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Introduction
Sandstone matrix acidizing is distinguished from car-
bonate acidizing in that it involves the dissolution of
damage that is blocking or bridging the pore throats
in the formation matrix, thus ideally recovering the
original reservoir permeability. Carbonate acidizing
dissolves the formation minerals around the damage,
creating new permeability. The mineral acids required
to dissolve the damage are usually highly reactive
with the numerous formation minerals. The resulting
chemical complexes can become insoluble in the
environment created and can precipitate, yielding
gelatinous or solid particles. Because the formation
and the damage can have complicated crystalline
structures that can yield a variety of reaction prod-
ucts, sandstone acidizing success requires a signi-
cantly better understanding of chemistry than does
carbonate acidizing. As discussed in Chapter 13,
75% of well-engineered sandstone acid treatments
should be successful, resulting in signicant produc-
tion enhancement.
The descriptor sandstone is derived from the
geologic classication of rocks with a high quartz sil-
ica content. Besides the obvious quartz component,
they contain other minerals such as aluminosilicates,
metallic oxides, sulfates, chlorides, carbonates and
noncrystalline (amorphous) siliceous material. The
minerals deposited in the original sediment are called
detrital species. Most have a high degree of associ-
ated water. As uids are produced through the matrix
of the rock, the drag forces can move some of these
minerals, clogging the pore throats.
Connate water in a sandstone contains many of the
dissolved native mineral species. This is due to equi-
librium and partial pressures of gaseous solvents
(such as carbon dioxide [CO
2
]) and the presence of
other ionic species. As uids are produced, the asso-
ciated pressure drop can disturb this equilibrium and
the normal ionic content of the formation brines,
resulting in precipitation and possible pore-throat
restriction. This type of diagenesis yields authigenic
species (e.g., scales such as calcium carbonates as
well as some clay species such as zeolites, illites,
kaolinites and smectites).
Various well operations can result in formation dam-
age (see Chapter 14). For example, drilling mud and
completion uid usually penetrate sandstone forma-
tions. This invasion of ltrate can introduce an entirely
different chemical environment, which the acid treat-
ment must address. Additional formation damage may
occur during perforating, gravel packing, and normal
production or injection operations. Acid dissolves a
variety of damaging materials along with most forma-
tion minerals. An understanding of the chemistry is
basic to the selection of the acid type and concentration.
This chapter includes the reaction chemistry of the
primary solvent used in sandstone acidizing, hydro-
uoric acid (HF). Acid systems that contain mixtures
of hydrouoric and hydrochloric acid (HCl) are com-
monly called mud acids because they were rst used
to remove mud damage.
18-2. Treating uids
18-2. 1. Hydrochloric acid chemistry
HCl reactions are discussed in Chapter 17, and details
of the reaction and by-products are omitted in this
chapter except for how they relate to sandstone min-
erals. The compatibility of the HF blends used in this
process is twofold; these mixtures must meet both
compatibility standards for the formation mineralogy
and dissolution of the damage mineralogy. HF mix-
tures are preceded by HCl to avoid precipitation of
the slightly soluble and insoluble reaction products
of HF with certain chemical species. The chemistry
of HCl with carbonate minerals is discussed in a pre-
vious chapter, so the focus here is on the chemistry
of the HF systems. Although the chemistry of the
reaction of HCl with carbonate or calcite is simple,
the chemistry of the reaction of HF and siliceous
minerals is complex.
Reservoir Stimulation 18-1
x
Sandstone Aci di zi ng
Harry O. McLeod, Conoco, USA
William David Norman, Schlumberger Dowell
Some complex reactions that occur with certain
siliceous minerals have only recently been included
in the reactions reported in mineralogy breakdowns.
These reactions involve HCl and the mineral family
known as zeolites. Zeolite minerals are crystalline, but
hydrated with active, porous channels in the crystalline
lattice. Zeolites are known in other industries as mol-
ecular sieves because their porosity allows the chem-
ical extraction and ltering of selective materials.
Zeolite minerals occur in nature as a by-product of
volcanic activity and precipitate from water that is
rich in silica. It is theorized that as zeolites are
exposed to progressively higher pressures and temper-
atures they metamorphose from extremely loose,
hydrated crystalline structures to more dense and
compact structures. The results of this process have
different mineral names. The hierarchy of their struc-
ture and crystalline nature is provided in Table 18-1.
Because these minerals are precipitates, they are
always authigenic and located in pore spaces.
Zeolite minerals are sensitive to HCl and strong
mineral acids. Several core studies have shown that
the use of HCl alone causes signicant damage,
whereas weak organic acid reduces the damage. The
problem is that the weak organic acid does not neces-
sarily remove the damaging mineralogy to restore per-
meability. The solution to the problems associated
with zeolites is to recognize the presence of these
minerals before a treatment is performed. The use of
an organic acid as one of two preush stages and fol-
lowing the preushes with a low-concentration HF
mixture that conforms with the remaining minerals
in the formation has proved to be highly effective in
restoring permeability and removing damage. All u-
ids that are injected should have an organic acid
included to maintain a low-pH environment. Some
operators have found the use of an all-organic-acid
system followed by an organic acidHF formulation
to be effective in high-temperature environments.
18-2. 2. Chemistry of hydrouoric
acid systems
HF is the only common, inexpensive mineral acid
able to dissolve siliceous minerals. For any acid sys-
tem to be capable of damage removal, it should con-
tain HF in some form. The most common formulation
is simply ammonium biuoride dissolved in HCl;
another is by diluting concentrated HCl-HF formula-
tions. The HCl:HF ratio is varied to accommodate the
solubility of the dissolved mineral species present in
the formation. This can be augmented by both pre-
ush and overush acid formulations. Several poten-
tial precipitates can be addressed simply by the use
of appropriate HCl:HF ratios in the formulations.
Numerous mineral species react with HF, and they
all generate aluminum silica uoride complexes
(Table 18-2).
