Guo, Boyun / Computer Assited Petroleum Production Engg 0750682701_chap16 Final Proof page 243 21.12.

2006 2:30pm

16 Matrix Acidizing

Contents
16.1 Introduction 16/244
16.2 AcidRock Interaction 16/244
16.3 Sandstone Acidizing Design 16/244
16.4 Carbonate Acidizing Design 16/247
Summary 16/248
References 16/248
Problems 16/249
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16/244 PRODUCTION ENHANCEMENT

16.1 Introduction
Matrix acidizing is also called acid matrix treatment. It is a
technique to stimulate wells for improving well inflow per-
formance. In the treatment, acid solution is injected into the
formation to dissolve some of the minerals to recover per-
meability of sandstones (removing skin) or increase per-
meability of carbonates near the wellbore. After a brief
introduction to acidrock interaction, this chapter focuses
on important issues on sandstone acidizing design and
carbonate acidizing design. More in-depth information
can be found from Economides and Nolte (2000).
16.2 AcidRock Interaction
Minerals that are present in sandstone pores include mont-
morillonite (bentonite), kaolinite, calcite, dolomite, sider-
ite, quartz, albite (sodium feldspar), orthoclase, and
others. These minerals can be either from invasion of
external fluid during drilling, cementing, and well comple-
tion or from host materials that exist in the naturally
occurring rock formations. The most commonly used
acids for dissolving these minerals are hydrochloric acid
(HCl) and hydrofluoric acid (HF).
16.2.1 Primary Chemical Reactions
Silicate minerals such as clays and feldspars in sandstone
pores are normally removed using mixtures of HF and
HCl, whereas carbonate minerals are usually attacked
with HCl. The chemical reactions are summarized in
Table 16.1. The amount of acid required to dissolve a
given amount of mineral is determined by the stoichiom-
etry of the chemical reaction. For example, the simple
reaction between HCl and CaCO3 requires that 2 mol of
HCl is needed to dissolve 1 mol of CaCO3 .
16.2.2 Dissolving Power of Acids
A more convenient way to express reaction stoichiometry
is the dissolving power. The dissolving power on a mass
basis is called gravimetric dissolving power and is defined as
nm MWm
b Ca , (16:1)
na MWa
where
b gravimetric dissolving power of acid
solution, lbm mineral=lbm solution
Ca weight fraction of acid in the acid solution
nm stoichiometry number of mineral
na stoichiometry number of acid
MWm = molecular weight of mineral
MWa molecular weight of acid.
For the reaction between 15 wt% HCl solution
and CaCO3 , Ca 0:15, nm 1, na 2, MWm 100:1,
and MWa 36:5. Thus,
(1)(100:1)
b15 (0:15)
(2)(36:5)
0:21 lbm CaCO3 =lbm 15 wt% HCl solution:
The dissolving power on a volume basis is called volumet-
ric dissolving power and is related to the gravimetric dis-
solving power through material densities:
r
X b a, (16:2)
rm
where
X volumetric dissolving power of acid solution,
ft3 mineral=ft3 solution
ra density of acid, lbm =ft3
rm density of mineral, lbm =ft3
16.2.3 Reaction Kinetics
The acidmineral reaction takes place slowly in the rock
matrix being acidized. The reaction rate can be evaluated
experimentally and described by kinetics models. Research
work in this area has been presented by many investigators
including Fogler et al. (1976), Lund et al. (1973, 1975), Hill
et al. (1981), Kline and Fogler (1981), and Schechter (1992).
Generally, the reaction rate is affected by the characteristics
of mineral, properties of acid, reservoir temperature, and
rates of acid transport to the mineral surface and removal of
product from the surface. Detailed discussion of reaction
kinetics is beyond the scope of this book.
16.3 Sandstone Acidizing Design
The purpose of sandstone acidizing is to remove the dam-
age to the sandstone near the wellbore that occurred dur-
ing drilling and well completion processes. The acid
treatment is only necessary when it is sure that formation
damage is significant to affect well productivity. A major
formation damage is usually indicated by a large positive
skin factor derived from pressure transit test analysis in a
flow regime of early time (see Chapter 15).
16.3.1 Selection of Acid
The acid type and acid concentration in acid solution used
in acidizing is selected on the basis of minerals in the
formation and field experience. For sandstones, the typical
treatments usually consist of a mixture of 3 wt% HF and
12 wt% HCl, preceded by a 15 wt% HCl preflush. McLeod
(1984) presented a guideline to the selection of acid on the
basis of extensive field experience. His recommendations
for sandstone treatments are shown in Table 16.2.
McLeods recommendation should serve only as a starting
point. When many wells are treated in a particular forma-
tion, it is worthwhile to conduct laboratory tests of the
responses of cores to different acid strengths. Figure 16.1
shows typical acidresponse curves.

