Chapter 54

Acidizing
A.W. Coulter Jr.,
A.R. Hendrickson,
S.J. Martine2.u. of

Dwell-Schlumberger
Dowell-Schlumberger
Tulsa

Introduction
The use of acids to stimulate or to improve oil production from carbonate reservoirs was first attempted in 1895.
Patents covering the use of both hydrochloric and sulfuric acids for this purpose were issued at that time. Although
several well treatments were conducted, the process
failed to arouse general interest because of severe corrosion of well casing and other metal equipment, The next
attempts to use acid occurred between 1925 and 1930.
These consisted of using hydrochloric acid (HCl) to dissolve scale in wells in the Glenpool field of Oklahoma
and to increase production from the Jefferson Limestone
(Devonian) in Kentucky. None of these efforts were successful and acidizing once again was abandoned.
The discovery of arsenic inhibitors, which allowed HCl
to react with the formation rock without seriously damaging the metal well equipment, revived interest in oilwell
acidizing in 1932. At that time, Pure Oil Co. and Dow
Chemical Co. used these inhibitors with HCl to treat a
well producing from a limestone formation in Isabella
County, MI. Results of this treatment were outstanding.
When similar treatments in neighboring wells produced
even more spectacular results, the acidizing industry was
born.
Throughout the years following those early treatments,
the acidizing industry has grown to one using hundreds
of millions of gallons of acid applied in tens of thousands
of wells each year. Technology has developed with increasing rapidity, and many changes and innovations have
been made to improve the effectiveness of acidizing treatments. Because of new techniques of application and development of additives to alter the characteristics of the
acid itself, acidizing has become a highly skilled science.
A knowledge of available materials, chemical reactions
Authors of the OrigInal chapter on this topic I the 1962 editlon Included th!s aulhor
(deceased). P E. Rlzgerald. and Harold E Staadt

at treating and well conditions, reservoir properties, and

rock characteristics are required to design an effective and
efficient acidizing treatment. Since it is beyond the scope
of this text to cover all aspects of acidizing in detail, this
discussion will be limited to a general description of materials, techniques, and design considerations. A bibliography is provided for those requiring a more detailed
discussion of a particular subject. Also, the major well
stimulation companies providing acidizing services offer
literature and technical assistance for problem analysis and
treatment design.

General Principles
The primary purpose of any acidizing treatment is to dissolve either the formation rock or materials, natural or
induced, within the pore spaces of the rock. Originally,
acidizing was applied to carbonate formations to dissolve
the rock itself. Over a period of time, special acid formulations were developed for use in sandstone formations
to remove damaging materials induced by drilling or completion fluids or by production practices.
There are two primary requirements that an acid must
meet to be acceptable as a treating fluid: (1) it must react
with carbonates or other minerals to form soluble products, and (2) it must be capable of being inhibited to prevent excessive reaction with metal goods in the well. Other
important considerations are availability, cost, and safety in handling. While there are many formulations available, only four major types of acid have found extensive
application in well treatments: hydrochloric, hydrofluoric,
acetic, and formic acids.
Hydrochloric

Acid (HCI)

An aqeuous solution of HCl is most commonly used for

acidizing treatments, for reasons of economy and because
it leaves no insoluble reaction product. When HCl is

PETROLEUM

54-2

In

3500

T
I

3000

/
16

ENGINEERING

HANDBOOK

pumped into a limestone formation, a chemical reaction

takes place, producing calcium chloride, CO*, and water.
This reaction is represented by the following equation:

I4
12
IO
n
b
4
2
0

4
STRENGTH

I2
OF ACID,

16

20

PERCENT

BY

24
WEIGHT

Fig. 54.1-Solution of limestone in acid.

TABLE
%

HCI

1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
12.00
13.00
14.00
15.00
16.00
17.00
18.00
19.00
20.00
21.00
22.00
23.00
24.00
25.00
26.00
27.00
28.00
29.00
30.00
31.00
32.00
33.00
34.00
35.00
36.00
37.00
38.00
39.00
40.00
41.00

54.1~-HYDROCHLORIC

ACID DENSITY

SpecificGravity' "Baume**
1.0048
1.0097
1.0147
1.0197
1.0248
1.0299
1.0350
1.0402
1.0447
1.0500
1.0550
1.0600
1.0646
1.0702
1.0749
1.0801
1.0849
1.0902
1.0952
1.1002
1.1057
1.1108
1.1159
1.1214
1.1261
1.1310
1.1368
1.1422
1.1471
1.1526
1.1577
1.1628
1.1680
1.1727
1.1779
1.1827
1.1880
1.1924
1.1963
1.2008
1.2053

145

0.7
1.4
2.1
2.8
3.5
4.2
4.9
5.6
8.2
6.9
7.6
8.2
8.8
9.5
10.1
10.8
11.4
12.0
12.6
13.2
13.9
14.5
15.1
15.7
16.3
16.9
17.5
18.0
18.6
19.2
19.8
20.3
20.9
21.4
21.9
22.4
22.9
23.4
23.8
24.3
24.7

lbmlgal
8.377
8.418
8.460
8.501
8.544
8.586
8.629
8.672
8.710
8.754
8 796
8.837
8.876
8.922
8.962
9.006
9.045
9.089
9.132
9.171
9.218
9.261
9.303
9.349
9.385
9.433
9.478
9.523
9.563
9.609
9.663
9.694
9.738
9.777
9.820
9.860
9.924
9.941
9.974
10.011
10.049

AT 6OF
psilft
depth
0.4351
0.4372
0.4392
0.4415
0.4437
0.4459
0.4482
0.4504
0.4524
0.4547
0.4568
0.4590
0.4610
0.4634
0.4654
0.4677
0.4698
0.4721
0.4743
0.4764
0.4788
0.4810
0.4832
0.4855
0.4876
0.4899
0.4922
0.4946
0.4967
0.4991
0.5012
0.5035
0.5057
0.5078
0.5100
0.5121
0.5144
0.5163
0.5180
0.5199
0.5219