Reactions of hydrouoric acid with formation
minerals
Details of HF reactions with formation minerals
have, for more than 60 years, been known and stud-
ied. As early as 1965, it was quantied that 1000 gal
of 2% HF can dissolve as much as 350 lbm of clay
(Smith et al., 1965).
An HCl preush is always injected in sandstones
prior to the HF. This is done to avoid the possible
precipitation of insoluble or slightly soluble reaction
products. Typically, the insoluble species are calcium
uoride (CaF
2
), which forms on reaction of HF with
calcium carbonate (CaCO
3
), or sodium or potassium
hexauosilicates (M
2
SiF
6
, where M = Na or K),
which result from the reaction of cations in forma-
tion brines with solubilized species. The dissolution
of calcium carbonate or magnesium carbonate by
reaction with HCl is discussed in detail in Chapter 17.
18-2 Sandstone Acidizing
Table 18-1. The zeolite family.
Mineral Description
Stilbite Hydrous calcium aluminum silicate
Dissolves in contact with HCl; no gelatin formed
Occurs in shallow environments and may occur
inside tubulars in silica-rich connate water
formations with high pressure drops
Heulandite Hydrous calcium/sodium/potassium aluminum
silicate
Dissolves in contact with HCl; no gelatin formed
Occurs in shallow environments
Chabazite Hydrous calcium/sodium/potassium aluminum
silicate
Dissolves in contact with HCl; no gelatin formed
Occurs in medium-depth environments
Natrolite Hydrous sodium/potassium aluminum silicate
Dissolves in contact with HCl; gelatin formed
Occurs in deeper environments
Analcime Hydrous sodium aluminum silicate
Dissolves in contact with HCl; gelatin formed
Occurs in deeper environments
Stoichiometric equations
Reactions of mud acid with the aluminosilicate
components of sandstones are those of HF; how-
ever, HF is a weak acid and, because of the equili-
brated reaction, is only slightly dissociated when
mixed with HCl:
HF + H
2
O H
3
O
+
+ F
K
a
= 10
3.2
at 75F [25C]
where K
a
is the acid equilibrium constant.
HF can also combine and form complexes, but
this reaction must be taken into account (Fogler et
al., 1976) only when the HF concentration is suffi-
ciently high (less than 10M) to allow numerous
collisions to occur between the uoride species.
This occurs only in the case of ultra mud acid
(25% HCl20% HF) formulations:
HF + F
HF
2
K = 3.86 at 75F
The reaction of HF with quartz grains (pure sil-
ica) is expressed in the following two equilibria:
SiO
2
+ 4HF SiF
4
+ 2H
2
O
SiF
4
+ 2F
SiF
6
2
The intermediate silicon complex, SiF
5
, which is
not stable in aqueous solution, is not considered. The
rst step of silica dissolution consists of the chemi-
sorption of the uoride anion at the silica surface
(Iler, 1979). Kline and Fogler (1981b), on the con-
trary, showed that it is the molecular HF rather than
the uoride anion that adsorbs (see Section 18-4).
Gaseous silicon tetrauoride usually remains dis-
solved in the liquid phase at bottomhole pressure, as
CO
2
does in the case of carbonate acidization, so the
equilibrium is shifted toward the formation of silicon
hexauoride anions and the remaining SiF
4
does not
represent more than 1% of the total dissolved silicon
(Labrid, 1971).
Silicon hexauoride anions can be hydrolyzed fur-
ther into monosilicic acid with the evolution of heat:
SiF
6
2
+ 8H
2
O Si(OH)
4
+ 4H
3
O
+
+ 6F
K = 1.2 10
27
at 75F
When the silicon concentration increases in the
aqueous phase, part of the hexauorosilicate anions
are also transformed into the acidic form of uosili-
cic acid according to the reaction
SiF
6
2
+ 2H
3
O
+
H
2
SiF
6
+ 2H
2
O
K = 6.7 10
4
at 75F
Reservoir Stimulation 18-3
Table 18-2. Chemical composition of typical sandstone minerals.
Classication Mineral Chemical Composition
Quartz SiO2
Feldspar Microcline KAlSi3O8
Orthoclase KAlSi3O8
Albite NaAlSi3O8
Plagioclase (Na,Ca)Al(Si,Al)Si2O8
Mica Biotite K(Mg,Fe
2+
)3(Al,Fe
3+
)Si3O10(OH)2
Muscovite KAl2(AlSi3)O10(OH)2
Chlorite (Mg,Fe
2+
,Fe
3+
)AlSi3O10(OH)8
Clay Kaolinite Al2Si2O5(OH)4
Illite (H3,O,K)y (Al4 Fe4 Mg4 Mg6)(Si8 y Aly )O20(OH)4
Smectite (Ca0.5Na)0.7(Al,Mg,Fe)4(Si,Al)8O20(OH)4 nH2O
Chlorite (Mg,Fe
2+
,Fe
3+
)AlSi3O10(OH)8
Carbonate Calcite CaCO3
Dolomite CaMg(CO3)2
Ankerite Ca(Fe,Mg,Mn)(CO3)2
Siderite FeCO3
Sulfate Gypsum CaSO4 2H2O
Anhydrite CaSO4
Chloride Halite NaCl
Metallic oxide Iron oxides FeO, Fe2O3, Fe3O4
This transformation is usually limited, because
uosilicic acid is a strong acid. Aluminosilicate
minerals generally have complex chemical compo-
sitions, such as those listed in Table 18-2. Their
overall dissolution reactions thus involve many
simple equilibria.
The disintegration of aluminosilicate minerals by
HF can be considered stoichiometric as a rst step;
i.e., the Al:Si ratio is the same in the solution as in
the mineral. Silicon is solubilized by the same pro-
cess mentioned for quartz, whereas aluminum is
involved in several uorinated complexes:
AlF
n
(3 n)+
AlF
n
(4 n)+
+ F
where 0 n 6.
The prominent form of aluminum complexed
varies as a function of the free uoride ion concen-
tration: the average ratio of uorine to aluminum
decreases as the dissolution reaction progresses
(fewer uoride anions are available), as shown
in Fig. 18-1 (Labrid, 1971).
