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Chapter 54

Acidizing
A.W. Coulter Jr., Dwell-Schlumberger

A.R. Hendrickson, Dowell-Schlumberger

S.J. Martine2.u. of Tulsa *

Introduction
The use of acids to stimulate or to improve oil produc- at treating and well conditions, reservoir properties, and
tion from carbonate reservoirs was first attempted in 1895. rock characteristics are required to design an effective and
Patents covering the use of both hydrochloric and sulfur- efficient acidizing treatment. Since it is beyond the scope
ic acids for this purpose were issued at that time. Although of this text to cover all aspects of acidizing in detail, this
several “well treatments” were conducted, the process discussion will be limited to a general description of ma-
failed to arouse general interest because of severe corro- terials, techniques, and design considerations. A bibli-
sion of well casing and other metal equipment, The next ography is provided for those requiring a more detailed
attempts to use acid occurred between 1925 and 1930. discussion of a particular subject. Also, the major well
These consisted of using hydrochloric acid (HCl) to dis- stimulation companies providing acidizing services offer
solve scale in wells in the Glenpool field of Oklahoma literature and technical assistance for problem analysis and
and to increase production from the Jefferson Limestone treatment design.
(Devonian) in Kentucky. None of these efforts were suc-
cessful and “acidizing” once again was abandoned. General Principles
The discovery of arsenic inhibitors, which allowed HCl The primary purpose of any acidizing treatment is to dis-
to react with the formation rock without seriously damag- solve either the formation rock or materials, natural or
ing the metal well equipment, revived interest in oilwell induced, within the pore spaces of the rock. Originally,
acidizing in 1932. At that time, Pure Oil Co. and Dow acidizing was applied to carbonate formations to dissolve
Chemical Co. used these inhibitors with HCl to treat a the rock itself. Over a period of time, special acid for-
well producing from a limestone formation in Isabella mulations were developed for use in sandstone formations
County, MI. Results of this treatment were outstanding. to remove damaging materials induced by drilling or com-
When similar treatments in neighboring wells produced pletion fluids or by production practices.
even more spectacular results, the acidizing industry was There are two primary requirements that an acid must
born. meet to be acceptable as a treating fluid: (1) it must react
Throughout the years following those early treatments, with carbonates or other minerals to form soluble prod-
the acidizing industry has grown to one using hundreds ucts, and (2) it must be capable of being inhibited to pre-
of millions of gallons of acid applied in tens of thousands vent excessive reaction with metal goods in the well. Other
of wells each year. Technology has developed with in- important considerations are availability, cost, and safe-
creasing rapidity, and many changes and innovations have ty in handling. While there are many formulations avail-
been made to improve the effectiveness of acidizing treat- able, only four major types of acid have found extensive
ments. Because of new techniques of application and de- application in well treatments: hydrochloric, hydrofluoric,
velopment of additives to alter the characteristics of the acetic, and formic acids.
acid itself, acidizing has become a highly skilled science.
A knowledge of available materials, chemical reactions Hydrochloric Acid (HCI)
An aqeuous solution of HCl is most commonly used for
‘Authors of the OrigInal chapter on this topic I” the 1962 editlon Included th!s aulhor acidizing treatments, for reasons of economy and because
(deceased). P E. Rlzgerald. and Harold E Staadt it leaves no insoluble reaction product. When HCl is
54-2 PETROLEUM ENGINEERING HANDBOOK

T 3500 pumped into a limestone formation, a chemical reaction


I I
In
takes place, producing calcium chloride, CO*, and water.
/ 3000
16 This reaction is represented by the following equation:
I4

