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Summary. Well treatments with only HCl are potentially damaging in formations that contain aluminosilicate minerals (clays, feldspars, and micas) because HCl reacts significantly with aluminosilicates, leaching aluminum and forming hydrated silica. Fluid flow
past leached mineral particles liberates mineral fragments and amorphous silica within the pore network. These fines can block pore
throats, reducing the rock permeability. Both field data and reservoir-condition coreflood test results are consistent with this chemical
reaction and permeability impairment mechanism. The average permeability reduction in our corefloods was 35 %.
Introduction
Acids have been used widely for increasing or restoring the permeability of subterranean formations. Acid reactions can produce
several side effects, however, that decrease formation permeability. In particular, mud acid can spawn a host of precipitates as it
reacts. I-3 As acid dissolves matrix and matrix cement, mineral
grains are liberated and can migrate to plug pores. 1,4-6 Recognition of these and other acid-induced damage mechanisms has led
to a variety of different formulations of acids and additives.
An unacknowledged potential source of damage from acid treatments arises from the reaction of HCl with aluminosilicate minerals. This reaction is largely overlooked in the oil industry. In fact,
it has been stated that HCl does not react with clay minerals, 1,7
although the extraction of iron from chlorites by HCl has been mentioned as a potential source of damage.I,s Gdanski and Peavy9 appear to have been first to point to the consumption of HCl upon
aluminosilicate minerals in well treatments. Their analysis, however, was based on samples ofretums from a mud-acid treatment,
and HClIaluminosilicate chemistry in the presence ofHF is greatly
complicated by the numerous precipitation/dissolution reactions involving fluorine.
Whatever the role of HCl in the presence of HF, workers in fields
such as catalyst activation 10 and aluminum production II have established that HCl alone reacts to a significant degree with aluminosilicates. For a generic aluminosilicate, this reaction can be written
as
MvAlwSix0Y<0H)z+yH+ ->wAI +3 +xH 4Si0 4 +vM+m,
where M represents collectively all the metal elements commonly
found in aluminosilicates (Na, K, Mg, Ca, Fe, etc.). Balancing mass
and charge in this reaction imposes two relations between the
stoichiometric coefficients: y=3w+mv, andz=4x-3w-mv. At low
pH, the precipitation of amorphous silica 12 limits the aqueous concentration of H 4 Si0 4 , and the reaction becomes
MvAlwSixOy(OH)z+yH+ ->wAI +3
+x(amorphous silica)+vM+m.
Aluminum and metal ions are extracted from the mineral, leaving
behind a siliceous residue.
Because aluminum is an essential constituent of aluminosilicate
mineral lattices, its removal by HCl must weaken the structure of
the mineral particles. The fraying and framentation of aluminosilicates exposed to strong acid are well documented. 13-15
This physical degradation into mineral fragments and amorphous
silica particles has important implications for well treatments. The
injection of HCl into argillaceous or feldspathic sandstones will create fines, independently of the formation of precipitates, the dissolution of cement, and the presence of HF. The potential for
formation damage from fines migration is well established. Consequently, the assumption that HCl cannot hurt and might help is
not always valid in sandstone-matrix stimulations, preflushes, and
cleanup treatments.
Mathematical Development:
Flow With RateLlmlted Reaction
We model a well treatment as steady, isothermal, single-phase, ID
flow with reaction. Because transfer of aluminum from the solid
matrix into the aqueous phase is the essential feature of HClIaluminosilicate reactions, we need consider only conservation equations for aluminum. In the absence of dispersion, these equations
take the form
aCalatD+aCalafD=twR ........................... (1)
............................... (4a)
andR(fD~tD,tD)=O,
.............................. (4b)
These approximations do not hold if the medium contains minerals that consume HCl rapidly, such as carbonates. In this case,
dissolution waves 3 form, and their progress determines the breakthrough of injected HCl concentration. For example, if the medium initially contains CaC0 3 at concentration C j , HCl will arrive
at the medium outlet at time
tb=l+2qcA+ .................................. (7)
if no minerals precipitate.
455
Interface Control. The rate of an interface-controlled reaction depends on two factors: the chemical driving force and the effective
surface area of the interface. In general, the chemical driving force
is a complicated function of species activities, surface energies, and
chemical potential gradients. 17 In acidic solution far from equilibrium, however, the driving force i~proportional to hydrogen ion
activity. 16 In our experiments, HCl concentration is nearly constant (Eq. 6), so we take the chemical driving force to be constant.