The dissolution reaction of all aluminosilicate
minerals in sandstones follows the previous equa-
tions for the basic lattice atoms (Si, Al) concerned.
Other metallic ions, such as Na, K, Mg, Ca and Fe,
which are in the minerals constituting the rock as
substitution cations in the lattice or as exchangeable
(adsorbed) cations, come into solution as free ions
during the reaction. In the case of iron, uorinated
complexes (FeF
z
(3 z )+
, where 1 < z < 3) also are
formed through reactions similar to those for alu-
minum. Thus, different global reactions can be
written as a function of the considered mineral:
Kaolinite clay
Al
4
Si
4
O
10
(OH)
8
+ 4(n + m) HF
+ (28 4(n + m))H
3
O
+
4AlF
n
(3 n)+
+ 4SiF
m
(4 m)
+ (46 4(n + m))H
2
O
Sodic or potassic feldspar
MAlSi
3
O
8
+ (n + 3m)HF + (16 n 3m)H
3
O
+
M
+
+ AlF
n
(3 n )+
+ 3SiF
m
(4 m)
+ (24 n 3m)H
2
O
where 0 n < 6 and m = 4 or 6.
18-3. Solubility of by-products
When minerals are dissolved by HF, numerous by-
products can form. Some potential precipitates are
listed in Table 18-3. In many cases, the increase in the
liquid-phase pH value resulting from acid mixture
spending constitutes the driving force for precipitate
formation; therefore, precipitation can be predicted
from consideration of the sole liquid phase. The extent
of precipitation should always be limited. If this is not
possible, the potential precipitation zone that would
cause a decrease in permeability should be diluted and
displaced from the wellbore (Walsh et al., 1982).
Should precipitation occur, most of the calcium and
sodium complexes that precipitate in the eld can be
redissolved by using boric acid. This is not true, how-
ever, for potassium and some of the magnesium com-
plexes. The very low solubility of potassium complexes
has been shown both in the laboratory and in the eld.
Colloidal silica precipitation cannot be avoided, as
it results partly from the greater affinity of uorine for
18-4 Sandstone Acidizing
Figure 18-1. Domains of existence of aluminum-uorine
complexes (Labrid, 1971).
A
I
F
c
o
n
c
e
n
t
r
a
t
i
o
n
(
%
)
100
50
10
4
10
3
10
2
Fluoride ion concentration (g ion L)
AIF5
AIF4
AIF3
AIF2
AIF
Table 18-3. Solubility in water at room temperature
of HF reaction by-products.
Secondary Product Solubility (g/100 cm
3
)
Orthosilicic acid (H4SiO4) 0.015
Calcium uoride (CaF2) 0.0016
Sodium uosilicate (Na2SiF6) 0.65
Sodium uoaluminate (Na3AlF6) Slightly soluble
Potassium uosilicate (K2SiF6) 0.12
Ammonium uosilicate ((NH4)2SiF6) 18.6
Calcium uosilicate (CaSiF6) Slightly soluble
Aluminum uoride (AlF3) 0.559
Aluminum hydroxide (Al(OH)3) Insoluble
Ferrous sulde (FeS) 0.00062
aluminum than for silicon. This process accelerates
the hydrolysis of SiF
6
because the released F
anions
are further involved in aluminum complexes and more
monosilicic acid (Si(OH)
4
) is generated. Certain
authors (Labrid, 1971; Shaughnessy and Kunze, 1981;
Walsh et al., 1982) have emphasized the highly dam-
aging potential of the precipitation of colloidal silica
in a porous medium; however, this damaging action
has never been demonstrated clearly and satisfactorily.
On the contrary, other authors (Crowe, 1986)
showed that such precipitation is actually the result
of a topochemical reaction (exchange of uoride from
the hexauorosilicate anion occurs with aluminum on
the surface of the silt and clay), and it does not induce
damage.
Precipitation begins earlier in the dissolution process
at higher temperatures (within 10 min at 200F [95C])
because of the increased thermal agitation. It also
occurs more quickly in montmorillonite-type clays than
in kaolinite clays because of the different initial Al:Si
ratios in these minerals (molar ratio of 1 for kaolinite
and less than 0.5, depending on the substitution extent,
for montmorillonite). Finally, aluminum can be totally
removed from clays, with a correlated silica deposition
at the surface (topochemical reaction).
18-3. 1. Calcium uoride
Some carbonates may remain after preushing, either
because of the initial amount of carbonate cementing
material in the sandstone or as a result of the carbon-
ates initial protective siliceous coating. Also, slightly
soluble, ne crystalline CaF
2
readily forms when cal-
cite contacts HF. This can lead to substantial damage:
CaCO
3
+ 2HF CaF
2
+ H
2
O + CO
2
Where this precipitate has formed but has not com-
pletely blocked the porosity of the formation, it may
partially redissolve when HF is near complete spend-
ing toward the end of the job. At this time, the con-
centration of uoride anions in solution is so low that
aluminum is hardly complexed and appears mainly as
free Al
3+
ions (Labrid, 1971). These aluminum ions
are then able to extract uorine from the CaF
2
precipi-
tates, as they did for silicouorides, and partly redis-
solve the CaF
2
according to the reaction
3CaF
2
+ 2Al
3+
3Ca
2+
+ 2AlF
2+
This reaction may be followed by subsequent equilibria
between the different aluminum and uorine complexes.
18-3. 2. Alkali uosilicates and
uoaluminates
The aluminum or silicon uorine complexes can react
with alkali ions released in the solution from highly
substituted clays or alkali feldspars as soon as their
concentration becomes sufficiently high to form insol-
uble alkali uosilicates and, probably, uoaluminates:
2Na
+
+ SiF
6
2
Na
2
SiF
6
K
s
= 4.2 10
5
2K
+
+ SiF
6
2
K
2
SiF
6
K
s
= 2 10
8
3Na
+
+ AlF
3
+ 3F
Na
3
AlF
6
K
s
= 8.7 10
18
2K
+
+ AlF
4
+ F
K
2
AlF
5
K
s
= 7.8 10
10
where K
s
is the solubility constant.