12

IO

n One thousand gallons of 15% HCI will dissolve approxi-


b mately 10.8 cu ft (1,840 lbm) of limestone. It will liber-
ate approximately 7,000 cu ft of CO1 , measured at
4
atmospheric conditions, and produce 2,042.4 lbm of cal-
2
cium chloride. This salt is dissolved in the original water
0
0 4 n I2 16 20 24 of the acid solution, plus 39.75 gal of water formed dur-
STRENGTH OF ACID, PERCENT BY WEIGHT ing the reaction. The specific gravity of this solution will
be 1.181 (20.4% calcium chloride). While 15 wt% HCI
Fig. 54.1-Solution of limestone in acid.
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 reac-
tion is the same and equivalent amounts of carbonate rock
TABLE 54.1~-HYDROCHLORIC ACID DENSITY AT 6O“F are dissolved. For example, 10,000 gal of 3% HCl solu-
tion will dissolve the same amount of rock as 1,000 gal
% HCI SpecificGravity' "Baume** lbmlgal psilft
depth of 28% HCl. Fig. 54.1 shows the effect of acid concen-
1.00 1.0048 0.7 8.377 0.4351 tration on the amount of limestone dissolved. The main
2.00 1.0097 1.4 8.418 0.4372 differences between the two solutions are their reaction
3.00 1.0147 2.1 8.460 0.4392
rates (or spending times) and their physical volumes.
4.00 1.0197 2.8 8.501 0.4415
5.00 1.0248 3.5 8.544 0.4437
Although lower concentrations of acid have greater
6.00 1.0299 4.2 8.586 0.4459 equivalent volumes, their reaction times and depth of
7.00 1.0350 4.9 8.629 0.4482 penetration into the reservoir, from the wellbore, are con-
8.00 1.0402 5.6 8.672 0.4504 siderably less than those of the higher-strength solutions.
9.00 1.0447 8.2 8.710 0.4524
10.00 0.4547
Reaction rates and penetration will be discussed later.
1.0500 6.9 8.754
11.00 1.0550 7.6 8 796 0.4568 Similar reactions occur when dolomite or impure lime-
12.00 1.0600 8.2 8.837 0.4590 stone is treated with HCI. Dolomitic lime contains a large
13.00 1.0646 8.8 8.876 0.4610 percentage of magnesium combined as calcium magnesi-
14.00 1.0702 9.5 8.922 0.4634
um carbonate. Although it reacts more slowly, this min-
15.00 1.0749 10.1 8.962 0.4654
16.00 1.0801 10.8 9.006 0.4677 eral also dissolves in HCl, and the resulting magnesium
17.00 1.0849 11.4 9.045 0.4698 chloride is soluble in the spent acid. Other impurities oc-
18.00 1.0902 12.0 9.089 0.4721 curring in limestone and dolomite are often insoluble in
19.00 1.0952 12.6 9.132 0.4743 acid, and if appreciable percentages of such components
20.00 1.1002 13.2 9.171 0.4764
are present, special additives must be included in the acid
21.00 1.1057 13.9 9.218 0.4788
22.00 1.1108 14.5 9.261 0.4810 solution to ensure their removal.
23.00 1.1159 15.1 9.303 0.4832 HCl ordinarily is manufactured in concentrations of 32
24.00 1.1214 15.7 9.349 0.4855 to 36 wt% HCl and is diluted at service company stations
25.00 1.1261 16.3 9.385 0.4876
to 15, 20, or 28% for field use. The concentrated acid,
26.00 1.1310 16.9 9.433 0.4899
27.00 1.1368 17.5 9.478 0.4922
the various chemical additives, and water are mixed in
28.00 1.1422 18.0 9.523 0.4946 the tank truck used to haul the acid to the wellsite. Table
29.00 1.1471 18.6 9.563 0.4967 54.1 lists the weights of various concentrations of HCI.
30.00 1.1526 19.2 9.609 0.4991 These data are useful in calculating mixing proportions
31.00 1.1577 19.8 9.663 0.5012
32.00 1.1628 20.3 9.694 0.5035
for acid dilution, using the following equation:
33.00 1.1680 20.9 9.738 0.5057
34.00 1.1727 21.4 9.777 0.5078
35.00 1.1779 21.9 9.820 0.5100 vda cda 7 da
36.00 1.1827 22.4 9.860 0.5121 vl-0 =
37.00 1.1880 22.9 9.924 0.5144 Cca(HCI)Yca '
38.00 1.1924 23.4 9.941 0.5163
39.00 1.1963 23.8 9.974 0.5180
40.00 1.2008 24.3 10.011 0.5199 where
41.00 1.2053 24.7 10.049 0.5219 V/da = final volume of dilute acid,
cdd = desired concentration of dilute acid,
?'du = specific gravity of dilute acid,
145
V,, = volume of concentrated acid required,
Cccr(HCI)= percent of HCI in concentrated acid, and
ycO = specific gravity of concentrated acid.

Approximate proportions of concentrated acid and water


required for dilution are shown in Fig. 54.2.
ACIDIZING 54-3

Determination of acid strength can be estimated in the FORMULA FOR MIXING ACID IN ANY DESIRED
field using either a hydrometer or a field titration kit. The CONCENTRATION:
accuracy of hydrometer readings depends on the care and VOLUME OF STRONG =
technique used by the field engineer. Both the hydrome- (VOL OF WEAK) (%WEAK) (SF? GR.OF WEAK)
ter and the glass cylinder in which the test is made should (=&OF STRONG) (SF’. GR.OF STRONG)
be free from oil or dirt. The spindle should float freely
GALLONS OFCONCENTRATED
in the acid, and all readings should be made at the lowest
7 HYDROCHLORIC ACID TO MAKE
level of the acid meniscus. The temperature of the acid
t 1,000 GALLONS OF DILUTE ACID
sample should be taken and the hydrometer reading cor- -8 - 32
rected to 60°F. - 30
Determination of acid strength by titration is simplified -9
-28
by the use of 0.59 N standard sodium hydroxide solution. - IO
If a 2-mL sample of the acid is titrated with this standard -II $? 3
solution to a methyl orange end point, the burette read- s-23
ing (milliliters of sodium hydroxide used) will be equal
to the acid strength (percent HCI).
-12
-13 0
1
& ’ 2:
Q-20
-14 2
2-I;
Acetic and Formic Acids I5 a -17
-16 z k-16
Acetic acid (CH3COOH) and formic acid (HCOOH) are -17 0
Z-15
weakly ionized, slowly reacting, organic acids. They are -189 E =-I4
used much less frequently than HCI and are suitable -2om
- 13
primarily for wells with high bottomhole temperatures
-2& k-12
(BHT’s above 250°F) or where prolonged reaction times
2,
are desired. The reaction of these acids with limestone
is described by the following equation: EKBG
-282
2HOrg+CaCOj +CaOrgz +HzO+CO,. :3oE
: 32 z
HAc is available in concentrations up to 100% as glacial -34w
:36g
HAc. while HCOOH is available in 70 to 90% concen-
1380
trations. For field use, HAc solutions normally are dilut- -400
ed to I5 % or less.
Above this concentration, one of the reaction products,
calcium acetate, can precipitate from its “spent acid” so-
lution because of its limited solubility. Similarly, the con-
centration of HCOOH normally is limited to 9 to 10% Fig. 54.2-Dilution of concentrated HCI
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 TABLE 54.2-DIFFERENT ACIDIZING SOLUTIONS
is desired, HCI is sometimes mixed with HCOOH or
Acid Relatwe
HAc. Such blends still provide extended reaction times.
Concentration CaCO, Eouivalent Reaction
when compared with HCl. HCOOH and HAc also may
Type (Ibm/l,i)OO
bal acid) time’
be blended together. Table 54.2 illustrates some of the
7.5 HCI 890 0.7
more common acid strengths and blends. 15 HCI 1,840 1.0
28 HCI 3,670 6.0
Hydrofluoric Acid (HF) 36 HCI 4,860 12.0
10 Formic 910 5.0
HF is used in combination with HCI and has been referred 10 Acetlc 710 12.0
to as “intensified acid” or “mud removal” acid. depend- 15 Acetic 1,065 18.0
ing on the formulation and use. HF is used primarily to
remove clay-particle damage in sandstone formations, to 7.5 Formic/
14 HCI mixture 2,420 6.0
improve permeability of clay-containing formations, and
to increase solubility of dolomitic formations. Its utility IO Acetic/
is based on the fact that some clays. silica, and other ma- 14 HCI mixture 2,380 12.0
terials normally insoluble in HCI have some degree of
solubility in HF. For example, I .OOOgal of an acid solu- 8 Formic/
14 Acetic mixture 1,700 18.0
tion containing 3% HF and 12% HCI will dissolve 500
lbm of clay and up to I .450 lbm of CaC03, ‘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
4HF+SiO? -tSiFJ +2H10