Table 16.1 Primary Chemical Reactions in Acid Treatments

Montmorillonite (Bentonite)-HF/HCl: Al4 Si8 O20 (OH)4 40HF 4H $ 4AlF
2 8SiF4 24H2 O
Kaolinite-HF/HCl: Al4 Si8 O10 (OH)8 40HF 4H $ 4AlF
2 8SiF4 18H2 O
Albite-HF/HCl: NaAlSi3 O8 14HF 2H $ Na AlF

2 3SiF4 8H2 O
Orthoclase-HF/HCl: KAlSi3 O8 14HF 2H $ K AlF 2 3SiF4 8H2 O
Quartz-HF/HCl: SiO2 4HF $ SiF4 2H2 O
SiF4 2HF $ H2 SiF6
Calcite-HCl: CaCO3 2HCl ! CaCl2 CO2 H2 O
Dolomite-HCl: CaMg(CO3 )2 4HCl ! CaCl2 MgCl2 2CO2 2H2 O
Siderite-HCl: FeCO3 2HCl ! FeCl2 CO2 H2 O
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MATRIX ACIDIZING 16/245

16.3.2 Acid Volume Requirement and

The acid volume should be high enough to remove near-

Vm p r2a
r2w 1
fCm , (16:4)
wellbore formation damage and low enough to reduce cost

of treatment. Selection of an optimum acid volume is VP p r2a
r2w f, (16:5)
complicated by the competing effects. The volume of acid
needed depends strongly on the depth of the damaged where
zone, which is seldom known. Also, the acid will never ra radius of acid treatment, ft
be distributed equally to all parts of the damaged forma- rw radius of wellbore, ft
tion. The efficiency of acid treatment and, therefore, acid f porosity, fraction
volume also depends on acid injection rate. To ensure that Cm mineral content, volume fraction.
an adequate amount of acid contacts most of the damaged
formation, a larger amount of acid is necessary. Example Problem 16.1 A sandstone with a porosity of
The acid preflush volume is usually determined on the 0.2 containing 10 v% calcite (CaCO3 ) is to be acidized with
basis of void volume calculations. The required minimum HF/HCl mixture solution. A preflush of 15 wt% HCl
acid volume is expressed as solution is to be injected ahead of the mixture to dissolve
the carbonate minerals and establish a low pH
Vm
Va VP Vm , (16:3) environment. If the HCl preflush is to remove all
X carbonates in a region within 1 ft beyond a 0.328-ft
where radius wellbore before the HF/HCl stage enters the
formation, what minimum preflush volume is required in
Va the required minimum acid volume, ft3 terms of gallon per foot of pay zone?
Vm volume of minerals to be removed, ft3
VP initial pore volume, ft3

Table 16.2 Recommended Acid Type and Strength for Sandstone Acidizing
HCl Solubility > 20% Use HCl Only

High-perm sand ( k > 100 md)

High quartz (80%), low clay ( <5%) 10% HCl-3% HFa
High feldspar ( >20%) 13.5% HCl-1.5% HFa
High clay ( >10%) 6.5% HCl-1% HFb
High iron chlorite clay 3% HCl-0.5% HFb

Low-perm sand ( k < 10 md)

Low clay ( <5%) 6% HCl-1.5% HFc
High chlorite 3% HCl-0.5% HFd
a
Preflush with 15% HCl.
b
Preflush with sequestered 5% HCl.
c
Preflush with 7.5% HCl or 10% acetic acid.
d
Preflush with 5% acetic acid.