Alkali uosilicate precipitation is favored by a high
level of HF. Fluosilicate precipitates, which form from
the attack of mud acid on alkali feldspars or clays, are
well crystallized and very damaging (Bertaux, 1989).
These damaging precipitates also form when the vol-
ume of preush is insufficient and HF contacts forma-
tion brine containing alkali ions.
18-3. 3. Aluminum uoride and hydroxide
Aluminum uoride (AlF
3
) or aluminum hydroxide
(Al(OH)
3
) in the gibbsite form can precipitate upon
spending of the acid. The precipitation of AlF
3
can be
reduced by maintaining a high proportion of HCl to
HF (Walsh et al., 1982). These precipitates form
according to the reactions
Al
3+
+ 3F
AlF
3
Al
3+
+ 3OH
Al(OH)
3
K
s
= 10
32.5
18-3. 4. Ferric complexes
This mechanism of forming iron uorine complexes
applies only to relatively clean sandstones. In the pres-
ence of clays, the dissolved aluminum ions have a
greater affinity for uorine than iron does. Therefore,
the iron uorine complexes do not form and iron
hydroxide still precipitates at pH levels greater than 2.2.
The nature of the precipitate (crystalline or amor-
phous) varies as a function of the anions present
(Smith et al., 1969). Ferric hydroxide can be strongly
bound to the quartz surface by electrostatic interac-
tions because its point of isoelectric charge is above
a pH value of 7. In the presence of excess calcite, the
Reservoir Stimulation 18-5
dissolved CO
2
can also lead to the precipitation of
insoluble ferric carbonates (siderite or ankerite).
Chapter 15 provides additional information about iron
control and solutions for problems.
18-4. Kinetics: factors affecting
reaction rates
This section summarizes qualitatively the results
described in detail in Chapter 16. Because theoretical
aspects are covered in Chapter 16, only the practical
implications are discussed here.
Kinetically controlled reactions (surface reaction limit-
ed) are effective during the acidization process of sand-
stones, and factors affecting reaction rates are discussed
to complete previous thermodynamic considerations.
18-4. 1. Hydrouoric acid concentration
Dissolution reaction rates are proportional to the HF
concentration (Fogler et al., 1976; Kline and Fogler,
1981b) for most sandstone minerals, except smectite.
This explains why formations with low competence
(i.e., weak cementation, potentially mobile ne parti-
cles) should be treated with a reduced-strength mud
acid (1.5% HF) to avoid crumbling, especially at bot-
tomhole temperatures greater than 200F. Fluoboric
acid performs similarly because of the low concentra-
tion of HF present at any time.
18-4. 2. Hydrochloric acid concentration
Dissolution reaction rates generally increase in a more
acidic medium because the leaching of constitutive
surface cations involves their replacement by protons,
but the dependence on HCl concentration is not
straightforward (Gdanski and Peavy, 1986). The prin-
cipal role of HCl is to prevent secondary precipitation
by maintaining a low pH value. The other main effect
of HCl is to catalyze the attack of sandstone minerals
by HF. The mechanism and degree of catalysis depend
on the type of mineral, as shown in the following.
For example, the reaction rate measured at 95F
[35C] for pure quartz has the following expression
(Fogler et al., 1976):
(18-1)
in mol quartz/cm
2
/s.
In the case of a feldspar with the overall formula
Na 0.72K0.08Ca 0.2Al 1.2Si 2.8O
8
, the following
expression has been determined (at 75F under
275-kPa pressure) as the reaction rate (Fogler et
al., 1976):
(18-2)
in mol feldspar/cm
2
/s.
An elemental mechanism proposed to explain the
previous variation involves the adsorption of protons
on the surface that weakens the siloxane bondings,
which is followed by the reaction of HF molecules
that creates unstable silicon-uorine bonds at the sur-
face, according to the scheme
H
|
XOSi +H
+
XOSi
+
+ HF
X + FSi
+ H
2
O
where X = Al or Si.
This is the acid (proton) catalysis mechanism pro-
posed by Kline (1980) for feldspar.
The dissolution reaction is a rst-order reaction
with respect to the HF concentration for most alumi-
nosilicate minerals. Nevertheless, dissolution kinetics
is better represented by a Langmuir-Hinshelwood
type law in the case of sodium montmorillonite (Kline
and Fogler, 1981):
(18-3)
where K
ads
is the equilibrium constant of the exother-
mic adsorption of HF molecules at surface-reactive
sites. This adsorption constant is independent of the
total acidity, whereas K increases with proton concen-
tration (acid catalysis). K
ads
is especially high for a
mineral with a high cation exchange capacity (CEC),
such as sodium montmorillonite. For most other clay
minerals, the value of this adsorption constant is
small. Therefore, when 1 >> K
ads
[HF] the expression
can be simplied to the experimentally determined
rst-order kinetics law. An elemental mechanism dif-
ferent from that mentioned for feldspars can be pro-
posed to explain the kinetics and to take into account
solely the HF adsorption:
18-6 Sandstone Acidizing
r
quartz
+
[ ] ( )
[ ]
+
9 2 10 1 0 8
9
. . H HF
r
feldspar
+
[ ] ( )[ ]
+
1 3 10 1 0 4
9
. . H HF
R
KK
K
ads
ads
[ ]
+ [ ]
HF
HF 1
,
F
|
HO OH HO H OH HO OH
| | | | | | |
XOX +HF XOX X F + HOX
where X = Al or Si.
18-4. 3. Temperature
The dissolution of minerals is a thermally activated phe-
nomenon; thus, the rates increase greatly as a function of
temperature (approximately multiplied by 2 for quartz
for a 25C increment), and the penetration depths of live
acid diminish accordingly. In the case of quartz, the acti-
vation energy is about 5.2 kcal/mol, and in the case of
the previous feldspar, it is about 8 kcal/mol (Fogler et
al., 1976).