One thousand gallons of 15% HCI will dissolve approximately 10.8 cu ft (1,840 lbm) of limestone. It will liberate approximately 7,000 cu ft of CO1 , measured at
atmospheric conditions, and produce 2,042.4 lbm of calcium chloride. This salt is dissolved in the original water
of the acid solution, plus 39.75 gal of water formed during the reaction. The specific gravity of this solution will
be 1.181 (20.4% calcium chloride). While 15 wt% HCI
has been the most commonly used, concentrations of 20
and 28% have become extremely popular over the past
2 decades. Regardless of the acid strength used, the reaction is the same and equivalent amounts of carbonate rock
are dissolved. For example, 10,000 gal of 3% HCl solution will dissolve the same amount of rock as 1,000 gal
of 28% HCl. Fig. 54.1 shows the effect of acid concentration on the amount of limestone dissolved. The main
differences between the two solutions are their reaction
rates (or spending times) and their physical volumes.
Although lower concentrations of acid have greater
equivalent volumes, their reaction times and depth of
penetration into the reservoir, from the wellbore, are considerably less than those of the higher-strength solutions.
Reaction rates and penetration will be discussed later.
Similar reactions occur when dolomite or impure limestone is treated with HCI. Dolomitic lime contains a large
percentage of magnesium combined as calcium magnesium carbonate. Although it reacts more slowly, this mineral also dissolves in HCl, and the resulting magnesium
chloride is soluble in the spent acid. Other impurities occurring in limestone and dolomite are often insoluble in
acid, and if appreciable percentages of such components
are present, special additives must be included in the acid
solution to ensure their removal.
HCl ordinarily is manufactured in concentrations of 32
to 36 wt% HCl and is diluted at service company stations
to 15, 20, or 28% for field use. The concentrated acid,
the various chemical additives, and water are mixed in
the tank truck used to haul the acid to the wellsite. Table
54.1 lists the weights of various concentrations of HCI.
These data are useful in calculating mixing proportions
for acid dilution, using the following equation:

vda

cda

7 da

vl-0 =
Cca(HCI)Yca '

where
V/da =
cdd =
?'du =
V,, =
Cccr(HCI)=
ycO =

final volume of dilute acid,

desired concentration of dilute acid,
specific gravity of dilute acid,
volume of concentrated acid required,
percent of HCI in concentrated acid, and
specific gravity of concentrated acid.

Approximate proportions of concentrated acid and water

required for dilution are shown in Fig. 54.2.

54-3

ACIDIZING

Determination of acid strength can be estimated in the

field using either a hydrometer or a field titration kit. The
accuracy of hydrometer readings depends on the care and
technique used by the field engineer. Both the hydrometer and the glass cylinder in which the test is made should
be free from oil or dirt. The spindle should float freely
in the acid, and all readings should be made at the lowest
level of the acid meniscus. The temperature of the acid
sample should be taken and the hydrometer reading corrected to 60F.
Determination of acid strength by titration is simplified
by the use of 0.59 N standard sodium hydroxide solution.
If a 2-mL sample of the acid is titrated with this standard
solution to a methyl orange end point, the burette reading (milliliters of sodium hydroxide used) will be equal
to the acid strength (percent HCI).
Acetic and Formic

FORMULA
FOR
CONCENTRATION:

MIXING

ACID

IN ANY

DESIRED

VOLUME OF STRONG =
(VOL OF WEAK) (%WEAK)
(SF? GR.OF WEAK)
(=&OF STRONG)
(SF. GR.OF STRONG)
GALLONS
OFCONCENTRATED
7 HYDROCHLORIC
ACID TO MAKE
OF DILUTE
ACID
t 1,000 GALLONS

-8

- 32
- 30

-9

-28

- IO
-II $?
-12

-13 0

&

-14 2
I5 a

Acids

-16

Acetic acid (CH3COOH) and formic acid (HCOOH) are

weakly ionized, slowly reacting, organic acids. They are
used much less frequently than HCI and are suitable
primarily for wells with high bottomhole temperatures
(BHTs above 250F) or where prolonged reaction times
are desired. The reaction of these acids with limestone
is described by the following equation:

-17 0

-189 E
-2om

3
s-23
2:
Q-20
2-I;
-17
k-16
Z-15
=-I4
- 13

-2&

k-12

2,
EKBG
-282

2HOrg+CaCOj

+CaOrgz

HAc is available in concentrations up to 100% as glacial

HAc. while HCOOH is available in 70 to 90% concentrations. For field use, HAc solutions normally are diluted to I5 % or less.
Above this concentration, one of the reaction products,
calcium acetate, can precipitate from its spent acid solution because of its limited solubility. Similarly, the concentration of HCOOH normally is limited to 9 to 10%
because of the limited solubility of calcium formate. At
a 10% concentration, 1,000 gal HAc will dissolve 740
Ibm of limestone, whereas 1,000 gal HCOOH dissolves
970 lbm. Where more dissolving power per gallon of acid
is desired, HCI is sometimes mixed with HCOOH or
HAc. Such blends still provide extended reaction times.
when compared with HCl. HCOOH and HAc also may
be blended together. Table 54.2 illustrates some of the
more common acid strengths and blends.
Hydrofluoric

Acid (HF)

HF is used in combination with HCI and has been referred

to as intensified acid or mud removal acid. depending on the formulation and use. HF is used primarily to
remove clay-particle damage in sandstone formations, to
improve permeability of clay-containing formations, and
to increase solubility of dolomitic formations. Its utility
is based on the fact that some clays. silica, and other materials normally insoluble in HCI have some degree of
solubility in HF. For example, I .OOOgal of an acid solution containing 3% HF and 12% HCI will dissolve 500
lbm of clay and up to I .450 lbm of CaC03,
4HF+SiO?

-tSiFJ +2H10

and
ZHF+SiF,+HzSiF,.

:3oE

+HzO+CO,.

: 32
-34w
:36g

1380
-400

Fig. 54.2-Dilution of concentrated HCI

TABLE

54.2-DIFFERENT
Acid

Concentration

Type
7.5
15
28
36

ACIDIZING

SOLUTIONS

Relatwe
CaCO,
Eouivalent Reaction
(Ibm/l,i)OO
bal acid) time

HCI
HCI
HCI
HCI
Formic
Acetlc
Acetic

890
1,840
3,670
4,860
910
710
1,065

0.7
1.0
6.0
12.0
5.0
12.0
18.0

7.5
14

Formic/
HCI mixture

2,420

6.0

IO
14

Acetic/
HCI mixture

2,380

12.0

8
14

Formic/
Acetic mixture

1,700

18.0

10
10

15

Approwlmale
time for acid react!on 10 be COmpleled ( %qx?nl ) to an equ~vaienf
strength of 2 5% HCI solution Values are compared by using spending lime 01
15% HCI as 1

