to personnel, usually require the use of pump
trucks, and sometimes dissolve the paraffin only to redeposit it deeper than before.
Chemical Methods: Chemical methods for paraffin control are separated into two distinct categories:
solvents and inhibitors.
Solvents: The best solvents for paraffin removal are too toxic, hazardous to handle, or damaging to
refinery catalysts.
Two such chemicals are carbon disulfide (CS2) and carbon tetrachloride (CCl4).
Aromatic hydrocarbons, such as xylene and toluene, are acceptable solvents and dissolve both wax
and asphaltenes; they are suitable for crude paraffin deposits. Solubility of paraffin in xylene is
shown in Figure 1 .

Figure 1

Inhibitors: A large number of paraffin inhibitors are also available. Explanations of their effectiveness
vary widely. Some are said to be dispersants; others, wax crystal modifiers; and still others claim to
alter the surface conditions of equipment. Most paraffin inhibitors also contain paraffin solvent as the
carrier.
Surfactants: Of the vast number of paraffin chemicals available, wetting agents and dispersants constitute
the highest percentage. Wetting agents are designed to work much like plastic pipe: the chemical reacts
with produced water or by itself and forms an aqueous film on the pipe surface. This surface film retards
paraffin deposition by covering the sites where paraffin can adhere. However, it is very difficult to get the
pipe surfaces water-wet and keep them that way. The theory behind the dispersant approach is that certain
chemicals tend to cause the crude paraffin molecules to repel each other as well as the metal surface.
Both wetting agents and dispersants have seen some success. The most serious drawback to
their use is that no supplier can be absolutely certain of their effectiveness. The operator has
to decide whether to continue a particular paraffin removal program or to run the trial and
error method with all available chemicals and hope to find one that is satisfactory.
Crystal Modifiers: Generally, crystal modifiers have many of the same drawbacks as
surfactants. Their effectiveness appears to be somewhat unpredictable. With the proper
placement technique, however, these chemicals seem to work fairly well and to show the most
promise among chemical inhibitors. When viewed under a microscope, they appear to modify
the wax crystals precipitating from a wax solution ( Figure 2 , paraffin crystal clustering and
Figure 3 , effect of inhibitor on paraffin crystals).

Figure 2

Figure 3

Crystal modification occurs for one of two reasons: (1) the chemical comes out of solution at
a temperature slightly higher than that required for paraffin precipitation, causing nucleation,
or (2) the modifier comes out of solution and co-crystallizes with the paraffin crystals. In
either case, the normal crystal habit of paraffin is deformed sufficiently to inhibit further
growth. This causes the crude oil to become saturated with much smaller paraffin crystals
than normal with less tendency to adhere to pipe surfaces. Although they do not completely
cure the paraffin problem, crystal modifiers offer the best chemical approach for reducing its
severity.

Method Of Diluting Hydrochloric Acid

The degrees Baume (Be) or specific gravity (sp gr) of the concentrated HCl must be known in order
to accurately mix HCl at 15% or any other strength. The first step in mixing HCl to a given strength
is to take the degrees Baume or specific gravity of the concentrated HCl. These steps in order are
1. Put a sample of concentrated HCl to be tested in a 250-ml graduate cylinder and take the degrees
Baume (or specific gravity) reading with a hydrometer. Also, take the temperature of the sample.
2. Correct the degrees Baume or specific gravity to the standard temperature of 60 F by
using the temperature corrections in Table 1 (below).
3. Convert the corrected degrees Baume or specific gravity to HCl percentage by using Figure
1 (conversion of degrees Baume or specific gravity to percentage of HCl.

Figure 1

)
4. Use the dilution charts in Figure 2 and Figure 3

Figure 3

(Acid dilution charts) to determine how much concentrated HCl is required to mix 1000 gal of
HCl to any desired strength. Most strengths are shown on the chart; if a desired strength is
not shown, use Formula 11 given in this text segment (below).

Figure 2

Different acid strengths may remain stratified in the tank and cannot be expected to mix themselves.
The degrees Baume (or specific gravity) of concentrated HCl should be taken as often as necessary
to ensure that the weight being used to calculate the dilution is as accurate as possible and that it
never is more than 0.50 Be (0.005 sp gr) in error.
[Use this table to correct the degrees Bauma or specific gravity readings of acid to the standard
temperature, 60 F. Choose the B or specific gravity reading nearest the observed reading obtained
from the hydrometer reading.]