Figure 18-2 shows the variation of the reaction rate
of mud acid with vitreous silica (more reactive than
quartz) as a function of both HF concentration and
temperature (Smith and Hendrickson, 1965). Alumi-
num and iron solubilities also increase slightly with
a rise in temperature.
18-4. 4. Mineralogical composition and
accessible surface area
The relatively high total specic surface area of sand-
stone rocks is the primary parameter determining mud
acid spending because of the heterogeneous nature of
the dissolution reaction. However, if the contribution
of each mineral to the total accessible surface area is
considered, great discrepancies between the reaction
rates of pure phases can be predicted and observed
(Table 18-4).
Clays react much faster than feldspars, which react
much faster than quartz, especially in the presence of high
proton (H
+
) concentrations. Thus, most of the quartz
matrix (about 95%) can be considered inert with respect
to the dissolution reaction, and the mineralogical nature
of the accessible rock components determines the overall
reaction rate. This situation also emphasizes the necessity
of HCl preushes and excess HCl in the HCl-HF mixture.
Calcite reacts at the highest rate of all the minerals that
can be present in a sandstone, leading to HF microchan-
neling, but the mechanism of attack is not comparable
because protons coming from either HCl or HF can pro-
voke the dissolution.
18-4. 5. Pressure
An increase in pressure speeds up the overall dissolution
reaction slightly, because dissolved silicon tetrauoride
can be transformed partially into an acidic species
(H
2
SiF
6
) and can quickly initiate further reactions. For
quartz, a 24% rise in the reaction rate was noticed
between the two extreme conditions (Smith et al., 1965).
In a radial injection situation, the mineral pore-
space texture that determines ow partition around the
wellbore (most live acid ows through the large
pores) is also a relevant parameter; clay clasts can
be bypassed by the acid ow (Williams, 1975).
18-5. Hydrouoric acid reaction
modeling
The parameters that affect the reaction rate of HF on
sandstone minerals are incorporated in a model that
Reservoir Stimulation 18-7
Figure 18-2. Reaction rate of HCl-HF on silicate glass
(Smith and Hendrickson, 1965).
R
e
a
c
t
i
o
n
r
a
t
e
(
l
b
m
f
t
2
/
s
1
0
6
)
7
6
5
4
3
2
1
0
0 1 2 3 4 5 6 7 8 9 10
HF (%)
Reaction time, 60 min
1
2
5
F
1
5
0
F
1
7
5
F
Table 18-4. Relative surface areas
of sandstone minerals.
Mineral Surface Area
Quartz <0.1 cm
2
/g
Feldspar Few m
2
/g
Kaolinite 1530 m
2
/g
Illite 113 m
2
/g
Smectite 82 m
2
/g
predicts the evolution of formation parameters when
acid is injected.
In terms of surface reaction rates, sandstones are
typically considered a two-component system:
slow-reacting pseudocomponent, forming the crys-
talline quartz fraction
fast-reacting pseudocomponent, comprising all
other species (e.g., clays, feldspars and poorly
crystallized silica).
For both pseudocomponents, the overall kinetics,
which includes the diffusion of HF-reactant species to
the surface, surface reactions and the diffusion of react-
ed products back to the bulk solution, is governed by
the surface reactions because they are the slowest step.
Therefore, matrix acidizing of sandstones with HF is
called surface reaction limited.
This is the major difference from the matrix acidiz-
ing of limestone, where the process is diffusion con-
trolled. In sandstones, the increase in permeability
results from damage removal and is correlated with
a small increase in rock porosity. Quartz reacts very
slowly with HF; reactions with most aluminosilicates
provoke a rapid spending of the acid. A pseudo-
stationary state reects the much faster variation in
species concentration (chemical modications) than
the one within the rock porosity (resulting in physical
modication). The HF progresses and homogeneously
dissolves every pore and never forms conductive
channels or wormholes. The ow is stable, and sharp
fronts are formed in response to the dissolution of dif-
ferent mineral species as acid injection progresses
radially (McCune et al., 1975).
Several authors have tried to model this process.
Taha et al. (1986) used the reaction model developed
by Fogler and various coworkers (see particularly
Hekim et al., 1982). Such a simplied, two-pseudo-
component model and macroscopic description can be
used because Fogler et al. (1976) showed that the order
of reaction of HF with each pseudocomponent is equal
to unity relative to the concentrations of HF and of the
pseudocomponent. The ow is considered stable.
In this model the mineral dissolution fronts can be
computed and the concentration of remaining clays
(or fast-reacting materials) can be calculated. Then,
the permeability increase can be estimated from the
change in porosity (or amount of material dissolved).
The velocity of the mineral dissolution front depends
on the acid capacity number A
c
, which is a function of
the volume of clays (or fast-reacting dissolvable mate-
rial) and of the acid concentration.
The acid concentration (or spending) front can be
modeled similarly. The thickness of the front depends
on the Damkhler number Da, which is a function of
the reaction rate and the acid velocity. These simula-
tions show why HF does not penetrate deeply into the
reservoir before spending unless unrealistically large
volumes are used. (These large volumes would almost
dissolve everything around the wellbore and thus
leave the reacted formation totally unconsolidated.)
18-6. Other acidizing formulations
Problems related to the use of mud acid to remove
damage in sandstone formations include the following:
Rapid spending provides only a short penetration,
especially at high temperatures (maximum depth
about 12 in.).
Fines, composed of either mostly quartz or mostly
clay minerals, can be generated during the acid
reaction and can migrate with the uid ow. The
destabilization of nes can lead to a quick produc-
tion decline after treatment. Gravel-packed gas
wells can exhibit a 50% productivity reduction.
The high dissolving power of mud acid destroys
rock integrity at the formation face.
New sandstone acidizing systems are designed to
alleviate these shortcomings.