and

ZHF+SiF,+HzSiF,.
54-4 PETROLEUM ENGINEERING HANDBOOK

; 0.41 I I I
0.4 I I
I
\-MUD ACID z 0.3u
0.3 7’

0.2
I

0. I
/-REGULAR ACID
I
0 I I I I
0 6 12 18 24 1
TIME OF CONTACT IN HOURS 2 TIME OF CONTACT IN HOURS

Fia. 54.3-Solubilitvof bentonite in mud removal acid Fia. 54.4-Solubilitvof silicasand in mud removal acid

Figs. 54.3 and 54.4 compare solubilities of bentonite and hydrolyzes to form hydroxyfluoboric acid and HF, which
silica in HCl and HF acids. will dissolve clays.
In carbonates, application of HF/HCl mixtures must be
controlled carefully because of cost and possible precipi- HBF4 +HZO-‘HBF30H+HF.
tation of reaction products such as calcium fluorides or
complex fluosilicates, which have a very limited solubil- This reaction provides a slow-release source of HF, which
ity. For reaction with silicates, such as natural clays or can penetrate deeply before spending. Perhaps more im-
clays in drilling fluids, the blends usually contain 2 to 10% portant, the slowly generated hydroxyfluoboric acid reacts
HF and 5 to 26% HCI. The concentration of HCl used with clays to form a nonswelling, nondispersing product
in the blend should be equal to or greater than that of the that stabilizes fine clays and holds fine particles of silica
HF. in place.
The so-called “intensified acids” used in dolomitic for-
mations are mainly HCl containing small concentrations Acid Reaction Rates
of HF, usually about 0.25 % Intercrystalline films of sil- A knowledge of the factors affecting the reaction rate of
ica, insoluble in HCl, often occur in the crystal structure acids is important for several reasons. First, these fac-
of dolomite. When such are present, they prevent the acid tors, correlated with reservoir and formation character-
from contacting the soluble portions of the rock. The pres- istics, form a guide for the selection of acid type and
ence of fluoride intensifier in the acid will destroy such volume for a given treatment. Next, a study of these fac-
films, allowing the acid to react more completely with tors can furnish an understanding of what parameters
the soluble portions of the rock. Fig. 54.5 illustrates the govern spending time, which will determine how far a
comparative reaction rates of HCI and intensified acid on given formulation can penetrate into the formation before
dolomite formations. spending. Many factors govern the reaction rate of an
More recent developments of HF involve the use of acid, such as pressure, temperature, flow velocity, acid
delayed-action agents in sandstone acidizing. The first of concentration, reaction products, viscosity, acid type,
these was a self-generating mud acid system, reported by area/volume ratio, and formation composition (physical
Templeton er al. ’ The system provides slow generation and chemical). These factors have been the subject of ex-
of acid from the hydrolysis of methyl formate. yielding tensively reported research for many years. Details of such
methyl alcohol and HCOOH acid. The acid then reacts studies are available in published literature. Only a brief
with ammonium fluoride to yield HF in situ. They attrib- general discussion will be presented here.
ute the success of the system to getting the HF reaction
away from the wellbore into areas that conventional HF Pressure
solutions normally do not reach before spending. Equal- Fig. 54.6 shows the effect of pressure on the reaction rate
ly important factors are the techniques of application and of 15% HCl with limestone and dolomite at 80°F. Above
of returning the well to production following treatment. 500 psi, pressure has little effect on reaction rate. At bot-
The treatment technique mvolves use of an aromatic sol- tomhole treating pressures, there is only a small differ-
vent and mud acid preflush, along with the self-generating ence (a factor of 1.5 to 2) in the comparative reaction of
mud acid (SGMA). The wells are returned to production acid with limestone and dolomite compared to the rather
by opening the choke gradually over a 90-day period and large difference (a factor of about 10) at atmospheric
never allowing an excessive drawdown. The process is pressure.
available from most service companies as SGMA.
A significant development in this area of slow-reacting, Temperature
HF-supplying, clay-dissolving acid has been the fluoboric Acid reaction rate increases directly with temperature. At
acid system reported by Thomas and Crowe.’ This acid 140 to 150”F, the reaction rate of HCI and limestone is
ACIDIZING 54-5

.INTENSIFIED

- MARBLE

5 IO 15 20 25 400 800 1200 1400 2000 2400


TIME IN MINUTES PRESSURE (PSI)

Fig. 54.5-Comparative reaction rates of conventional and Fig. 54.6-Effect of pressureon reaction rate (15% HCI tit
80°F).
intensified
acids.

approximately twice that at 80°F. 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 I
reaction rate of 15 % HCl with CaCO 3. This velocity ef- 10 IO0 1,000 10,000 40,000

fect is more pronounced in narrower fractures. Reaction , ACID FLOW VELOCITY ,s,ce,

rate is a function of shear rate, 6 v/b, set - ’ as illustrat- FIAClUlE WIDTII


ed by the following equation:
Fig. 54.7-Effect of flow on reaction rate (15% HCI with
R=[(28.5 v/b)0.8+184]x10-6, . . . . . . . . . . . ...(l) CaCO,).