PETROLEUM

54-4

0.4
0.3 7

\-MUD

I
I
ACID

0.41

0.3u

ENGINEERING

HANDBOOK

0.2
I
0. I
0

/-REGULAR
ACID
I
I
I
I
6
12
18
TIME OF CONTACT IN HOURS

Fia. 54.3-Solubilitvof bentonite in mud

I
24

removal acid

Figs. 54.3 and 54.4 compare solubilities of bentonite and

silica in HCl and HF acids.
In carbonates, application of HF/HCl mixtures must be
controlled carefully because of cost and possible precipitation of reaction products such as calcium fluorides or
complex fluosilicates, which have a very limited solubility. For reaction with silicates, such as natural clays or
clays in drilling fluids, the blends usually contain 2 to 10%
HF and 5 to 26% HCI. The concentration of HCl used
in the blend should be equal to or greater than that of the
HF.
The so-called intensified acids used in dolomitic formations are mainly HCl containing small concentrations
of HF, usually about 0.25 % Intercrystalline films of silica, insoluble in HCl, often occur in the crystal structure
of dolomite. When such are present, they prevent the acid
from contacting the soluble portions of the rock. The presence of fluoride intensifier in the acid will destroy such
films, allowing the acid to react more completely with
the soluble portions of the rock. Fig. 54.5 illustrates the
comparative reaction rates of HCI and intensified acid on
dolomite formations.
More recent developments of HF involve the use of
delayed-action agents in sandstone acidizing. The first of
these was a self-generating mud acid system, reported by
Templeton er al. The system provides slow generation
of acid from the hydrolysis of methyl formate. yielding
methyl alcohol and HCOOH acid. The acid then reacts
with ammonium fluoride to yield HF in situ. They attribute the success of the system to getting the HF reaction
away from the wellbore into areas that conventional HF
solutions normally do not reach before spending. Equally important factors are the techniques of application and
of returning the well to production following treatment.
The treatment technique mvolves use of an aromatic solvent and mud acid preflush, along with the self-generating
mud acid (SGMA). The wells are returned to production
by opening the choke gradually over a 90-day period and
never allowing an excessive drawdown. The process is
available from most service companies as SGMA.
A significant development in this area of slow-reacting,
HF-supplying, clay-dissolving acid has been the fluoboric
acid system reported by Thomas and Crowe. This acid

1
TIME

OF CONTACT

IN HOURS

Fia. 54.4-Solubilitvof silicasand in mud

hydrolyzes to form hydroxyfluoboric

will dissolve clays.

removal acid

acid and HF, which

HBF4 +HZO-HBF30H+HF.
This reaction provides a slow-release source of HF, which
can penetrate deeply before spending. Perhaps more important, the slowly generated hydroxyfluoboric acid reacts
with clays to form a nonswelling, nondispersing product
that stabilizes fine clays and holds fine particles of silica
in place.

Acid Reaction Rates

A knowledge of the factors affecting the reaction rate of
acids is important for several reasons. First, these factors, correlated with reservoir and formation characteristics, form a guide for the selection of acid type and
volume for a given treatment. Next, a study of these factors can furnish an understanding of what parameters
govern spending time, which will determine how far a
given formulation can penetrate into the formation before
spending. Many factors govern the reaction rate of an
acid, such as pressure, temperature, flow velocity, acid
concentration, reaction products, viscosity, acid type,
area/volume ratio, and formation composition (physical
and chemical). These factors have been the subject of extensively reported research for many years. Details of such
studies are available in published literature. Only a brief
general discussion will be presented here.
Pressure
Fig. 54.6 shows the effect of pressure on the reaction rate
of 15% HCl with limestone and dolomite at 80F. Above
500 psi, pressure has little effect on reaction rate. At bottomhole treating pressures, there is only a small difference (a factor of 1.5 to 2) in the comparative reaction of
acid with limestone and dolomite compared to the rather
large difference (a factor of about 10) at atmospheric
pressure.
Temperature

Acid reaction rate increases directly with temperature. At

140 to 150F, the reaction rate of HCI and limestone is

54-5

ACIDIZING

.INTENSIFIED

IO

15

20

25

400

800
1200 1400
PRESSURE (PSI)

TIME IN MINUTES
Fig. 54.5-Comparative
reaction rates of conventional and
intensified
acids.

MARBLE

Fig. 54.6-Effect of pressureon

2000

reaction rate (15%

2400

HCI tit
80F).

approximately twice that at 80F. It must be recognized

that the temperature controlling the reaction is affected
by the injection temperature of the acid (a major factor),
and by the heat liberated by the reaction itself (a minor
factor). Computerized programs are used to estimate the
bottomhole fluid temperature at various stages, allowing
more effective acid treatment design.
Flow Velocity
Fig. 54.7 shows that increased flow velocity increases the
reaction rate of 15 % HCl with CaCO 3. This velocity effect is more pronounced in narrower fractures. Reaction
rate is a function of shear rate, 6 v/b, set - as illustrated by the following equation:
R=[(28.5

v/b)0.8+184]x10-6,

. . . . . . . . . . . ...(l)

where R is the reaction rate in lbmisq ft-set, v is the flow

velocity in fracture, ft/sec, and b is the fracture width,
ft. (The reaction rate is for 15% HCl with marble at 80F
under 1,100 psi pressure.)
The flow velocity in fractures and channels depends on
injection rate and actual geometry of the flow path.
vd=O. 18i,,l(rfb)

vlf= 1,15i,,l(hb)
v,, = 17.2i,,/d2

(radial fracture),
(linear fracture),
(cylindrical

. . .(2a)
. ..

channel).

(2b)
.

. . .(2c)

where
v = flow velocity in fractures and channels,
ftlsec,
=
acid
injection rate, bbl/min,
1ac
rf = fracture radius, ft,
h = fracture height, ft,
d = channel diameter, in., and
b = fracture width, in.
Acid Concentration

Reaction rate increases with acid concentration up to 24

to 25% HCl, but not proportionally, as shown in Fig.

I
IO0

10
,

ACID FLOW

1,000
VELOCITY

10,000

40,000

,s,ce,

FIAClUlE WIDTII

Fig. 54.7-Effect of flow on

reaction

rate

(15%

HCI with

CaCO,).

54.8. Above 25% HCl, the reaction rate actually decreases

because of reduced acid activity. As acid spends, the reaction rate decreases as a result of reduced acid concentration and the retarding effect of dissolved reaction products,
such as calcium or magnesium chloride.
Area/Volume

Ratio

Area/volume (A/V) ratio is one of the major factors affecting reaction rate spending time, and may vary over a wide
range. This ratio, the area in contact with a given volume
of acid, is inversely proportional to pore radius or fracture width. Fig. 54.9 shows the time required for 15%
HCl to spend on marble, at 80F and 1,100 psi, for three
different A/V ratios.
The term spending time has very little meaning or
value by itself. It must be related to flow geometry and,
thus, to the distance the acid penetrates before it is spent.
In matrix acidizing, extremely high A/V ratios may be
encountered. For example, a IO-md, 20%-porosity limestone may have an A/V ratio of 28,000 to 1. In such a
formation, it would be very difficult to obtain significant
penetration before spending. A natural fracture, 0.00 1 in.
wide, has an A/V ratio of 3,200: 1. A 0. l-in. fracture has
an A/V ratio of 32: 1. The smaller ratios in wider frac-

PETROLEUM

10

20

30

ENGINEERING

40

50

HANDBOOK

60

Th4E (min)
Fig. 54.9-Effect of A/V ratioon spending time (15% HCI, 80F
and 1,100 psi).

Two formations having the same acid solubility and permeability may respond differently to acid treatment because of variances in physical structure.
I

IO

I5

20

PERCENT

25

30

35

HCI

Fig. 54.8-Effect of concentrationon reactionrate and spending rate.