300

8 wt% HF

250
4 wt% HF
Percent of Original Permeability

2 wt% HF
200

150

100

50
Berea
sandstone
80 F-100 psi
0.1 1 10 100 1,000
Pore Volumes of Acid

Figure 16.1 Typical acid response curves (Smith and Hendrickson, 1965).
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16/246 PRODUCTION ENHANCEMENT

Solution lution and reaction product precipitation. Fortunately,

research results have shown that acidizing efficiency is
Volume of CaCO3 to be removed:

relatively insensitive to acid injection rate and that the
Vm p r2a
r2w 1
fCm highest rate possible yields the best results. McLeod

(1984) recommends relatively low injection rates based
p 1:3282
0:3282 1
0:2(0:1)
on the observation that acid contact time with the forma-
0:42 ft3 CaCO3 =ft pay zone tion of 24 hours appears to give good results. da Motta
(1993) shows that with shallow damage, acid injection rate
Initial pore volume: has little effect on the residual skin after 100 gal/ft of


VP p r2a
r2w f injection rate; and with deeper damage, the higher the

injection rate, the lower the residual skin. Paccaloni et al.
p 1:3282
0:3282 (0:2) 1:05 ft3 =ft pay zone
(1988) and Paccaloni and Tambini (1990) also report high
Gravimetric dissolving power of the 15 wt% HCl solution: success rates in numerous field treatments using the high-
y m MWm est injection rates possible.
b Ca There is always an upper limit on the acid injection rate
ya MWa that is imposed by formation breakdown (fracture) pres-
(1)(100:1) sure pbd . Assuming pseudosteady-state flow, the max-
(0:15)
(2)(36:5) imum injection rate limited by the breakdown pressure is
0:21 lbm CaCO3 =lbm 15 wt% HCl solution expressed as


Volumetric dissolving power of the 15 wt% HCl solution: 4:917  10
6 kh pbd
p
Dpsf
qi, max   , (16:6)
r ma ln 0:472r
rw S
e
X b a
rm
where
(1:07)(62:4)
(0:21)
(169) qi maximum injection rate, bbl/min
0:082 ft3 CaCO3 =ft3 15 wt% HCl solution k permeability of undamaged formation, md
h thickness of pay zone to be treated, ft
The required minimum HCl volume pbd formation breakdown pressure, psia
p reservoir pressure, psia
Vm
Va VP Vm Dpsf safety margin, 200 to 500 psi
X ma viscosity of acid solution, cp
0:42 re drainage radius, ft
1:05 0:42
0:082 rw wellbore radius, ft
6:48 ft3 15 wt% HCl solution=ft pay zone S skin factor, ft.
(6:48)(7:48) The acid injection rate can also be limited by surface
48 gal 15 wt% HCl solution=ft pay zone injection pressure at the pump available to the treatment.
This effect is described in the next section.
The acid volume requirement for the main stage in a mud
acid treatment depends on mineralogy and acid type and
strength. Economides and Nolte (2000) provide a listing of 16.3.4 Acid Injection Pressure
typical stage sequences and volumes for sandstone acidizing In most acid treatment operations, only the surface tubing
treatments. For HCl acid, the volume requirement increases pressure is monitored. It is necessary to predict the surface
from 50 to 200 gal/ft pay zone with HCl solubility of HF injection pressure at the design stage for pump selection.
changing from less than 5% to 20%. For HF acid, the volume The surface tubing pressure is related to the bottom-hole
requirement is in the range of 75100 gal/ft pay zone with flowing pressure by
3.013.5% HCl and 0.53.0% HF depending on mineralogy. psi pwf
Dph Dpf , (16:7)
Numerous efforts have been made to develop a rigorous
method for calculating the minimum required acid volume where
in the past 2 decades. The most commonly used method is psi surface injection pressure, psia
the two-mineral model (Hekim et al., 1982; Hill et al., 1981; pwf flowing bottom-hole pressure, psia
Taha et al., 1989). This model requires a numerical tech- Dph hydrostatic pressure drop, psia
nique to obtain a general solution. Schechter (1992) pre- Dpf frictional pressure drop, psia.
sented an approximate solution that is valid for Damkohler
number being greater than 10. This solution approximates The second and the third term in the right-hand side of
the HF fast-reacting mineral front as a sharp front. Readers Eq. (16.7) can be calculated using Eq. (11.93). However, to
are referred to Schechter (1992) for more information. avert the procedure of friction factor determination,
Because mud acid treatments do not dissolve much of the the following approximation may be used for the frictional
formation minerals but dissolve the materials clogging the pressure drop calculation (Economides and Nolte, 2000):
pore throats, Economides and Nolte (2000) suggest taking
the initial pour volume (Eq. [16.5]) within the radius of treat- 518r0:79 q1:79 m0:207
Dpf L, (16:8)
ment as the minimum required acid volume for the main stage 1,000D4:79
of acidizing treatment. Additional acid volume should be where
considered for the losses in the injection tubing string. r density of fluid, g=cm3
q injection rate, bbl/min
m fluid viscosity, cp
16.3.3 Acid Injection Rate D tubing diameter, in.
Acid injection rate should be selected on the basis of L tubing length, ft.
mineral dissolution and removal and depth of damaged
zone. Selecting an optimum injection rate is a difficult Equation (16.8) is relatively accurate for estimating fric-
process because the damaged zone is seldom known with tional pressures for newtonian fluids at flow rates less than
any accuracy and the competing effects of mineral disso- 9 bbl/min.
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MATRIX ACIDIZING 16/247