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 80°F 54.8. Above 25% HCl, the reaction rate actually decreases
under 1,100 psi pressure.) because of reduced acid activity. As acid spends, the reac-
The flow velocity in fractures and channels depends on tion rate decreases as a result of reduced acid concentra-
injection rate and actual geometry of the flow path. tion and the retarding effect of dissolved reaction products,
such as calcium or magnesium chloride.
vd=O. 18i,,l(rfb) (radial fracture), . . .(2a)
Area/Volume Ratio
vlf= 1,15i,,l(hb) (linear fracture), . .. (2b) Area/volume (A/V) ratio is one of the major factors affect-
ing reaction rate spending time, and may vary over a wide
v,, = 17.2i,,/d2 (cylindrical channel). . . . .(2c) range. This ratio, the area in contact with a given volume
of acid, is inversely proportional to pore radius or frac-
where ture width. Fig. 54.9 shows the time required for 15%
v = flow velocity in fractures and channels, HCl to spend on marble, at 80°F and 1,100 psi, for three
ftlsec, different A/V ratios.
= acid injection rate, bbl/min, The term “spending time” has very little meaning or
1ac
value by itself. It must be related to flow geometry and,
rf = fracture radius, ft,
thus, to the distance the acid penetrates before it is spent.
h = fracture height, ft,
In matrix acidizing, extremely high A/V ratios may be
d = channel diameter, in., and encountered. For example, a IO-md, 20%-porosity lime-
b = fracture width, in. stone may have an A/V ratio of 28,000 to 1. In such a
formation, it would be very difficult to obtain significant
Acid Concentration penetration before spending. A natural fracture, 0.00 1 in.
Reaction rate increases with acid concentration up to 24 wide, has an A/V ratio of 3,200: 1. A 0. l-in. fracture has
to 25% HCl, but not proportionally, as shown in Fig. an A/V ratio of 32: 1. The smaller ratios in wider frac-
PETROLEUM ENGINEERING HANDBOOK

“0 10 20 30 40 50 60 ‘0
Th4E (min)

Fig. 54.9-Effect of A/V ratioon spending time (15% HCI, 80°F


and 1,100 psi).

Two formations having the same acid solubility and per-


meability may respond differently to acid treatment be-
cause of variances in physical structure.
I
Acid Additives
0 5 IO I5 20 25 30 35
The use of a corrosion inhibitor as an additive made pos-
PERCENT HCI sible the firstcommercially feasible acidizing treatments.
Since that time, many auxiliary chemicals have been de-
veloped to modify acid solutions, influencing their appli-
Fig. 54.8-Effect of concentrationon reactionrate and spend-
ing rate. cation and recovery.

Corrosion Inhibitors
Inhibitors are chemical materials that, when dissolved in
TABLE 54.3-EFFECT OF TEMPERATURE acid solutions, greatly retard the reaction rate of the acid
ON ORGANIC INHIBITOR PROTECTION
TIME
with metals. They are used in acidizing to avoid damage
to casing, tubing, pumps, valves. and other well equip-
Protection ment. Inhibitors cannot completely stop all reaction be-
Concentration Temperature Time tween the acid and metal; however, they do slow the
WI C’F) (hours)
reaction, eliminating 95 to 98% of the metal loss that
0.6 175 24 would otherwise occur. Most inhibitors have practically
1.0 250 6
2.0 300 6
no effect on the reaction rate of acid with limestone, dolo-
2.0’ 350 4 mite, or acid-soluble scale deposits.
The length of time that an inhibitor is effective depends
‘With mhtbltor aId on the acid temperature, type of acid, acid concentration,
type of steel, and the inhibitor concentration.
Organic inhibitors in HCI are effective up to 400”F,
but above 200°F relatively large concentrations are re-
tures allow greater penetration of the acid into the reser- quired. The effect of temperature on corrosion inhibition
voir before spending is complete. is illustrated in Table 54.3.
Equations have been developed for estimating BHT’s
Formation Composition during acid treatments. By knowing these temperatures,
Probably the most important factor that governs effective- adequate corrosion protection can be provided, even in
ness of an acidizing treatment is the rock composition. wells with static BHT’s up to 400°F.
Its chemical and physical characteristics determine how
and where the acid will react with and dissolve the rock. Surfactants
From the standpoint of chemical composition, there is Surfactants are chemicals used to lower the surface terl-
little difference in the reaction rate of HCI on most lime- sion or interfacial tension of fresh acid or spent acid so-
stones, all other factors remaining constant. The physi- lutions. The use of a surfactant improves the treating
cal rock texture. however, can control pore size efficiency in a number of ways.
distribution. A/V ratio, pore geometry, and other prop- The presence of a surfactant improves the penetrating
erties. This, in turn, influences the type of flow channels ability of the acid solution entering a formation. This is
created by acid reaction and is the key to acid response. extremely desirable in matrix acidizing treatments. be-
ACIDIZING 54-7

z
-
ST
3; I
2 lpoo
0’800yORDlNARY
a A C I D ,
0
g 6 0 0 /
i;i

Egjpek&
k!
3
0 5 IO 15 20
PENETRATION IN FORMATION- FEET
z
E PHI t-942 PH3 PHI PH5

Fig. 54.10—Effect of surface-tension-reducing agent in facili- Fig. 54.11—Photograph showing effect of pH on the volume of
tating return of spent acid. silicate particles.