B
(b)

Correction
factorc
(Be') for each F

sp gr
(b)

Correction
factorc
(sp gr) for each F

0.01

1.014

0.0001

.02

1.028

.0001

.02

1.043

.0002

.02

1.058

.0002

10

.03

1.074

.0002

12

.03

1.090

.0002

14

.03

1.107

.0003

16

.03

1.124

.0003

18

.04

1.142

.0003

20

.04

1.160

.0003

22

.04

1.179

.0004

24

.04

1.198

.0004

aBaum gravity is a measurement of fluid weight based on specific gravity. The Baum gravity (B)
applies to liquids heavier than water. It is calculated from specific gravity through the relationship
Table 1 : Temperature corrections for HCl hydrometer readings:

B = 145 The Baume' gravity of 15% HCl acid is 10.1.

b

Degrees Baume' or specific gravity nearest the observed reading.

Correction factor for temperature(F): These temperature corrections are based on information
appearing in the International Critical Tables.
c

Above 60 F: If the observed temperature is above 60 F, add the amount shown above for every 1
F above 60 F.
Below 60 F: If the observed temperature is below 60 F, subtract the amount shown above for every
1 F below 60 F.

HCl, %

oBaume

Weight of
specific
gravity

Solution,b
lb/gal.

HCl/gal., lb.

2.11

1.015

8.47

0.25

3.52

1.025

8.55

0.43

7.5

5.23

1.037

8.65

0.65

10

6.89

1.050

8.76

0.88

15

10.10

1.075

8.97

1.35

15.4

10.36

1.077

8.98

1.38

19.8

13.10

1.099

9.17

1.82

28

18.05

1.142

9.52

2.67

31.45

20.0

1.160

9.67

3.04

35.21

22.0

1.179

9.83

3.46

aAll figures in this column are rounded to the third decimal point.
bAll figures here are rounded to the second decimal point.
Table 2: Physical constants of acid solution strengths.

Calculating Acid Solution Ingredients

Because HCl is the primary base fluid for many acidizing systems, the definition of acid strength
needs to be well understood. Strength, or concentration, of HCl is conveniently expressed as
percentage by weight of the active materials in the acid solution. For example, a 15% HCl solution
means that for each 100 lb of solution, 15 lb of hydrogen chloride gas is dissolved in 85 lb of water.
Concentration is expressed by using the specific gravity of the liquid or solution. The concentration is
just a measurement of the relative weight of the material in relation to the weight of an equal
volume of pure water. Pure water weighs 8.34 lb/gal at 60 F.
Table 2 lists the physical constants for some of the most frequently used HCl acid strengths.
The percentages and specific gravities from Table 1 and Table 2 satisfy what is needed in Equation
11 for determining concentrated HCl volume to transpose acid strengths. Since equal weights of HCl
are involved in both weak and strong acid solutions, Equation 11 is used most often to determine the
amount of ingredients for a HCl solution.
(vol. of strong acid) x (% strength of strong acid)
x (sp gr of strong acid) = (vol. of weak acid)
x (% strength of weak acid) x.(sp gr of weak acid) (11)
This formula is symbolized as:
Vs x %s x sp grs = Vw x %w x sp gr
(12)
Therefore,
Vs = (Vw x %w x sp grw)/(%s x sp grs)
(13)
For example, if a job specifies 1000 gal of 15% HCl, volume of 200 o Be HCl (31.45%) can be calculated:
Vs = (1000 x 0.15 x l.075)/(0.3l45 x 1.16)
= 161.25/0.36482
= 442 gal
Volume of strong acid = 442 gal of 200 Be HCl
Volume of water = 1000 - 442 = 558 gal water *
Water - inhibitor - additives = required water
* When obtaining the volume of water required for proper dilution of concentrated HCl, inhibitor and additives are
considered part of the dilution water. Therefore, whatever determined volume of additives is used in the acid
treatment should be subtracted from the volume of dilution water required.
Once you have solved the dilute acid calculations, most service company data books can provide a
listing of calculated volumes of stock acid and water volumes necessary for a 1000 gal final volume
of frequently used HCl strengths. Although the volume of acid and water totals more than 1000 gal,
only 1000 gal of dilute acid will result after mixing. Chemical contraction of the two liquids results in
this phenomenon. Service company listings generally makes no allowance for subtraction of inhibitor
and additive volumes in the listed amounts of water. This subtraction can be solved to determine the
correct amount of dilution for the HCl solution.