Acid Additives
The use of a corrosion inhibitor as an additive made possible the firstcommercially feasible acidizing treatments.
Since that time, many auxiliary chemicals have been developed to modify acid solutions, influencing their application and recovery.
Corrosion

TABLE 54.3-EFFECT
OF TEMPERATURE
ON ORGANIC
INHIBITOR PROTECTION
TIME

Concentration

Temperature

WI

CF)

0.6
1.0
2.0
2.0

175
250
300
350

Protection
Time
(hours)
24
6
6
4

With mhtbltor aId

tures allow greater penetration of the acid into the reservoir before spending is complete.
Formation

Composition

Probably the most important factor that governs effectiveness of an acidizing treatment is the rock composition.
Its chemical and physical characteristics determine how
and where the acid will react with and dissolve the rock.
From the standpoint of chemical composition, there is
little difference in the reaction rate of HCI on most limestones, all other factors remaining constant. The physical rock texture. however, can control pore size
distribution. A/V ratio, pore geometry, and other properties. This, in turn, influences the type of flow channels
created by acid reaction and is the key to acid response.

Inhibitors

Inhibitors are chemical materials that, when dissolved in

acid solutions, greatly retard the reaction rate of the acid
with metals. They are used in acidizing to avoid damage
to casing, tubing, pumps, valves. and other well equipment. Inhibitors cannot completely stop all reaction between the acid and metal; however, they do slow the
reaction, eliminating 95 to 98% of the metal loss that
would otherwise occur. Most inhibitors have practically
no effect on the reaction rate of acid with limestone, dolomite, or acid-soluble scale deposits.
The length of time that an inhibitor is effective depends
on the acid temperature, type of acid, acid concentration,
type of steel, and the inhibitor concentration.
Organic inhibitors in HCI are effective up to 400F,
but above 200F relatively large concentrations are required. The effect of temperature on corrosion inhibition
is illustrated in Table 54.3.
Equations have been developed for estimating BHTs
during acid treatments. By knowing these temperatures,
adequate corrosion protection can be provided, even in
wells with static BHTs up to 400F.
Surfactants

Surfactants are chemicals used to lower the surface terlsion or interfacial tension of fresh acid or spent acid solutions. The use of a surfactant improves the treating
efficiency in a number of ways.
The presence of a surfactant improves the penetrating
ability of the acid solution entering a formation. This is
extremely desirable in matrix acidizing treatments. be-

54-7

ACIDIZING

z
-

ST
3;
I
2 lpoo
a
0800yORDlNARY

A C I D ,

g 6 0 0
i;i

Egjpek&
k!
3
z

20
15
5
IO
PENETRATION IN FORMATION- FEET

PHI

Fig. 54.10Effect of surface-tension-reducing agent in facili-

tating return of spent acid.

cause it provides deeper penetration of acid into the formation. In addition, surfactants permit the acid to
penetrate oily films clinging to the surface of the rock and
lining the pores, so that the acid can come in contact with
the rock and dissolve it.
The use of surfactants also facilitates the return of spent
acid following the treatment (Fig. 54.10). Wetting of the
formation is more nearly complete and there is less
resistance to flow of the acid, so that the spent acid is
readily returned through the treated section. This is especially important in low-pressure wells.
Another advantage in the use of surfactants in acid is
the demulsifying action obtained. Many surfactants are
capable of inhibiting the occurrence of emulsions or destroying those already formed.
Surfactants also promote dispersion and suspension of
fine solids to provide better cleanup following treatment.
These solids may be either mud solids or natural fines
released from the formation. They are suspended and
physically removed from the formation.
Special surfactants are used as antisludge agents. Some
crudes form an insoluble sludge when in contact with acid.
The sludge consists of asphaltenes, resin, paraffin, and
other complex hydrocarbons. The acid reacts with the
crude at the interface, forming an insoluble film. The
coalescence of this film, which results on the sludge particles, can be avoided by use of proper additives. Ethylene glycol monobutyl ether is a mutual solvent surfactant
used in matrix sandstone acidizing to water-wet the formation. This agent prevents particle migration and subsequent particle plugging. It improves cleanup by
preventing the stabilization of emulsions by fine particles.
Many different surfactants are used in acidizing. Type and
concentration for a particular application should be selected on the basis of laboratory testing.
Silicate-Control Agents
Various silicate compounds, commonly known as clays
and silts, usually are present in most limestones and dolo-

t-942

PH3

PHI

PH5

Fig. 54.11Photograph showing effect of pH on the volume of

silicate particles.

mites. One of the characteristics of these silicates is that

they will swell in spent acid. Naturally, this is undesirble
because swollen silicate particles may block formation
flow channels, reducing well production.
Silicate-control additives are chemicals that prevent
released silicate particles from adsorbing water. Some
buffer the pH of the solution near the isoelectric point
(where the volume of the swelled clays is at a minimum).
Others cause shrinkage of the silicate particles by replacing the adsorbed water molecules with a water-repellent
organic film. Thus, possible formation plugging is
prevented, treating pressures are lowered, faster cleanup
is provided, and the occurrence of particle-stabilized emulsions is minimized. This is illustrated in Fig. 54.11.
Iron-Control Agents
Iron control is approached two ways. The oldest and most
common approach is to use sequestering agents, which
act by complexing iron ions, thereby preventing precipitation when the acid spends. A second method is use of
reducing agents that reduce any ferric ions (Fe3+) to ferrous ions (Fe2+), which do not precipitate as the hydroxide or hydrous oxide until the pH of the system is above
7. Since acids in contact with the formation rock will not
spend to a pH that high, the hydroxide will not damage
the well. Spent acid usually has a pH between 4.5 and
6.5, no higher.
Erythorbic acid is one of the most effective reducing
agents that can be used for this purpose. The reduction
of all the ferric iron to ferrous iron, however, does not
prevent the precipitation of ferrous sulfide (FeS), which
precipitates when the acid spends to a pH of 2, as it will
readily in almost any formation. To protect fully against
iron precipitation in a sour well, a complexing agent is
needed. Citric, lactic, and acetic acids as well as EDTA
or NTA are popular sequestrants. In some wells where
H 2S can become mixed with the acid it also may be advisable to use both the reducing agent and the sequestering agents, since ferric iron can react with H 2S to

PETROLEUM

54-8

precipitate free sulfur, which itself can damage permeability The loss of effectiveness of acetic acid at temperatures above 125F and the possibility of precipitating
calcium citrate also are factors that should be considered
in guarding against iron precipitates.
Alcohols

Methyl and isopropyl alcohols sometimes are used at concentrations of 5 to 20 ~01% of acid to reduce surface tension. Methyl alcohol is sometimes used at concentrations,
up to 66 % to increase vapor pressure of the acid and spent
acid solution. Use of alcohols thus improves both rate and
degree of cleanup, which can be particularly helpful in
dry gas wells.
Gelling and Fluid Loss Agents