18-6. 1. Fluoboric acid
Fluoboric acid is recommended by Thomas and
Crowe (1981) as an alternative to mud acids. It does
not contain large amounts of HF at any given time
and thus has a lower reactivity. However, it generates
more HF, as HF is consumed, by its own hydrolysis.
Therefore, its total dissolving power is comparable to
a 2% mud acid solution. Fluoboric acid solutions are
used as a preush before treating formations sensitive
to mud acid; this avoids nes destabilization and sub-
sequent pore clogging. They are also used as a sole
treatment to remove damage in a sandstone matrix
with carbonate cement or in ssures that contain many
clay particles. Another use is as an overush after a
mud acid treatment that has removed near-wellbore
damage (up to 0.5 ft) to allow easier penetration of the
18-8 Sandstone Acidizing
uoboric acid solution (a few feet). Fluoboric acid is
recommended when the sandstone contains potassic
minerals to avoid damaging precipitates and in the
case of nes migration owing to its nes stabilization
properties.
In the eld, uoboric acid is easily prepared by
mixing boric acid (H
3
BO
3
), ammonium biuoride
(NH
4
F HF) and HCl. Ammonium biuoride, an
acidic salt of HF, reacts rst with HCl to generate HF:
NH
4
F HF + HCl 2HF + NH
4
Cl
Tetrauoboric acid is formed as a reaction product
of boric acid with HF, according to
H
3
BO
3
+ 3HF HBF
3
OH + 2H
2
O (quick reaction)
HBF
3
OH + HF HBF
4
+ H
2
O (slow reaction)
Hydroxyuoboric acid (HBF
3
OH) probably does not
exist in aqueous solutions unless it is in equilibrium
with uoboric acid (Wamser, 1948). The preceding
slow reaction is of an order equal to unity with respect
to both HF and HBF
3
OH. For this reaction, equilibrium
is attained at room temperature after nearly 40 min for
a resulting lM HBF
4
solution. Because the equilibrium
constant at 75F is K = 2.3 10
3
(Wamser, 1948),
about 6% (molar) HBF
4
is converted into HBF
3
OH at
equilibrium for a lM HBF
4
solution. These equilibrium
considerations mean that at any given time and place
there is only between 0.1% and 0.2% (weight) of free
HF at ambient temperature and 212F [100C], respec-
tively.
Fluoboric acid is a strong acid with strength compa-
rable to that of HCl (Maya, 1977); thus, the following
reaction occurs in solution:
HBF
4
+ H
2
O H
3
O
+
+ BF
4
instead of HBF
4
. Acid strength diminishes in the fol-
lowing order: uoboric, hydroxyuoboric (the strength
of which can be compared to that of trichloroacetic
acid; Maya, 1977) and boric acid (K
H
3
BO
3
= 9.2 at
75F).
The dissolving power of uoboric acid results from
the generation of HF through its hydrolysis:
BF
4
+ H
2
O BF
3
OH
+ HF
The BF
3
OH anions can be further hydrolyzed suc-
cessively into BF
2
(OH)
2
, BF(OH)
3
and H
3
BO
3
with
correlated HF formation, but these reactions must be
taken into account only when the BF
3
OH
concentra-
tion is lower than 3 10
3
at 75F (Wamser, 1948). In
the following text, BF
3
OH
hydrolysis is neglected at
the usual acid concentrations.
The hydrolysis reaction kinetics of uoborate ions
is affected by
concentration of the uoborate ions
medium acidity, which has a catalyzing effect (reac-
tion is proportional to the proton concentration)
temperature, through the usual activation energy
effect.
Thus, the reaction rate, assuming the reverse reac-
tion is negligible, can be expressed after Kunze and
Shaughnessy (1983) as
(18-4)
where
in (mol/L)
1
min
1
and T is the temperature in kelvin.
Thus, the reaction rate is increased 300-fold when the
mixture is heated from 75 to 150F [25 to 65C] and
is increased 12,000-fold when heated from 75 to 220F
[105C]. Because the hydrolysis reaction kinetics is
not affected by clays, uoboric acid can be considered
a retarded acid in normal use (i.e., less than 200F). In
the presence of excess bentonite, pure 0.1M uoboric
acid is spent within 30 min at 150F (Kunze and
Shaughnessy, 1983). In a slurry test, which has an in-
nite surface area (1 L of acid with 20 g of bentonite or
1600 m
2
of surface area, which is equivalent to several
football elds of exposed area), the reaction rate is a
function of the rate of hydrolysis. However, in the
matrix, where there is a nite amount of clay surface,
the reaction rate is a function of the amount of HF pres-
ent, which in the case of uoboric acid is low.
The reaction of uoboric acid in sandstones
involves at the same time the hydrolysis reaction of
uoboric acid, standard reactions of the generated HF
with minerals and additional slow reactions related to
the uoborate ions in the liquid phase. As expected,
the dissolution reaction of clays with uoboric acid
is a rst-order reaction with respect to the uoborate
concentration, similar to the relation of the reaction
of mud acid to the HF concentration.
The spending rate of uoboric acid on glass slides
at 150F is one-tenth that of a mud acid with the same
total HF content (Thomas and Crowe, 1981). Amor-
Reservoir Stimulation 18-9
r
d
dt
K
[ ]
[ ][ ]
+
BF
H O BF
4
3 4
,
K
T
]
]
]
1 44 10
26 183
1 987
17
.
,
.
exp
phous silica reacts faster than quartz, which limits the
destruction of cores near the injection face during ow
tests with uoboric acid. Signicantly less destruction
is noted than during mud acid ow testing. The
reduced destruction with uoboric acid results in 30%
to 50% higher compressive strengths than observed
for mud acid.
The unique advantage of uoboric acid is that it pro-
vides efficient stabilization of clays and nes through
reactions related to borate and uoborate ions. Swelling
clays are desensitized by uoboric acid, and there is a
large decrease in the CEC (e.g., a 93% decrease after
18 hr in uoboric acid at 150F for a Wyoming ben-
tonite was observed by Thomas and Crowe).