Thus, the interface-controlled rate expression is
and ceff =Iwkss for tD > Iss (steady state) ............... (16)
As a reaction proceeds, it is possible for the kinetics to change
between interface control and diffusion control. When such a transition occurs, the effluent history changes accordingly. Suppose,
for example, that HCl attack is interface-controlled and first-order
(p= 1) until the solid concentration decreases to some critical value
Csc. Suppose further that at this critical value steady-state diffusion
becomes rate-limiting. Then R will have the form
R=O
for iD>ID
and R=kss
for tc<tD,
Experimental Procedure
Materials. Cores from two sandstone formations were used in this
surface reaction rate expression is 16,20 R=k/t'h. For a linear coreflood, we must modify this expression to
perimental conditions used during this study. The long-core samples (up to 85x3.8 cm) were assembled from shorter plugs of
similar permeability and porosity (typically either 6.4 or 20 cm in
length). The core material was confined in the experimental apparatus at simulated reservoir conditions (up to 69-MPa confining
pressure, 48-MPa pore pressure, and 115C).
The permeability to a reference brine was measured initially. The
test material was then treated with a volume of HCI containing no
additives. The total volumes of HCl used were chosen to simulate
typical field treatments. The total residence time of acid in the samples was usually comparable with the contact time of acid in a formation during a typical matrix treatment. The permeability to a
reference brine of the core was redetermined after acid injection.
Several experiments entailed sequential flushing of the sample
with alternate stages of acid and referen~e brine at different flow
rates. This enabled the precise determination of the influence of
residence time on the acid/clay interaction.
Discussion of Results
In all experiments, the effluent silicon concentration after HCI breakthrough was constant and equal to the silicon concentration in equi-
to account for the time required for the HCl front to travel through
the medium.
The continued extraction of aluminum establishes a leached surface layer on the mineral. It is possible for the leached layer to attain a steady-state thickness 20 when the rate of advance of the layer
into the unreacted mineral equals the rate of the destruction of the
layer's outer edge. (This destruction may be caused by dissolution
of the layer constituents into the bulk solution or physical disintegration.) At steady state, the leaching rate is constant:
R=kss for tss<tD (steady state) ..................... (12)
where tss = time when a steady-state layer is established on all reactive minerals in the core.
456
1
2
3
4
5
6
7
8
9
Core PV
(cm 3)
PV Injected
Birchover gritstone
Birchover gritstone
Synthetic core; 9.5 wt%
kaolinite
Synthetic core; 2.5 wt%
kaolinite
Synthetic core; 5 wt% montmorillonite
166
173
75
4.2
4.2
8.3
9
1.7
7.6
111
85
1
2
1
2
3
4
8.3
8.3
245
8.3
10
95
33
Material
86
115
Stage
Stage
Stage
Stage
Stage
Stage
16.7
8.3
8.3
25
50
83
1.8
6.6
2.2
4.3
4.3
8.7
25
10
eoc,
All tests used 15% HCI except Test 1. which used 7.5% HC!. All tests were carried out at
except lor Tests 1 and 9,
which were conducted at 30 and IISC, respectively. Confining and pore pressures were kept constant for individual tests;
between tests, the confining and pore pressures varied from 21 to 69 MPa and from 11 to 52 MPa, respectively. Alternating
stages of reference brine and acid were used during Tests 4 and 5.
5~--------~-----------------'
<=
o
:;::;
o
[;J
.
observed (Expt. 6)
- - First order (Eq. 14)
- - Steady state (Eq. 16)
'-.
<=
'-
'<="
..
'-.~
>-
0.5
...,
...,c...
Ql
U
C
o
u
...,
C
Ql
0.25
:J
......
....
....
UJ
'"o
-'
'"
~--------
I Expt. 7
I [AI)
j [Cal 110
'M
III
'"E 10
"01
11
13
15
17
19
21
10
12
14
Time (PV)
Time (PV)
it is practically insoluble in HCl. Thus, only physical disintegration can destroy the layer's outer edge fast enough to establish a
steady state. Hydrodynamic forces arising from flow in the porous
medium may achieve this disintegration. Thus, the HCl flow through
a rock containing aluminosilicate minerals can be expected to induce migration of aluminosilicate mineral fragments and amorphous
silica.
The results of Experiment 7, summarized in Table 2, provide
an example of this fines production. Before HCl injection, brine
eluted from the core contained about 4 x 10 6 particles/cm 3 . HCI
eluted from the core contained nearly 1,000 times as many fines.
Analysis with polarized light and quantitative scanning electron
microscopy showed these fines to be mostly amorphous silica with
some mineral fragments. Brine injected after HCl also contained
far more fines than the brine that preceded the HCI treatment, though
at a lower concentration than in the acid. When HCI injection resumed, fines production increased again. The fact that both brine
and HCI eluted substantial quantities of fines after HCI injection
through the medium supports the hypothesis of physical disintegration of the leached layer by hydrodynamic forces.