Example Problem 16.2 A 60-ft thick, 50-md sandstone

pay zone at a depth of 9,500 ft is to be acidized with an
acid solution having a specific gravity of 1.07 and a
viscosity of 1.5 cp down a 2-in. inside diameter (ID) coil
tubing. The formation fracture gradient is 0.7 psi/ft. The
wellbore radius is 0.328 ft. Assuming a reservoir pressure
of 4,000 psia, drainage area radius of 1,000 ft, and a skin
factor of 15, calculate
(a) the maximum acid injection rate using safety margin
300 psi.
(b) the maximum expected surface injection pressure at
the maximum injection rate.

Solution

(a) The maximum acid injection rate:

4:917  10
6 kh pbd
p
Dpsf
qi, max  
ma ln 0:472r
rw S
e

4:917  10
6 (50)(60)(0:7)(9,500)
4,000
300

 
(1:5) ln 0:472(1,000) 15
(0:328) Figure 16.2 Wormholes created by acid dissolution of
1:04 bbl=min limestone (Hoefner and Fogler, 1988; courtesy AIChE).

(b) The maximum expected surface injection pressure:

pwf pbd
Dpsf (0:7)(9,500)
300 6,350 psia 16.4.2 Acidizing Parameters
Acidizing parameters include acid volume, injection rate,
Dph (0:433)(1:07)(9,500) 4,401 psi and injection pressure. The acid volume can be calculated
518r0:79 q1:79 m0:207 with two methods: (1) Daccords wormhole propagation
Dpf L model and (2) the volumetric model, on the basis of desired
1,000D4:79
penetration of wormholes. The former is optimistic, whereas
518(1:07) (1:04)1:79 (1:5)0:207
0:79
the latter is more realistic (Economides et al., 1994).
(9,500)
1,000(2)4:79 Based on the wormhole propagation model presented by
218 psi Daccord et al. (1989), the required acid volume per unit
thickness of formation can be estimated using the follow-
psi pwf
Dph Dpf ing equation:
6,350
4,401 218 2,167 psia 1=3 d
pfD2=3 qh rwhf
Vh (16:9)
bNAc

16.4 Carbonate Acidizing Design where

The purpose of carbonate acidizing is not to remove Vh required acid volume per unit thickness
the damage to the formation near the wellbore, but to of formation, m3 =m
create wormholes through which oil or gas will flow after f porosity, fraction
stimulation. Figure 16.2 shows wormholes created by acid D molecular diffusion coefficient, m2 =s
dissolution of limestone in a laboratory (Hoefner and qh injection rate per unit thickness of
Fogler, 1988). formation, m3 =sec-m
Carbonate acidizing is a more difficult process to pre- rwh desired radius of wormhole penetration, m
dict than sandstone acidizing because the physics is much df 1:6, fractal dimension
more complex. Because the surface reaction rates are very b 105  10
5 in SI units
high and mass transfer often plays the role of limiting NAc acid capillary number, dimensionless,
step locally, highly nonuniform dissolution patterns are
usually created. The structure of the wormholes depends where the acid capillary number is defined as
on many factors including flow geometry, injection rate, fbg a
NAc , (16:10)
reaction kinetics, and mass transfer rates. Acidizing de- (1
f)gm
sign relies on mathematical models calibrated by labora-
tory data.