Natural gums and synthetic polymers are added to acid

to increase the viscosity of the acid solution. 3 This
reduces leakoff into large pore spaces and, to some extent, into natural hairline fractures. It also provides some
degree of reaction rate retardation.
Other materials used to control leakoff are fine (IOOmesh) sand4 and fine salt.5 These materials bridge in
hairline fractures to reduce fluid flow out of the main fracture during fracture acidizing treatments.
Another successful fluid-loss control agent is a mixture
of finely ground, oil-soluble resins. 6 Originally designed
as a diverting agent for use through gravel packs during
sandstone matrix acidizing treatments, this agent was later
shown to be effective as a fluid-loss agent in fracture
acidizing, when used at higher concentrations.
Liquefied

Gases

Liquid nitrogen and liquid CO2 sometimes are used in

acid solutions to provide added energy for better well
cleanup. Nitrogen also is used to make foamed acid, which
provides excellent leakoff control in low permeability
rock. 8.9
Retarded

Acids

It is often desirable in acid fracturing treatments to retard

the reaction rate of the acid to provide deeper penetration of active acid into the formation. Retardation may
be accomplished by use of slower-reacting acids (HAc
and HCOOH), by adding chemicals to reduce reaction
rate, or by increasing concentration to extend spending
time.
HAc and HCOOH are weakly ionized and sometimes
are used to obtain longer reaction time. The additional
cost of these acids may prohibit extensive use in certain
formations. Deeper matrix penetration than would be obtained by HAc or HCOOH is obtained by the fasterreacting HCl because the channeling or wormhole effect
produced by the HCl reduces the A/V ratio, thus prolonging reaction time. In fractures, the HAc and HCOOH
would obtain deeper penetration than HCl; however, larger volumes would be required to dissolve an equivalent
amount of rock.
Some chemicals, added to HCl, form a barrier on the
rock surface, which interferes with its normal contact and
retards the reaction rate of the acid. Acid-in-oil emulsions generally exhibit retarded reaction rates. The acid
in the emulsion does not completely contact the rock sur-

ENGINEERING

HANDBOOK

face because of the presence of an interfering oil film.

This is particularly true for emulsions with at least 20%
oil as the outer phase. Certain surfactants recently have
been found to be beneficial in reducing reaction rate and,
thus, extending spending time and penetration distance.
These surfactants, in the presence of oil, provide a
hydrophobic or water-repellent, oil-like film on the rock
surface that restricts acid/rock contact. Fluid-loss materials and gelling agents (acid-thickening additives) also
tend to reduce the reaction of HCl by film development
on rocks.
High concentrations of an acid provide longer reaction
times than lower concentrations because (1) there is more
acid to react, (2) the additional reaction products further
retard reaction rates, and (3) the enlarged flow path, with
reduced A/V ratio, extends the spending time and penetration of a high-concentration acid. For example, 28% HCl
may take four to six times longer to react completely than
does 15% HCl. In this case, the reaction time is extended in spite of the initially faster reaction rate of the
28% HCl.

Acidizing Techniques
There are three fundamental techniques used in acidizing
treatments.
1. We&ore Cleunup. This entails fill-up and soak of
acid in the wellbore. Fluid movement is at a minimum,
unless some mechanical means of agitation is used.
2. Matrix Acidiz,ing. This is done by injecting acid into
the matrix pore structure of the formation, below the
hydraulic fracturing pressure. Flow pattern is essentially
through the natural permeability structure.
3. Acid Fmcturing. This is injection into the formation above hydraulic fracturing pressure. Flow pattern is
essentially through hydraulic fractures: however, much
of the fluid does leak off into the matrix along the fracture faces.
The technique selected will depend on what the operator wishes to accomplish with the treatment.
Matrix acidizing may be selected as a proper technique
for one or more of the following reasons: (1) to remove
either natural or induced formation damage, (2) to achieve
low-pressure breakdown of the formation before fracturing, (3) to achieve uniform breakdown of all perforations,
(4) to leave zone barriers intact, or (5) to achieve reduced
treating costs.
The principal types of formation damage are mud invasion, cement, precipitates, saturation changes, and
migration of fines. The effect of damage on injectivity
or productivity is shown in Figs. 54.12 and 54.13. It can
be seen that the greatest flow increase results from restoring the natural rock permeability. The magnitude of this
primary flow increase depends on the extent (radius) of
the damage. Further increase in pore size by matrix acidizing results in only a limited increase in flow (stimulation).
If the producing formation does not have enough natural
permeability, then a hydraulic fracturing treatment should
be considered. The primary purpose of fracturing is to
achieve injectivity or productivity beyond the natural
reservoir capability. An effective fracture may create a
new permeability path, interconnect existing permeability streaks, or break into an untapped portion of the
reservoir.

ACIDIZING

54-9

00

25

5 m

2
RADIAL

3
4
EXTENTd c4ALGul

7
ZorE.

lo

FEET

IO
PERCENT

100

OF NATURAL

1000

PERMEAElllTY

Fig. 54.12-Effect of damaged zone on flow.

Fig. 54.13-Effect

of permeabilitychanges on radialflow.

The success of any fracturing treatment depends on two

factors: fracture conductivity and effective penetration,
as illustrated in Fig. 54.14. If enough etched fracture conductivity can be achieved, then increased penetration becomes important. For any given formation, there will be
an optimum conductivity and penetration, which will be
controlled by cost. In other words, there will be some
point where production increase per dollar spent will be
a maximum. This must be determined by pretreatment
design.

Laboratory Testing
The physical and chemical characteristics of the formation rock often affect the results of an acidizing treatment.
In some cases, the use of special additive chemicals will
improve the action of the acid or avoid cleanup difficulties in returning the spent acid following the job. It is important, therefore, that samples of the formation rock
(either cores or cuttings) and, if possible, samples of the
crude oil and formation brine be subjected to laboratory
testing before acidizing to design the most effective
treatment.
Customarily, permeability. porosity, and oil- and watersaturation tests are run on formation core samples, using
standardized core-analysis procedures. In addition, acidsolubility tests are run to determine to what extent the formation will respond to an acidizing treatment.
Formation solubility may be determined two different
ways. In the first method, a weighed chunk of the rock
is immersed in an excess of acid and maintained at formation temperature. After an hour, any insoluble residue
is washed. dried, and weighed. With samples known to
contain silicates, additional tests may be run in which the
rock is exposed to the dissolving action of combined HCl
and HF.
A more rapid test, suitable for samples known to consist largely of limestone or dolomite, entails dissolving
a weighed sample of the rock in an excess of HCl and
measuring the volume of CO* gas evolved during the
reaction. A simple apparatus for conducting this test is
shown in Fig. 54.15.
In addition to these tests of the formation rock, the emulsifying tendencies of the formation crude should be determined whenever possible. Samples of the crude are mixed

McGUlRE
IO'

IO'

RELATIVE

CONDUCTIVITY,

IO'

AND
ID'

SIKORA
IO'

bk#,,-In

Fig. 54.14-Relationship of conductivityand penetration to

productivity
increase.J= productivity
index of well
after stimulation,J, = productivityindex before
stimulation,
ri= radiusof fracture(ft),
re = drainage
radius (ft).k,=permeability of fracture (md),
k, = permeabilityof formation (md), and b = fracture width (in.).

with the acid to be used in the acidizing treatment and

then are shaken. The mixture is allowed to stand, and the
time required for the oil and acid to separate is observed.
Additional tests are run on mixtures of the crude oil with
acid that has been spent completely on pulverized formation rock. If the formation crude shows a tendency to
emulsify with either the fresh acid or the spent acid, the
use of an appropriate surfactant is indicated.
Similar tests using a mixture of crude and acid are made
to determine acid sludging tendencies. Sludge is identified by filtering the mixture through a small mesh screen.
Appropriate surfactants that are added to the acid to prevent sludge formation are evaluated.
Other determinations of rock characteristics include
tests for clay swelling tendencies and tests to determine
rock composition (such as X-ray diffraction analysis) to
indicate need for stabilizers, sequestering agents, or other
acid additives.