cause it provides deeper penetration of acid into the for- mites. One of the characteristics of these silicates is that
mation. In addition, surfactants permit the acid to they will swell in spent acid. Naturally, this is undesirble
penetrate oily films clinging to the surface of the rock and because swollen silicate particles may block formation
lining the pores, so that the acid can come in contact with flow channels, reducing well production.
the rock and dissolve it. Silicate-control additives are chemicals that prevent
The use of surfactants also facilitates the return of spent released silicate particles from adsorbing water. Some
acid following the treatment (Fig. 54.10). Wetting of the buffer the pH of the solution near the isoelectric point
formation is more nearly complete and there is less (where the volume of the swelled clays is at a minimum).
resistance to flow of the acid, so that the spent acid is Others cause shrinkage of the silicate particles by replac-
readily returned through the treated section. This is es- ing the adsorbed water molecules with a water-repellent
pecially important in low-pressure wells. organic film. Thus, possible formation plugging is
Another advantage in the use of surfactants in acid is prevented, treating pressures are lowered, faster cleanup
the demulsifying action obtained. Many surfactants are is provided, and the occurrence of particle-stabilized emul-
capable of inhibiting the occurrence of emulsions or de- sions is minimized. This is illustrated in Fig. 54.11.
stroying those already formed.
Surfactants also promote dispersion and suspension of Iron-Control Agents
fine solids to provide better cleanup following treatment. Iron control is approached two ways. The oldest and most
These solids may be either mud solids or natural fines common approach is to use sequestering agents, which
released from the formation. They are suspended and act by complexing iron ions, thereby preventing precipi-
physically removed from the formation. tation when the acid spends. A second method is use of
Special surfactants are used as antisludge agents. Some reducing agents that reduce any ferric ions (Fe3+) to fer-
crudes form an insoluble sludge when in contact with acid. rous ions (Fe2+), which do not precipitate as the hydrox-
The sludge consists of asphaltenes, resin, paraffin, and ide or hydrous oxide until the pH of the system is above
other complex hydrocarbons. The acid reacts with the 7. Since acids in contact with the formation rock will not
crude at the interface, forming an insoluble film. The spend to a pH that high, the hydroxide will not damage
coalescence of this film, which results on the sludge par- the well. Spent acid usually has a pH between 4.5 and
ticles, can be avoided by use of proper additives. Ethyl- 6.5, no higher.
ene glycol monobutyl ether is a mutual solvent surfactant Erythorbic acid is one of the most effective reducing
used in matrix sandstone acidizing to water-wet the for- agents that can be used for this purpose. The reduction
mation. This agent prevents particle migration and sub- of all the ferric iron to ferrous iron, however, does not
sequent particle plugging. It improves cleanup by prevent the precipitation of ferrous sulfide (FeS), which
preventing the stabilization of emulsions by fine particles. precipitates when the acid spends to a pH of 2, as it will
Many different surfactants are used in acidizing. Type and readily in almost any formation. To protect fully against
concentration for a particular application should be select- iron precipitation in a sour well, a complexing agent is
ed on the basis of laboratory testing. needed. Citric, lactic, and acetic acids as well as EDTA
or NTA are popular sequestrants. In some wells where
Silicate-Control Agents H 2S can become mixed with the acid it also may be ad-
Various silicate compounds, commonly known as clays visable to use both the reducing agent and the sequester-
and silts, usually are present in most limestones and dolo- ing agents, since ferric iron can react with H 2S to
54-8 PETROLEUM ENGINEERING HANDBOOK