After a uoboric acid treatment, migrating clays
and other nes stabilize as a result of the rocks expo-
sure to acid. This is why a long shut-in time is recom-
mended in uoboric acid treatments. During injection,
while the acid spends normally, cores treated only
with uoboric acid exhibit a normal increase in per-
meability. However, no long-term stabilization occurs
after treatment because only a portion of the clay was
dissolved; the remainder did not have time to stabi-
lize. Additional shut-in time allows this stabilization.
When treated by uoboric acid, montmorillonite pro-
gressively decreases in aluminum content and then pro-
gressively incorporates boron atoms; silicon precipitates
from the solution. Cores originally containing 30% sili-
coaluminates at 150F attain maximum static solubili-
ties after only 24 hr in the presence of lM HBF
4
(4 hr
for mud acid), whereas the maximum increase in per-
meability is obtained after only 4 hr under dynamic
conditions (Thomas and Crowe, 1981). These results
prove the dissociated effects of mineral dissolution by
the generated HF (essentially kinetically controlled) and
of particle stabilization resulting from the slow complex
dissolution/reprecipitation mechanisms (toward thermo-
dynamic equilibrium) during the shut-in period.
Examination under a scanning electron microscope
(SEM) shows that the original kaolinite clay platelets
pure aluminosilicatesthat are not dissolved by uo-
boric acid appear welded together and to the quartz
grains. A type of chemical fusion of any nes seems to
take place slowly onto the silica surface. The formation
of borosilicate glass has been assumed to account for
this reaction.
Bertaux (1989) observed that in silicoaluminates con-
taining potassium, such as illite, potassium uoborate
forms after treatment with uoboric acid as a nondam-
aging coating on the clay; potassium hexauosilicate
forms after treatment with mud acid. This shows that
nondamaging by-products are formed by uoboric acid,
whereas formation plugging by alkali uosilicates can
occur with mud acid. This is another advantage of using
uoboric acid in some acid-sensitive formations.
During the injection period, uoboric acid behaves
like a weak HF solution, but one in which the HF is
constantly replenished. The small amount of uoride
ions available at any time limits the danger of precipi-
tating aluminum species. Only the rst acidity is used
during this step. Hydroxytriuoboric acid (HBF
3
OH)
buffers the solution and prevents other undesirable
precipitations.
During shut-in, HBF
4
and HBF
3
OH continue to
react, but at a slow pace because the hydrolysis is
minimal. The liberated HF reacts further with mineral
species. It also reacts by topochemical reactions, in
which the aluminum from the undissolved clay struc-
ture is put into solution by forming one of the uoalu-
minate complex ions (depending on F
), and the
surface of the mineral is therefore enriched in silicon
and boron. An amorphous coating of silica and boro-
silicate glass is then formed over the remaining silicate
and ne silica grains, welding them to the framework
and thus preventing their migration.
This effect is clearly seen in Figs. 18-3 and 18-4,
where the same pore, containing two different clays
(kaolinite and illite), is shown before and after reac-
tion with a uoboric acid solution. The quartz is
barely etched, whereas the high-surface-area, fast-
reacting illite is completely dissolved. The kaolinite
platelets are about half-dissolved, and an amorphous
material is coating the undissolved kaolinite, welding
them together and to the underlying quartz grain.
18-6. 2. Sequential mud acid
The sequential mud acid system involves the in-situ
generation of HF, occurring from the alternate injec-
tion of HF and ammonium uoride (Hall et al., 1981).
The reactions of HF are thought by some to take place
at the rock surface by adsorption followed by ion
exchange, but the yield of this heterogeneous process
seems highly doubtful for several reasons:
If HF were generated through such a process, it
would be a small quantity, hardly enough to etch
the surface of the clay material.
Because this process is based on the CEC of the
clays, migrating kaolinite would hardly be touched.
18-10 Sandstone Acidizing
This process supposes the initial adsorption of the
hydronium (H
3
O
+
) ions on the clay surface, fol-
lowed by their exchange with NH
4
+
, to generate HF
in situ. Exchange and replacement of H
3
O
+
by NH
4
+
depends on many parameters and cannot be ascer-
tained. Therefore, even the generation of HF is
dubious.
18-6. 3. Alcoholic mud acid
Alcoholic mud acid formulations are a mixture of
mud acid and isopropanol or methanol (up to 50%).
The main application is in low-permeability dry gas
zones. Dilution with alcohol lowers the acid-mineral
reaction rate and provides a retarding effect.
Cleanup is facilitated; acid surface tension is
decreased by the alcohols while the vapor pressure
of the mixture is increased, which improves gas perme-
ability by reducing water saturation.
18-6. 4. Mud acid plus aluminum chloride
for retardation
An acidizing system to retard HF-mineral reactions has
been proposed in which aluminum chloride (AlCl
3
) is
added to mud acid formulations to complex some of
the uoride ions in the injected mixture, according to
the reactions (Gdanski, 1985)
AlCl
3
+ 4HF + H
2
O AlF
4
+ 3HCl + H
3
O
+
AlF
4
+ 3H
3
O
+
AlF
2
+
+ 3HF + 3H
2
O
This procedure is tantamount to adding dissolution
reaction products to the mixture before the reactions
occur (i.e., the injection of spent acid). In theory this
should slow the rates. However, the retardation of clay
dissolution has not been proved experimentally because
of the prime importance of the high surface area on
clay reactivity, which is much more important than a
slight depletion of acid at high temperatures. The risk
of early precipitation of damaging products, such as
AlF
3
or uoaluminates, is probably increased by the use
of an acid that already contains aluminum ions before
reaction. Flow tests have shown a smaller effective live
acid penetration than in the case of mud acid. In addi-
tion, eld experience has shown that the addition of
aluminum to the system increases the precipitation of
amorphous aluminosilicate scale. This white material
plugs near-wellbore perforations and gravel packs.