PETROLEUM

54-10

TABLE

54.4-FLOW

Diameter of Pore
(A
il
1 to 2
2 to 5
5 and above

Fig. 54.15-Laboratory solubillty

tester(carbon dioxide evolution method).

Acid Treatment Design

Three techniques of acidizing have been described previously. Wellbore cleanup treatments normally do not require complicated design procedures. Matrix and fracture
acldlzmg treatments. on the other hand, can involve extensive predesign laboratory testing and complicated design procedures and calculations.
Matrix Acidizing-Carbonate

Formations

Matrix acidizing in carbonates normally is used to break

down all perforations and to remove damage. Plugging
materials can be removed and permeability restored in
two ways: (1) by dissolving the damaging material itself
or (2) by dissolving part of the rock in which the damage
exists. In carbonate rocks with acid solubilities greater
than 50%) the latter method is often most effective. The
dislodged solid particles or liquids then can bc removed
physically by the return of the spent acids to the well.
HCI normally is used in matrix treatments of carbonates, but HAc and/or HCOOH should be considered

ENGINEERING

THROUGH
SIZES
Pore Volume
w
60
25
12
3

PORES

HANDBOOK

OF VARIOUS

Flow Through Pores

(% of Total Flow)
10
15
30
45

for wells with temperatures in excess of 250 to 300F.

Any acid solution should be modified by use of proper
additives to meet special situations.
Acid inhibitor selection must be based primarily on
treating temperature and, to some extent, on the type of
acid formulation.
Surfactant type and concentration should be selected to
minimize emulsion tendencies and, perhaps, to aid in dispersing fine undissolved solids. These may be drilling
mud, cement solids, or natural clay particles released from
the formation. Suspension and removal of these materials can play an important part in the overall treatment
results.
Diverting agents may be used to promote uniform
penetration in long sections. Acid-swellable synthetic
polymers, controlled-solubility particulate solids, perforation ball sealers, gel slugs, etc., have been used successfully to provide more uniform injectivity. Assuring
the distribution of acid into the entire interval is a critical
part of carrying out a matrix treatment. Otherwise, large
portions of the interval may get very little, if any, acid.
In matrix acidizing, injection rates should be controlled
so that the formation is not fractured. The use of as high
a rate as possible without exceeding the fracturing pressure is recommended. In certain cases, it may be necessary to create a fracture to open perforations, after which
pressure can be reduced below fracturing pressure, thus
providing a matrix flow pattern.
Controlling the injection pressure is the primary concern. Maintaining bottomhole pressures below hydraulic
fracturing pressures may restrict injection rates to only
fractional barrels per minute. An increasing rate may then
be possible as the treatment progresses.
Because of differences in the size and shape of the pores,
penetration of acid in a carbonate rock is far from uniform. Porosity anomalies may result from vugs, hairline
fissures, or tortuous capillary-like pores. Because of these
heterogeneities, a channeling or wormholing occurs
with most acid formulations. The resultant effect is the
attainment of much greater acid penetration of matrix than
expected.
The wide distribution of flow in a rock of varying pore
diameters (Table 54.4) is further accentuated by acidizing. As discussed in a preceding section, the fast-reacting
HCl may provide greater penetration of the limestone
matrix than the slow-reacting acetic acid, but not as great
as with the emulsified or gelled acids. Evidently, the slow
reaction of acetic acid does not change the flow distribution rapidly enough to channel, but rather results in
several small pore enlargements for short distances as opposed to a few large, long channels.
Since the formation damage normally does not exist for
a great distance from the wellbore, the volume of acid
needed is small. With a formation porosity of IO%, 60

54-11

ACIDIZING

gal of acid per foot of section will fill the porosity to a

radius of 5 ft. Usually, matrix treatment volumes range
from 50 to 250 gal per foot of section. If damage is deeper than 5 to 10 ft, then larger volumes of acid, a means
of retarding the reaction rate, or, perhaps, fracturing techniques, may be required. Very little rock must be dissolved to result in a significant amount of damage repair
or permeability increase. Removal of only 1% of limestone or dolomite rock for a distance of about 5 ft from
the wellbore requires only 70 gal of 15 % HClift of vertical interval.
An overflush in the matrix acidizing treatment is recommended. This will ensure efficient displacement of the
acid into the matrix. A minimum shut-in time is recommended before returning the spent acid to the well. Since
the spending time of acid is short, a long shut-in time of
several hours is not necessary, even for the so-called
retarded acid. The overflush fluid may be brine, water,
oil, or a weak acid. Enough volume should be used to
ensure maximum penetration of the last portion of the
acid, before it is spent.
Matrix Acidizing--Sandstone

Formations

The purpose of sandstone acidizing is to restore permeability by dissolving away formation-damaging clay-like
minerals or other acid-soluble materials. The clay may
be inherent in the formation or may be the result of drilling mud or workover fluid invasion.
The type of acid used most often in sandstones is a mixture of HF and HCl. These mixtures commonly are rem
ferred to as mud acids or mud removal acids. As
previously discussed, fluoboric acid also has become
popular in sandstone formations. Concentrations of 2 to
6 % HF and 8 to 12 % HCl normally are used. If a significant amount of calcium carbonate is present in the formation (5 to lo%), a spearhead of HCl should be used
to react with it before the HF/HCl is injected. With carbonate content above 20%, HF acid probably is not needed, except to give entry through clay damage.
As in any matrix-type treatment, injection of the
HF/HCl should he below fracturing pressure. The volume
of acid required depends on the depth and severity of the
damage. A total of 50 to 250 gal of acid per foot of interval is the normal treatment volume, if damage is not extensive. An acid solubility test may not be a realistic
evaluation of acid requirements.
Results of a field study by Gidley et al. lo confirmed
some earlier recommendations based on laboratory core
flow studies. These results showed much greater success
when more than 125 gal/t? acid was used.
The reported core flow test showed what response the
formation will have to acid. This is illustrated in Fig.
54.16. Although some of these formations have approximately the same acid (HF/HCI) solubility, permeability,
and porosity, the response to acid is quite different.
Initial reduction in permeability is a common occurrence
observed with many formation core flow tests. It is attributed to sloughing particles (clays, silica, fines, etc.)
that apparently bridge in the flow channels and restrict
flow, before their further reaction with the acid. An inadequate acid volume treatment could lead to a restricted
permeability in a formation, if the bridging is severe.
Since secondary reactions may occur, resulting in possible precipitation of damaging reaction products, mud