precipitate free sulfur, which itself can damage permea- face because of the presence of an interfering oil film.
bility The loss of effectiveness of acetic acid at tempera- This is particularly true for emulsions with at least 20%
tures above 125°F and the possibility of precipitating oil as the outer phase. Certain surfactants recently have
calcium citrate also are factors that should be considered been found to be beneficial in reducing reaction rate and,
in guarding against iron precipitates. thus, extending spending time and penetration distance.
These surfactants, in the presence of oil, provide a
Alcohols hydrophobic or water-repellent, oil-like film on the rock
Methyl and isopropyl alcohols sometimes are used at con- surface that restricts acid/rock contact. Fluid-loss mate-
centrations of 5 to 20 ~01% of acid to reduce surface ten- rials and gelling agents (acid-thickening additives) also
sion. Methyl alcohol is sometimes used at concentrations, tend to reduce the reaction of HCl by film development
up to 66 % to increase vapor pressure of the acid and spent on rocks.
acid solution. Use of alcohols thus improves both rate and High concentrations of an acid provide longer reaction
degree of cleanup, which can be particularly helpful in times than lower concentrations because (1) there is more
dry gas wells. acid to react, (2) the additional reaction products further
retard reaction rates, and (3) the enlarged flow path, with
Gelling and Fluid Loss Agents reduced A/V ratio, extends the spending time and penetra-
tion of a high-concentration acid. For example, 28% HCl
Natural gums and synthetic polymers are added to acid may take four to six times longer to react completely than
to increase the viscosity of the acid solution. 3 This does 15% HCl. In this case, the reaction time is extend-
reduces leakoff into large pore spaces and, to some ex-
ed in spite of the initially faster reaction rate of the
tent, into natural hairline fractures. It also provides some
28% HCl.
degree of reaction rate retardation.
Other materials used to control leakoff are fine (IOO-
mesh) sand4 and fine salt.5 These materials bridge in Acidizing Techniques
hairline fractures to reduce fluid flow out of the main frac-
There are three fundamental techniques used in acidizing
ture during fracture acidizing treatments.
treatments.
Another successful fluid-loss control agent is a mixture
1. We&ore Cleunup. This entails fill-up and soak of
of finely ground, oil-soluble resins. 6 Originally designed
acid in the wellbore. Fluid movement is at a minimum,
as a diverting agent for use through gravel packs during
unless some mechanical means of agitation is used.
sandstone matrix acidizing treatments, this agent was later
2. Matrix Acidiz,ing. This is done by injecting acid into
shown to be effective as a fluid-loss agent in fracture
the matrix pore structure of the formation, below the
acidizing, when used at higher concentrations. ’
hydraulic fracturing pressure. Flow pattern is essentially
through the natural permeability structure.
Liquefied Gases
3. Acid Fmcturing. This is injection into the forma-
Liquid nitrogen and liquid CO2 sometimes are used in tion above hydraulic fracturing pressure. Flow pattern is
acid solutions to provide added energy for better well essentially through hydraulic fractures: however, much
cleanup. Nitrogen also is used to make foamed acid, which of the fluid does leak off into the matrix along the frac-
provides excellent leakoff control in low permeability ture faces.
rock. 8.9 The technique selected will depend on what the opera-
tor wishes to accomplish with the treatment.
Retarded Acids Matrix acidizing may be selected as a proper technique
It is often desirable in acid fracturing treatments to retard for one or more of the following reasons: (1) to remove
the reaction rate of the acid to provide deeper penetra- either natural or induced formation damage, (2) to achieve
tion of active acid into the formation. Retardation may low-pressure breakdown of the formation before fractur-
be accomplished by use of slower-reacting acids (HAc ing, (3) to achieve uniform breakdown of all perforations,
and HCOOH), by adding chemicals to reduce reaction (4) to leave zone barriers intact, or (5) to achieve reduced
rate, or by increasing concentration to extend spending treating costs.
time. The principal types of formation damage are mud in-
HAc and HCOOH are weakly ionized and sometimes vasion, cement, precipitates, saturation changes, and
are used to obtain longer reaction time. The additional migration of fines. The effect of damage on injectivity
cost of these acids may prohibit extensive use in certain or productivity is shown in Figs. 54.12 and 54.13. It can
formations. Deeper matrix penetration than would be ob- be seen that the greatest flow increase results from restor-
tained by HAc or HCOOH is obtained by the faster- ing the natural rock permeability. The magnitude of this
reacting HCl because the channeling or wormhole effect primary flow increase depends on the extent (radius) of
produced by the HCl reduces the A/V ratio, thus prolong- the damage. Further increase in pore size by matrix acidiz-
ing reaction time. In fractures, the HAc and HCOOH ing results in only a limited increase in flow (stimulation).
would obtain deeper penetration than HCl; however, larg- If the producing formation does not have enough natural
er volumes would be required to dissolve an equivalent permeability, then a hydraulic fracturing treatment should
amount of rock. be considered. The primary purpose of fracturing is to
Some chemicals, added to HCl, form a barrier on the achieve injectivity or productivity beyond the natural
rock surface, which interferes with its normal contact and reservoir capability. An effective fracture may create a
“retards” the reaction rate of the acid. Acid-in-oil emul- new permeability path, interconnect existing permeabil-
sions generally exhibit retarded reaction rates. The acid ity streaks, or break into an untapped portion of the
in the emulsion does not completely contact the rock sur- reservoir.
ACIDIZING 54-9

00 25

5 m

0
I 2 3 4 6 7 0 9 lo
RADIAL EXTENTd c4ALGul ZorE. FEET I IO 100 1000
PERCENT OF NATURAL 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 con-
ductivity can be achieved, then increased penetration be-
comes 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 forma-
tion rock often affect the results of an acidizing treatment.
McGUlRE AND SIKORA
In some cases, the use of special additive chemicals will
improve the action of the acid or avoid cleanup difficul- IO' IO' IO' ID' IO'

ties in returning the spent acid following the job. It is im- RELATIVE CONDUCTIVITY, bk#,,-In

portant, therefore, that samples of the formation rock


(either cores or cuttings) and, if possible, samples of the Fig. 54.14-Relationship of conductivityand penetration to
crude oil and formation brine be subjected to laboratory productivityincrease.J= productivity index of well
testing before acidizing to design the most effective after stimulation,J, = productivityindex before
stimulation,ri= radiusof fracture(ft),
re = drainage
treatment.
radius (ft).k,=permeability of fracture (md),
Customarily, permeability. porosity, and oil- and water- k, = permeabilityof formation (md), and b = frac-
saturation tests are run on formation core samples, using ture width (in.).
standardized core-analysis procedures. In addition, acid-
solubility tests are run to determine to what extent the for-
mation will respond to an acidizing treatment. with the acid to be used in the acidizing treatment and
Formation solubility may be determined two different then are shaken. The mixture is allowed to stand, and the
ways. In the first method, a weighed chunk of the rock time required for the oil and acid to separate is observed.
is immersed in an excess of acid and maintained at for- Additional tests are run on mixtures of the crude oil with
mation temperature. After an hour, any insoluble residue acid that has been spent completely on pulverized forma-
is washed. dried, and weighed. With samples known to tion rock. If the formation crude shows a tendency to
contain silicates, additional tests may be run in which the emulsify with either the fresh acid or the spent acid, the
rock is exposed to the dissolving action of combined HCl use of an appropriate surfactant is indicated.
and HF. Similar tests using a mixture of crude and acid are made
A more rapid test, suitable for samples known to con- to determine acid sludging tendencies. Sludge is identi-
sist largely of limestone or dolomite, entails dissolving fied by filtering the mixture through a small mesh screen.
a weighed sample of the rock in an excess of HCl and Appropriate surfactants that are added to the acid to pre-
measuring the volume of CO* gas evolved during the vent sludge formation are evaluated.
reaction. A simple apparatus for conducting this test is Other determinations of rock characteristics include
shown in Fig. 54.15. tests for clay swelling tendencies and tests to determine
In addition to these tests of the formation rock, the emul- rock composition (such as X-ray diffraction analysis) to
sifying tendencies of the formation crude should be deter- indicate need for stabilizers, sequestering agents, or other
mined whenever possible. Samples of the crude are mixed acid additives.
54-10 PETROLEUM ENGINEERING HANDBOOK