In all but one experiment, fines migration arising from HClIaluminosilicate reaction resulted in losses of permeability, as Fig. 4
shows. The average degree of damage was 35%. Synthetic cores
containing both calcite and a clay suffered damage, despite complete calcite removal. The conditions under which plugs suffered
permeability impairment, however, varied considerably. In some
cases, permeability declined steadily during the first PV of acid
injection and then leveled off. In other cases, the rate of permeability loss was steady throughout acid injection. In still other cases,
';;;8
Expt. B
c
0
III
Ql
permeability was not impaired until a high flow rate was used, consistent with a critical velocity threshold for fines migration. The
degree of damage was also temperature-dependent because the HCI
reaction rate increases with temperature. The permeability of an
outcrop sandstone declined by a factor of three when HCl was injected at 30C, but at 80C the loss of conductivity was nearly total.
Quantitative prediction of the degree of permeability loss caused
by the HClIaluminosilicate reaction requires more data about the
sizes of the fines generated within the core and the rate at which
they are released from the minerals. We can, however, make some
qualitative assessments. The rates at which fines are created, entrained into the flowing fluid, and trapped at pore constrictions determine the permeability loss from HClIaluminosilicate attack. The
rate of the creation of fines is essentially the rate of the HCl/aluminosilicate reaction, possibly augmented by the extent of the reaction. The rate at which created fines are released from mineral
surfaces is a complicated function of the nature and velocity of the
flowing fluid and stress differences within the rock matrix, but in
general we may expect more fines to be released at higher flow
rates (cf. Table 2). The rate of trapping of fines within the pore
network depends on the respective size distributions of the fines
and the pore throats. 22 ,23 Thus, a high-temperature, lowpermeability formation that contains a high concentration of aluminosilicate minerals can be expected to be most susceptible to
damage from HCl. Of course, not all formations are susceptible
to damage by fines migration (see below for an example), and in
some situations the benefit from HCl may outweigh any damage
incurred. Thus, we do not suggest that the use of HCl guarantees
damage in sandstones.
HCI/Aluminosilicate Reactions in the Field. Because our experiments were conducted at typical reservoir conditions, we expected
HCIIaluminosilicate reactions to occur in the field. Recent experience confirms this expectation. Before a workover, one of our North
Sea wells was killed with calcium carbonate lost circulation material (LCM). After the workover, 28% HCl containing corrosion
inhibitor, surfactant, and iron-controlling additives was injected to
remove the LCM. The formation contains some feldspar and about
10 wt% clay minerals, mostly illite and kaolinite. Analysis of sam-
iT)
E
....
...,
...,c...
[AI]
[Ca]/10
U
C
0
U
...,
c
Ql
:J
..............
UJ
0
0
Time (PV)
Fig. 3-HCl/montmorlllonlte reaction exhibits transition klnet
Ics after calcite Is dissolved from core.
458
Flow Rate
(10 -3 em 3 /s)
8.3
8.3
8.3
17
Fines
(number/em 3 fluid)
4.0x 10 6
3.0x10 9
9.6x 10 8
3.8x10 9
......
1.2
enE
'OJ
+'
.....
co
0.8
.....
'"
>-
+'
.....
...
'- 0.6
0.4
.Cl
'"E
OJ
+'
C
.0.... 1.5
+'
r~~
co
'-
+'
cQ}
c
u
.....
0.5
<t
rn
0.2
::J
0
Q}
OJ
~--
"\ ..
'-
n..
......
CJ)
::J
c-
40
80
120
160
200
240
280
pIes of the returned acid (Fig. 5) showed that the HCI did not spend
on the LCM. Live acid contacted the formation, and significant
aluminum leaching occurred. The aluminum history in Fig. 5 is
consistent both quantitatively and qualitatively with the laboratory
effluent histories (Figs. 1 through 3). Although fines are likely to
have been released in the formation as a result of acid invasion,
the well productivity was not impaired in this case because production was principally through a system of natural fractures.
Conciuslons
Under typical reservoir conditions, HCI reacts significantly with
aluminosilicate minerals (clays, feldspars, and micas). This reaction creates fines, and as a result HCI has the potential to damage
sandstones containing aluminosilicates. Whether permeability loss
occurs depends on the susceptibility of the formation to damage
from fines migration. The presence of minerals that rapidly consume HCl delays but ultimately does not prevent the HCl/aluminosilicate reaction.
The HClIaluminosilicate reaction creates fines within the porous
medium by two mechanisms. First, HCI extracts aluminum and
weakens the crystalline structure of the minerals. Second, the HCI
attack establishes a siliceous leached layer on the surface of the
mineral particles. Seepage forces associated with flow of fluid
through the medium disintegrate the weakened mineral particles
and steadily erode the leached layers, creating aluminosilicate fragments and amorphous silica particles. Because hydrodynamic forces
are responsible for releasing fines, any fluid that follows HCI will
continue to release fines. The rates at which these fines are released
and trapped control the degree of permeability impairment.