"0
MUD

ACID

VOLUMf

IO
RfPUIRfMENT5

15

20

(p.l/f12)

Fig. 54.16--Response of cores from producing formations to

mud acid.

acid should be returned to the wellbore as soon as the initial spending time has elapsed. The spent HF/HCl acids
should not be allowed to mix with formation brine, if at
all possible because of the danger of precipitates.
Inhibitors, surfactants, and diverting methods should
be selected just as in an HCl acid treatment. As in the
case of matrix acid treatment in carbonates, an overflush
is recommended. Suitable fluids include weak acid, oil,
or water. Formation brine should not be used to overflush HF/HCl. Short shut-in times should be used-a few
hours at the most.
Fracture

Acidizing-Carbonate

Formations

The primary purpose of an acid fracturing treatment of

a carbonate formation is to achieve productivity or injectivity beyond the natural capabilities of the reservoir. It
is most applicable in formations with a low and/or ineffective permeability structure. The effectiveness of an induced hydraulic fracture is a function of both its
conductivity and the extent of penetration of the drainage
radius of the well.
These factors will depend on well and reservoir properties, formation characteristics, injection rate, type and
volume of acid used, and shape and orientation of the fracture. All these factors have been correlated by several
companies into guides to acid fracture treatment design. Such guides provide mathematical relationships for
determining the fracture area and conductivity achieved
by different volumes of specific acid formulations at various injection formulations. These guides are programmed
for computer calculation, so that rapid comparison of various treatment designs can be made for selection of best
results per dollar of treatment cost. These guides are not
sufficiently similar to get clear comparison between different companies but should be compared only with other
calculations from the same system.

Critical Wells
In ultradeep, high-temperature wells, many factors must
be considered in the stimulation treatment design. First,
the high BHT can drastically affect reaction rate of acid,
inhibition, and other properties of the acid formulation.

54-12

These effects can be partially offset by formation cooldown techniques. Basically, this consists of pumping a
pad volume of fluid (generally gelled water) into the formation to cool the rock to a more normal treating temperature. Most companies have computer programs
available to calculate pad volumes required for a given
temperature reduction.
Another problem is created when fluids with temperatures lower than BHTs are used. This problem is mechanical and involves tubing movement. In ultradeep
wells, such contraction can create stress in the tubing
greater than tubing strength, resulting in a parted string.
The solution to this problem is to slack off or to release
tension at the top of the tubing string as the job progresses. Again, computer programs are available from most
service companies to predict tubing movement under given
conditions.

Summary
In summary, acidizing is a process that uses reactive materials to increase well production by dissolving either the
reservoir rock or damaging materials blocking the pore
spaces of the rock. Different kinds of acids and additives
are available, so that treating fluids can be tailored to meet
individual well needs. Acid formulations may be applied
in either matrix- or fracture-type treatment, depending on
the degree of stimulation or production increase desired.
While acidizing, and acidizing treatment design, in detail are beyond the scope of this text, published literature
offers answers and assistance in solving many of the problems encountered. The General References cover many
of the recent technical developments in this field. In addition, most service companies providing acidizing service offer laboratory facilities, technical assistance, and
computer programs for problem analyses and treatment
design.

References
I. Templeton, C.C. er al.: Self-Generating Mud Acid, J. Per. Tech.
(Oct. 1975) 1199-1203.
2. Thomas, R.L. and Crow, C.W.: Matrix Treatment Employs New

3.

4.

5.

6.

7.

8.

Acid System for Stimulation and Control of Fines Migration in Sandstone Formations, paper SPE 7566 presented at the 1978 SPE
Annual Technical Conference and Exhibition, Houston, Oct. l-3.
Crowe, C.W., Martin, R.C., and Michaelis, A M.: Evaluation
of Acid Gelling Agents for Use m Well Stimulation, paper SPE
9384 presented at the 1980 SPE Annual Technical Conference and
Exhibition, Dallas, Sept. 21-24.
Miller, B.D. and Warembourg. P.A.: Prepack Technique Using
Fine Sand Improves Results of Fracturing and Fracture Acidizing
Treatments.. paper SPE 5643 presented-at the 1975 SPE Annul?
Technical Conference and Exhibition, Dallas, Sept. 2%Oct. I.
Schrieter, F.E. and Shaw, M.S.: Use of Fine Salt as a Fluid Loss
Material in Acid Fracturmg Stimulation Treatments, paper SPE
7570 presented at the 1978 SPE Annual Technical Conference and
Exhibition, Houston, Oct. l-3.
Crowe, C.W.: Evaluation of Oil-Soluble Resm Mixtures as Divenmg Agents for Matrix Acidizing, paper SPE 3505 presented
at the 1971 SPE Annual Meeting, New Orleans, Oct. 3-6.
N&ode. D.E. and Kmk. K.F.: An Evaluation of Acid Fluid Loss
Additives. Retarded Acids, and Acidized Fracture Conductivity,
paper SPE 4549 presented at the 1973 SPE Annual Fall Meecmg,
La5 Vegas. Sept. 30-Oct. 3.
King, G.E. and Hollingsworth, F.H.: Evaluation of Dwertmg
Agent Effectiveness and Clean-up Characteristics Using a Dynamic
Laboratory Model-High
Permeability Case. paper SPE 8400
presented at the 1979 SPE Annual Technical Conference and
ExhIbition, Las Vegas, Sept. 23-26.

PETROLEUM

ENGINEERING

HANDBOOK

9. Scherubel, GA. and Crowe, C.W.: Foamed Acid: A New

Concept in Fracture Acidiaing, paper SPE 7568 presented at&he
1978 SPE Annual Technical Conference and Exhibition. Houston,
Oct. 1-3.
10. Gidley, J.L., Ryan, J.C., and Mayhill, T.D. : Study of Field
Applications of Sandstone Acidizing, /. Per. Tech. (Nov. 1976)
1289-94.

General References
Abram, A. ef al: The Development and Application of a High pH Acid
Stimulation System for a Deep Mississippi Gas Well, paper SPE 7565
presented at the 1978 SPE Annual Technical Conference and
Exhibition, Houston, Oct. 1-3.