18-6. 5. Organic mud acid
Because total acidity speeds mineral dissolution with
mud acid, organic mud acid involves replacement of
the 12% HCl component with organic acids (9%
formic acid, a weak acid that only partially dissoci-
ates), mixed with 3% HF, to retard HF spending. This
system is particularly suited for high-temperature
wells (200 to 300F [90 to 150C]), for which pipe
corrosion rates are diminished accordingly. This sys-
tem also reduces the tendency to form sludge.
Reservoir Stimulation 18-11
Figure 18-3. SEM photograph of kaolinite (K) and illite (I)
clays in a pore (Q = quartz), before attack.
Figure 18-4. SEM photograph of the same pore after an 8%
HBF4 treatment.
18-6. 6. Self-generating mud acid systems
Self-generating acidizing systems were originally
developed by Templeton et al. (1975), and their appli-
cation was widened by Abrams et al. (1983). They
involve the hydrolysis of organic esters into the corre-
sponding carboxylic acids, followed by the reaction of
these acids with ammonium uoride to yield HF.
Because the hydrolysis reaction is activated by tem-
perature and the acidity obtained is not as strong as
with mud acid, a low corrosion rate of tubular goods
and delayed reaction of the progressively generated
HF are expected. The latter would allow deep penetra-
tion of live HF.
Depending on the bottomhole temperature, different
organic esters are used:
methyl formate between 130 and 180F [55 and
80C] with the reactions
HCOOCH
3
+ H
2
O HCOOH + CH
3
OH
HCOOH + NH
4
F NH
4
+
+ HCOO
+ HF
(the latter is the slow, rate-controlling reaction).
ammonium salt of monochloroacetic acid between
180F and 215F [102C]:
NH
4
+
+ ClCH
2
COO
+ H
2
O
HOCH
2
COOH + NH
4
+
+ Cl
( )
[ ]
+
|
.
`
,
4 917 10
6
.
,
ln
V r r
p s w
( )
[ ]
7 48
2 2
. ,
p
q
D
pipe friction
518
0 79 1 79 0 207
4 79
. . .
.
,
sion). Because the acid does not follow the ideal
mode, adjustments to the injection volumes must be
made. Signicant changes in the uid can also occur
in the tubulars, before the uid reaches the forma-
tion. The dilution of stage composition and spending
are just some of the complications that must be
addressed by the designer. The use of smaller tubu-
lars, such as coiled tubing, during acid treatments can
contribute to a better acid job by facilitating the main-
tenance of stage integrity and reducing displacement
volumes. Mechanical limitations associated with arti-
cial lift (e.g., gas lift) are more easily overcome by
the use of coiled tubing. The risks of leaking valves,
undiluted acid remaining in the mandrels and acid
leaking into the tubing/casing annulus are avoided.
The limited injection rate coincidentally controls the
contact time. The pump rate and extraction out of
the tanks holding the acid can create a bottleneck
during execution. A complete understanding of the
operational aspects is necessary for proper execution.
One of the considerations in selecting the stage
volumes is the tubulars. The volumes of diverter and
their location in the tubulars while injecting must be
considered, especially for the use of foam diverters.
When using foam diversion techniques, brief shut-
downs or momentum changes are called for to maxi-
mize diversion. If the foam is in the tubulars when
the shutdown occurs, phase separation of the foam
can occur, affecting the foam diverter performance.
Another consideration is the preush activity.
If formations do not have much solubility in HCl,
operators have tended to lower the volume of acid
preush and use brine. However, Gdanski and
Peavy (1986) reported that this is not a good idea
because the HCl preush performs the vital func-
tion of cation exchange, which prepares the mineral
surfaces for the HF mixture. The cation exchange
must otherwise be done by the HCl portion of the
HF mixture, which raises the pH of the acid system
and induces the precipitation of silicate complexes.
As a minimum, the preush should penetrate the
same distance as the HF mixture (e.g., if the HF
blend volume penetrates 2 ft, then the preush
should penetrate a minimum of 2 ft).
Where the HCl solubility is moderate to high,
more HCl is necessary. The following equation is
used to calculate this volume and address the HCl-
soluble materials:
(18-8)
where
V
HCl
is the volume of HCl required in gal/ft, X
HCl
is
the fraction of the bulk rock dissolved by HCl, and
is the dissolving coefficient expressed as the
amount of rock dissolved per gallon of acid and is
related to the acid strength.
18-10. 2. Flowback and cleanup techniques
Selection of the correct owback procedure is critical.
The owback during multiphase transition periods can
cause irreversible damage. The nes loosened during
the acid job are invariably produced back into the
near-wellbore area. These nes can be removed in
diluted concentrations that pass through the comple-
tion if small, gradual pressure drops are created. This
was demonstrated by Krueger (1986).
The following are key factors to consider for ow-
back in sandstone formations:
The uids owing back are more viscous than
those injected. They are capable of carrying natural
formation nes and other partially dissolved solids
at lower velocities, which can cause plugging
before the well cleans up completely.
The spent acid usually has a higher density than the
formation water. The tubing pressure should be
lower than when connate water is produced, owing
to the higher hydrostatic pressure of the spent acid.
Spent acid has an equilibrium established of poten-
tial precipitants, held in place by dissolved gases and
dissolved salts. Should these gases (e.g., CO
2
) be
removed from the spent uid as a result of creating
an excessive pressure drop, precipitation will occur.
A minimum velocity is necessary for liquid to be
voided from the tubing without slippage occurring.
The minimum velocity to the unload tubing can be
calculated. The ow rate and tubing pressure in this
calculation should include the heavier liquid den-
sity. The ow rate should be achieved gradually but
sufficiently soon to avoid precipitation in the for-
mation. The rate should then be maintained until all
injected uids are returned and both the tubing
pressure and production rate are steady. Plotting the
gradual incremental choke changes as pressure and
rate stabilize provides insight to the affect of the
acid treatments on the formation and completion.
Reservoir Stimulation 18-25
V
X r r
HCl
HCl s w
( )
[ ]
7 48
1
2 2
. ,