Nomenclature
A = effective surface area of minerallsolution interface,
m 2 /m 3
<t
20
40
k = rate constant
kd = diffusion-limited rate constant, kg/m3 PV' s
kp = power-law rate constant, (m 3 PV/kg)l-Pls
kss = steady-state diffusion-limited rate constant, kg/m3
PV's
= length, cm
D = dimensionless distance in PV's
L = characteristic length of porous medium, cm
p = exponent in power-law rate expression
q = acid flow rate, cm 3 Is
R = rate of HClIaluminosilicate reaction, kg/m3 PV's
t = time, seconds
tb = acid breakthrough time in PV's
tc = time at which HClIaluminosilicate reaction becomes
diffusion-limited in PV's
tD = dimensionless time in PV's
tss = time when rate reaches steady state throughout
porous medium (in PV's)
tw = residence time in porous medium, seconds
V = volume of mineral particle in porous medium,
m 3 /m 3 PV
rJ> = porosity
Acknowledgment
We thank the British Petroleum Co. for supporting this work and
for permitting publication of this paper.
References
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22-25.
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459
Authors
Stavan L Bryant
earned a PhD
degree In chemical
engineering from
the U. of Texas,
where he focused
on flow through
permeable media
with preclpltatlonl
dissolution reactions. In 1986, he
Buller
Joined BP Research
Bryant
Centre In Sunburyon-Thames to Investigate the role of reactive flow In formation
damage. David C. Bullar leads a team conducting special
core analysis at the BP Research Centre. He previously specialized In formation damage and matrix stimulation. He holds
a PhD degree In chemistry from the U. of Stirling, Scotland.
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26-27.
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Minerals (1970) 8, 337-45.
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Wiley & Sons Inc., New York City (1981) 523-98.
13. Miller, R.: "Electron Micrographs of Acid-Edge Attack of Kaolinite, "
Soil Sci. (1968) lOS, 166-71.
14. Ross, G.: "Acid Dissolution ofChlorites: Release of Magnesium, Iron
and Aluminum and Mode of Acid Attack," Clays arul Clay Minerals
(1969) 17, 347-54.
15. Gastuche, M., Delmon, B., and Vielvoye, L.: "Lacinetique des reactions beterogenes. Attaque du reseau silico-aluminique des kaolinites
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16. Lasaga, A.: "Chemical Kinetics of Water-Rock Interactions," J. Geophys. Res. (1984) 89, 4009-25.
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Interactions-I. Model for Interface-Controlled Reactions," Geochim.
Cosmochim. Acta (1981) 45, 79-92.
18. Hofmann, H. and Schoenborn, N.: "Zum Verhalten ausgewaehlter Tone
bei der Behandlung mit Saeure," Z. geol. Wiss. (1984) 4, 429-42.
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of Alumina in Acidic Solution," AIChE J. (1987) 33, 267-73.
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Water and Granitic Rock," Geochim. Cosmochim. Acta (1973) 37,
2641-63.
460
21. Bertaux, J.: "Treatment-Fluid Selection for Sandstone Acidizing: Permeability Impairment in Potassic Mineral Sandstones," SPEPE (Feb.
1989) 41-48.
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AIChE J. (1987) 33, 1654-62.
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Particle Entrapment in Porous Media," Chem. Eng. Sci. (1987) 42,
1553-64.
Appendlx-Nucleatlon.Rate Expressions
The evolution of a reaction limited by nucleation takes the general
integrated form ll ,18,19
f(E)=kt n , .................................... (A-I)
R=nkCsot~t
.......... (A-2)
where N=(m2 -1)/ml' Substituting Eq. A-4 into Eq. A-2 yields
a reaction rate R of the form R= -(kIN)(Cs ICso ) I +N, which is
also of the form of Eq. 10. Thus, the power law of Eq. 10 is satisfactory for describing interface-controlled dissolution of aluminosilicates by HCI.
OF
gal
in.
Ibm
psi
(OF-32)/1.8
x
x
x
x
3.785412
2.54*
4.535924
6.894757
E-03
E+OO
E-Ol
E+OO
C
m3
cm
kg
kPa
SPEPE
Original SPE manuscript received for review Nov. 1, 1988. Paper accepted for publication
July 17, 1990. Revised manuscript received Oct. 20, 1989. Paper (SPE 17597) first presented
at the 1988 SPE Inti. Meeting on Petroleum Engineering held in Tlan)in, Nov. 1-4.