TABLE 54.4-FLOW THROUGH PORES OF VARIOUS


SIZES

Diameter of Pore Pore Volume Flow Through Pores


(A w (% of Total Flow)
il 60 10
1 to 2 25 15
2 to 5 12 30
5 and above 3 45

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


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 dis-
persing fine undissolved solids. These may be drilling
mud, cement solids, or natural clay particles released from
the formation. Suspension and removal of these materi-
als 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, perfo-
ration ball sealers, gel slugs, etc., have been used suc-
cessfully 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 pres-
sure is recommended. In certain cases, it may be neces-
sary 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 con-
Fig. 54.15-Laboratory solubillty
tester(carbon dioxide evolu- cern. Maintaining bottomhole pressures below hydraulic
tion method). fracturing pressures may restrict injection rates to only
fractional barrels per minute. An increasing rate may then
be possible as the treatment progresses.
Acid Treatment Design Because of differences in the size and shape of the pores,
penetration of acid in a carbonate rock is far from uni-
Three techniques of acidizing have been described previ- form. Porosity anomalies may result from vugs, hairline
ously. Wellbore cleanup treatments normally do not re- fissures, or tortuous capillary-like pores. Because of these
quire complicated design procedures. Matrix and fracture heterogeneities, a “channeling” or “wormholing” occurs
acldlzmg treatments. on the other hand, can involve ex- with most acid formulations. The resultant effect is the
tensive predesign laboratory testing and complicated de- attainment of much greater acid penetration of matrix than
sign procedures and calculations. expected.
The wide distribution of flow in a rock of varying pore
Matrix Acidizing-Carbonate Formations diameters (Table 54.4) is further accentuated by acidiz-
Matrix acidizing in carbonates normally is used to break ing. As discussed in a preceding section, the fast-reacting
down all perforations and to remove damage. Plugging HCl may provide greater penetration of the limestone
materials can be removed and permeability restored in matrix than the slow-reacting acetic acid, but not as great
two ways: (1) by dissolving the damaging material itself as with the emulsified or gelled acids. Evidently, the slow
or (2) by dissolving part of the rock in which the damage reaction of acetic acid does not change the flow distribu-
exists. In carbonate rocks with acid solubilities greater tion rapidly enough to “channel,” but rather results in
than 50%) the latter method is often most effective. The several small pore enlargements for short distances as op-
dislodged solid particles or liquids then can bc removed posed to a few large, long channels.
physically by the return of the spent acids to the well. Since the formation damage normally does not exist for
HCI normally is used in matrix treatments of car- a great distance from the wellbore, the volume of acid
bonates, but HAc and/or HCOOH should be considered needed is small. With a formation porosity of IO%, 60
ACIDIZING 54-11

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 deep-
er than 5 to 10 ft, then larger volumes of acid, a means
of retarding the reaction rate, or, perhaps, fracturing tech-
niques, may be required. Very little rock must be dis-
solved to result in a significant amount of damage repair
or permeability increase. Removal of only 1% of lime-
stone or dolomite rock for a distance of about 5 ft from
the wellbore requires only 70 gal of 15 % HClift of verti-
cal interval.
An overflush in the matrix acidizing treatment is rec-
ommended. This will ensure efficient displacement of the
acid into the matrix. A minimum shut-in time is recom-
mended before returning the spent acid to the well. Since "0 5 IO 15 20
the spending time of acid is short, a long shut-in time of MUD ACID VOLUMf RfPUIRfMENT5 (p.l/f12)
several hours is not necessary, even for the so-called
‘‘retarded acid. ’’The overflush fluid may be brine, water, Fig. 54.16--Response of cores from producing formations to
oil, or a weak acid. Enough volume should be used to mud acid.
ensure maximum penetration of the last portion of the
acid, before it is spent.