Barron, A.N., Hendrickson,A.R., and Wieland, D.R.: The Effect

of Flow on Acid Reactivity in a Carbonate Fracture,
(April 1962) 409-15; Trans., AIME, 225

J. Per. Tech.

Black, H.N. and Stubbs, B.A.: A Case History Study-Evaluation

of San Andres Stimulation Results, paper SPE 5649 presented at the
1975 SPE Annual Technical Conference and Exhibition, Dallas, Sept.
29-Oct. 1.
Broddus, E.C. and Knox, J.A.: Influence of Acid Type and Quantity
in Limestone Etching, paper API No. 851-39-I presented at API
Production Dev. Mid-Continent Dist., Wichita, March 31-April 2,
1965.
Burkill, G.C.C. and Pierre, M.L.: Successful Matrix Acidizing of
Sandstones Requires a Reliable Estimate of Wellbore Damage, paper
SPE 5590 presented at the 1975 SPE Annual Technical Conference
and Exhibition, Dallas, Sept. 29-Oct. I,
Chat&in, J-C., Silberberg, I.H., and Schechter, R.S.: Thermodynamic
Limitations in Organic Acid-Carbonate Systems, Sot. Per. Eng. J.
(Aug. 1976) 189-95.
Church, D.C., Quisenberry, J.L., and Fox, K.B.: Field Evaluation
of Gelled Acid for Carbonate Formations, J. Pet. Tech. (Dec. 1981)
241 l-74
Clark. G.J., Wong, T.C.T., and Mungan, N.: New Acid Systems for
Sandstone Stimulation, Proc., SPE Formation Damage Control
Symposium, Lafayette, LA (March 24-25, 1982) 187-97.
Coppel, C.P.: Factors Causing Emulsion Upsets in Surface Facilities
Following Acid Stimulation, J. Per. Tech. (Sept. 1975) 1060-66.
Coulter, G.R. and Purvis, S.B.: Successful Stimulation PracticesOffshore Holland, J. Per. Tech. (June 1982) 121 l-18.
Coulter, A.W. Jr., Copeland, C.T., and Harrisberger, W.H.: A Laboratory Study of Clay Stabilizers, Sot. Pet. Eng J. (Oct. 1979)
267-69.

Coulter, A.W. Jr. er al.: Alternate Stages of Pad Fluid and Acid Provide
Improved Leakoff Control for Fracture Acldizing, paper SPE 6124
presented at the 1976 SPE Annual Technical Conference and
Exhibition, New Orleans, Oct. 3-6.
Coulter, A.W. Jr et al. : Mathematical Model Simulates Actual Well
Conditions In Fracture Acidizing Treatment Design. paper SPE 5004
presented at the 1974 SPE Annual Meeting, Houston, Oct. 6-9
Crawford, D.L., Coulter, A.W. Jr.. and Osborn, F.E. III: Removal
of Wellbore Damage From Highly Permeable Formations and Naturally
FracturedReservoirs, paper SPE 8796 presented at the 1980 SPE
Formation Damage Control Symposann, Bakersfield, CA, Jan. 28-29.
Crenshaw, P.L., Flippen, F.F., and Pauley. P.O.: Stimulation
Treatment Design for the Delaware Basin Ellenburger. paper SPE
2375 presented at the 1968 SPE Annual Meeting. Houston. Sept.
29-Oct. 2.
Crowe, C.W. and Minor, S.S.: Effect of Acid Corrosion Inhibitors
Upon Matrix Stimulation Results, paper SPE I I1 I9 presented at the
1982 SPE Annual Technical Conference and Exhibmon. New Orleans.
Sept. 26-29

54-13

ACIDIZING

Davis. J.J., Mantillas, G., and Melnyk. J.D.: Improved Actd

Treatments by Use of the Spearhead Film Technique. paper SPE
1164 presented at the 1965 SPE Rocky Mountain Regional Meeting,
Billings. MT, June 3-4.
Deysarkar, A.K. cf al. : Crosslinked Fracture Acidizing Acid Gel.
paper 82-33-16 presented at the 1982 CIM Annual Meeting, Calgary.
June 6-9.

Hendrickson. A.R.. Rosme, R.B., and Wieland. D.R.: The Role of

Acid Reaction Rates in Planning Acidizing Treatments. Truns.,
AIME, 222 (1961).
Hendrickson, A.R., Hurst. R.E., and Wieland. D.R.: Engmeered
Guide for Planning Acidizing Treatments Based on Specific Reservoir
Characteristics. J. Per Twh. (Feb. 19M)) 16-23: Trans.. AIME. 219.

Dill, W.R.: Retarded Acidizing Fluids. U.S. Patent No. 4.322.306

(1982).

Hill, D.G. and DeMort, D.N.: Effect of Hydrogen Sulfide on Inhibition

of Oil Field Tubing in Hydrochloric Acid, paper SPE 6660 presented
at the 1977 SPE East Texas Section, Sour Gas Symposium, Tyler.
Nov. 14-15.

Dill. W.R. and Keeney, B.R.: Optimtzing HCI-Formic Acid Mixtures

for High Temperature Stimulation, paper SPE 7567 presented at the
1978 SPE Annual Technical Conference and Exhibition, Houston,
Oct. l-3.

Holman, G-B.: State-of-the-Art

1982) 239-41.

Dunlap, P.M. and Hegner, IS.: An Improved Acid for Calcium Sulfate
Bearing Formations, J. Pet. Tech. (Jan. 1960) 67-70: Trans..
AIME. 219.
Eiy, .I., McDow. G., and Turner, I.: Stimulation Techniques Used
in the Austin Chalk, Proc., 29th Annual Southwestern Pet. Assn.
Short Course, Lubbock (1982) 110-2 1.
Fogler, H.S., Lund, K., and McCune, C.C.: Predictmg the Flow and
Reaction of HCliHF Acid Mixtures in Porous Sandstone Cores, Sue.
Per. Eng. J. (Oct. 1976) 248860; Trans., AIME, 261.
Ford, W.G.F. and Roberts, L.D.: The Effect of Foam on Surface
Kinetics m Fracture Acidizing. J. Pet. Tech. (Jan. 1985) 89-97.
Ford, W.G.F.: Foamed Acid, An Effective Stimulation Fluid, paper
SPE 9385 presented at the 1980 SPE Annual Technical Conference
and Exhibition, Dallas, Sept. 21-24.
Ford, W.G.F.. Burkleca. L.F., and Squire, K.A.: Foamed Acid
Stimulation Success in the Illmois and Michigan Basins, paper SPE
9386 presented at the 1980 SPE Annual Technical Conference and
Exhibition, Dallas, Sept. 21-24.
Graham. 1.W.: Well Stimulation by Two-Phase Flow, U.S. Patent
No. 4,174,753 (1979).
Green, E.B., Lybarger. J.H., and Richardson, E.A.: In-Situ
Neutralization System Solves Facility Upset Problems, Paper SPE
4796 presented at the 1974 SPE Annual Meetmg, Houston, Oct. 6-9.
Haafkens, R., Luque, R.F., and DeVries, W.: Method for Formmg
Channels of High Fluid Conductivity in Formation Parts Around a
Borehole, U.S. Patent No. 4,249,609 (1981).
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