Loading and Mixing the Acid Solution

The acid desired for the treatment should always be within 1% of the desired strength. To ensure
that concentration is uniform throughout the tank, the HCl, dilution water, and all additives must be
thoroughly mixed together. A good method for loading and mixing follows.
1. Load the volume of fresh water less required additives into the acid tank.
2. Add the required inhibitor and additives separately. Never mix additives in the same
container before adding to the fresh water. If chemical reactions should occur, emulsion tests
for proper additive selection would become useless.
3. Add the concentrated HCl required to the volume of water and additives already in the acid
tank to arrive at the total volume. Keep the acid-loading hose end above the fluid level to aid
in mixing the water, additives, and acid.
4. After all the required volume is placed in the acid tank, mix it further by circulating it with a
pump.
Keep the following general rules in mind:
Use a gauge stick to measure the volumes needed. If the total volume falls short of the predetermined
mark, add more water.
Measure quantities of additives using a loading system or 5-gal container.
Prepare HCl-HF mixtures by diluting concentrated HCl and liquid HF or by adding ammonium
bifluoride with water and then concentrated HCl. The ammonium bifluoride dissolved in water
releases HF when mixed with HCl.
Fresh water should always be used for mixing HCl-HF. Water containing sulfate, calcium,
sodium, or potassium ions should not be used because the precipitate formation can reduce
permeability in the reservoir.
Data is available from service companies for determining the amounts of concentrated HCl, water, and ammonium
bifluoride (NH4HF2) needed to prepare most HCl-HF mixtures, Because some of the HCl is used to change
ammonium bifluoride to HF, the HCl concentration required is greater than the total final concentration of the
mixture.
The following are needed to prepare 1000 gal of 12% HCl-3% HF:
HCl (959 gal of 15.4%)
NH4HF2 (384 lb)
With the above information and physical constants of HCl given in Table 2 , required volumes of concentrated HCl
and fresh water can be determined.
Mixing HCl-HF solutions requires rapid agitation or circulation of the water to facilitate the dissolving
of the NH4HF2 and proper mixing of all acid ingredients. Use the following procedure to prepare HClHF:
1. Place the required volume of dilution water in the acid tank.
2. While agitating, add the remaining ingredients in this order to allow complete
mixing or dissolving of the additives:
(a)inhibitor, (b) additives, and (c) NH4HF2.

3. Add the proper amount of concentrated HCl and agitate the final mixture until
uniform.
Using the gauge stick, follow the same measuring procedures for loading HCl.

Testing Acids
The use of specific gravity or degrees Baume measurements for determining acid strength is subject
to error. Only the total amount of dissolved solids is measured. If an HCl solution contains salt, the
density of this solution will indicate a higher acid strength because the total amount of dissolved
solids has been increased by other ions dissolved in the solution.
Here, then, is the best, most common method of determining acid strength: a simple acid-base
titration. This method can be used in the laboratory or in the field. For mixtures of HCl-HF, titration
can also be used to determine total acid concentration.
To determine acid strength by titration, the following equipment and reagents are needed:
a syringe (1 ml or 5 ml)
a beaker (150 ml)
stirring rods (if available, use instead of swirling)
distilled water
2N sodium hydroxide (NaOH) solution
phenolphthalein indicator solution (dropper bottle)
The procedure for determining HCl strength is
1. Place 1 ml of acid to be tested into a 150-mi beaker. Dilute with distilled water to about 50 ml, and add 2
drops of phenolphthalein indicator to the acid sample.
2. Using a l-ml or 5-ml syringe, add the 2N NaOH by drops, while swirling the acid sample,
until the acid turns pink. Record the number of ml of 2N NaOH used.
3. Determine the percentage of HCl in the acid from Figure 4 (Determination of HCl strength
with NaOH ).

Figure 4

4. Try to remove all air bubbles that may form in the syringes.
This procedure gives the approximate percentage of HCl (plus or minus 1%). It is ideally suited for field use.