Matrix Acidizing--Sandstone Formations acid should be returned to the wellbore as soon as the in-
The purpose of sandstone acidizing is to restore permea- itial spending time has elapsed. The spent HF/HCl acids
bility by dissolving away formation-damaging clay-like should not be allowed to mix with formation brine, if at
minerals or other acid-soluble materials. The clay may all possible because of the danger of precipitates.
be inherent in the formation or may be the result of drill- Inhibitors, surfactants, and diverting methods should
ing mud or workover fluid invasion. be selected just as in an HCl acid treatment. As in the
The type of acid used most often in sandstones is a mix- case of matrix acid treatment in carbonates, an overflush
ture of HF and HCl. These mixtures commonly are rem is recommended. Suitable fluids include weak acid, oil,
ferred to as mud acids or mud removal acids. As or water. Formation brine should not be used to over-
previously discussed, fluoboric acid also has become flush HF/HCl. Short shut-in times should be used-a few
popular in sandstone formations. Concentrations of 2 to hours at the most.
6 % HF and 8 to 12 % HCl normally are used. If a signifi-
cant amount of calcium carbonate is present in the for- Fracture Acidizing-Carbonate Formations
mation (5 to lo%), a spearhead of HCl should be used The primary purpose of an acid fracturing treatment of
to react with it before the HF/HCl is injected. With car- a carbonate formation is to achieve productivity or injec-
bonate content above 20%, HF acid probably is not need- tivity beyond the natural capabilities of the reservoir. It
ed, except to give entry through clay damage. is most applicable in formations with a low and/or ineffec-
As in any matrix-type treatment, injection of the tive permeability structure. The effectiveness of an in-
HF/HCl should he below fracturing pressure. The volume duced hydraulic fracture is a function of both its
of acid required depends on the depth and severity of the conductivity and the extent of penetration of the drainage
damage. A total of 50 to 250 gal of acid per foot of inter- radius of the well.
val is the normal treatment volume, if damage is not ex- These factors will depend on well and reservoir prop-
tensive. An acid solubility test may not be a realistic erties, formation characteristics, injection rate, type and
evaluation of acid requirements. volume of acid used, and shape and orientation of the frac-
Results of a field study by Gidley et al. lo confirmed ture. All these factors have been correlated by several
some earlier recommendations based on laboratory core companies into “guides” to acid fracture treatment de-
flow studies. These results showed much greater success sign. Such guides provide mathematical relationships for
when more than 125 gal/t? acid was used. determining the fracture area and conductivity achieved
The reported core flow test showed what response the by different volumes of specific acid formulations at var-
formation will have to acid. This is illustrated in Fig. ious injection formulations. These guides are programmed
54.16. Although some of these formations have approxi- for computer calculation, so that rapid comparison of var-
mately the same acid (HF/HCI) solubility, permeability, ious treatment designs can be made for selection of best
and porosity, the response to acid is quite different. results per dollar of treatment cost. These guides are not
Initial reduction in permeability is a common occurrence sufficiently similar to get clear comparison between differ-
observed with many formation core flow tests. It is at- ent companies but should be compared only with other
tributed to sloughing particles (clays, silica, fines, etc.) calculations from the same system.
that apparently bridge in the flow channels and restrict
flow, before their further reaction with the acid. An in- Critical Wells
adequate acid volume treatment could lead to a restricted In ultradeep, high-temperature wells, many factors must
permeability in a formation, if the bridging is severe. be considered in the stimulation treatment design. First,
Since secondary reactions may occur, resulting in pos- the high BHT can drastically affect reaction rate of acid,
sible precipitation of damaging reaction products, mud inhibition, and other properties of the acid formulation.
54-12 PETROLEUM ENGINEERING HANDBOOK

These effects can be partially offset by formation cool- 9. Scherubel, GA. and Crowe, C.W.: “Foamed Acid: A New
down techniques. Basically, this consists of pumping a Concept in Fracture Acidiaing,” paper SPE 7568 presented at&he
1978 SPE Annual Technical Conference and Exhibition. Houston,
pad volume of fluid (generally gelled water) into the for- Oct. 1-3.
mation to cool the rock to a more normal treating tem- 10. Gidley, J.L., Ryan, J.C., and Mayhill, T.D. : “Study of Field
perature. Most companies have computer programs Applications of Sandstone Acidizing,” /. Per. Tech. (Nov. 1976)
available to calculate pad volumes required for a given 1289-94.

temperature reduction.
General References
Another problem is created when fluids with tempera-
tures lower than BHT’s are used. This problem is me- Abram, A. ef al: “The Development and Application of a High pH Acid
Stimulation System for a Deep Mississippi Gas Well,” paper SPE 7565
chanical and involves tubing movement. In ultradeep
presented at the 1978 SPE Annual Technical Conference and
wells, such contraction can create stress in the tubing Exhibition, Houston, Oct. 1-3.
greater than tubing strength, resulting in a parted string.
The solution to this problem is to slack off or to release Barron, A.N., Hendrickson,A.R., and Wieland, D.R.: “The Effect
tension at the top of the tubing string as the job progress- of Flow on Acid Reactivity in a Carbonate Fracture,” J. Per. Tech.
(April 1962) 409-15; Trans., AIME, 225
es. Again, computer programs are available from most
service companies to predict tubing movement under given Black, H.N. and Stubbs, B.A.: “A Case History Study-Evaluation
conditions. of San Andres Stimulation Results,” paper SPE 5649 presented at the
1975 SPE Annual Technical Conference and Exhibition, Dallas, Sept.
29-Oct. 1.
Summary
In summary, acidizing is a process that uses reactive ma- 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
terials to increase well production by dissolving either the Production Dev. Mid-Continent Dist., Wichita, March 31-April 2,
reservoir rock or damaging materials blocking the pore 1965.
spaces of the rock. Different kinds of acids and additives
are available, so that treating fluids can be tailored to meet Burkill, G.C.C. and Pierre, M.L.: “Successful Matrix Acidizing of
individual well needs. Acid formulations may be applied Sandstones Requires a Reliable Estimate of Wellbore Damage,” paper
SPE 5590 presented at the 1975 SPE Annual Technical Conference
in either matrix- or fracture-type treatment, depending on and Exhibition, Dallas, Sept. 29-Oct. I,
the degree of stimulation or production increase desired.
While acidizing, and acidizing treatment design, in de- Chat&in, J-C., Silberberg, I.H., and Schechter, R.S.: “Thermodynamic
tail are beyond the scope of this text, published literature Limitations in Organic Acid-Carbonate Systems,” Sot. Per. Eng. J.
(Aug. 1976) 189-95.
offers answers and assistance in solving many of the prob-
lems encountered. The General References cover many Church, D.C., Quisenberry, J.L., and Fox, K.B.: “Field Evaluation
of the recent technical developments in this field. In ad- of Gelled Acid for Carbonate Formations,” J. Pet. Tech. (Dec. 1981)
dition, most service companies providing acidizing serv- 241 l-74
ice offer laboratory facilities, technical assistance, and
Clark. G.J., Wong, T.C.T., and Mungan, N.: “New Acid Systems for
computer programs for problem analyses and treatment Sandstone Stimulation,” Proc., SPE Formation Damage Control
design. 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.
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