Table 16.3 Recommended Acid Type and

16.4.1 Selection of Acid Strength for Carbonate Acidizing
HCl is the most widely used acid for carbonate matrix
acidizing. Weak acids are suggested for perforating fluid Perforating fluid: 5% acetic acid
and perforation cleanup, and strong acids are recom- Damaged perforations: 9% formic acid
mended for other treatments. Table 16.3 lists recom- 10% acetic acid
mended acid type and strength for carbonate acidizing 15% HCl
(McLeod, 1984). Deep wellbore damage: 15% HCl
All theoretical models of wormhole propagation predict 28% HCl
deeper penetration for higher acid strengths, so a high Emulsified HCl
concentration of acid is always preferable.
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16/248 PRODUCTION ENHANCEMENT

where The designed acid volume and injection rate should be

g a acid specific gravity, water 1:0
g m mineral specific gravity, water 1:0.
Based on the volumetric model, the required acid volume
per unit thickness of formation can be estimated using the
following equation:
2

and a guideline to acidizing design for both sandstone and
Vh pf rwh
rw2 PV bt , (16:11)
where (PV )bt is the number of pore volumes of acid
injected at the time of wormhole breakthrough at the end
of the core. Apparently, the volumetric model requires
data from laboratory tests.
Example Problem 16.3 A 28 wt% HCl is needed to
propagate wormholes 3 ft from a 0.328-ft radius wellbore
in a limestone formation (specific gravity 2.71) with a
porosity of 0.15. The designed injection rate is 0.1 bbl/
min-ft, the diffusion coefficient is 10
9 m2 =sec, and the
density of the 28% HCl is 1:14 g=cm3 . In linear core
floods, 1.5 pore volume is needed for wormhole
breakthrough at the end of the core. Calculate the acid
volume requirement using (a) Daccords model and (b) the
volumetric model.
Solution
(a) Daccords model:
y m MWm (1)(100:1)
b Ca (0:28)
ya MWa (2)(36:5)
0:3836 lbm CaCO3 =lbm 28 wt% HCl solution:
fbga (0:15)(0:3836)(1:14)
NAc 0:0285
(1
f)g m (1
0:15)(2:71)
qh 0:1 bbl= min -ft 8:69  10
4 m3 =sec-m
rwh 0:328 3 3:328 ft 1:01 m
1=3 d
pfD2=3 qh rwhf
Vh
bNAc
p(0:15)(10
9 )2=3 (8:69  10
4 )1=3 (1:01)1:6
(1:5  10
5 )(0:0285)
0:107 m3 =m 8:6 gal=ft
(b) Volumetric model:
2

Acidization II: the dissolution of calcite in hydro-
Vh pf rwh
rw2 PV bt
p(0:15)(3:3282
0:3282 )(1:5)
7:75 ft3 =ft 58 gal=ft:
This example shows that the Daccord model gives opti-
mistic results and the volumetric model gives more realistic
results.
The maximum injection rate and pressure for carbon-
ate acidizing can be calculated the same way as that for
sandstone acidizing. Models of wormhole propagation
predict that wormhole velocity increases with injection
rate to the power of 12 to 1. Therefore, the maximum
injection rate is preferable. However, this approach may
require more acid volume. If the acid volume is con-
strained, a slower injection rate may be preferable. If a
sufficient acid volume is available, the maximum injection
rate is recommended for limestone formations. However,
a lower injection rate may be preferable for dolomites.
This allows the temperature of the acid entering the for-
mation to increase, and thus, the reaction rate increases.
adjusted based on the real-time monitoring of pressure
during the treatment.
Summary
This chapter briefly presents chemistry of matrix acidizing
carbonate formations. More in-depth materials can be
found in McLeod (1984), Economides et al. (1994), and
Economides and Nolte (2000).
References
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acidizing: toward a quantitative model of the worm-
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