Formation Damage

From Acid Treatments

Steven L. Bryant and David C. Buller, SPE, BP Research

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.

In this paper, we develop analytical expressions for aluminum

extraction resulting from HCl flow in porous media. Comparing
these expressions to reservoir-condition experiments suggests a consistent mechanism for the HClIaluminosilicate reaction. This reaction is shown to be responsible for the permeability losses observed
in the corefloods. We then consider the potential for damage from
the HClIaluminosilicate reaction in the field.

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)

and aCslatD=-twR, ................................ (2)

where tD=tlt w, fD=fIL, and tw=t/>LAc1q.In Eqs. 1 and 2, we
assumed that porosity does not change appreciably during HCI flow,
that any moving solid particles contain insignificant amounts of aluminum, and that exchange of H + for other cations is negligible.
To supply boundary conditions for Eqs. 1 and 2, we assume that
the injected acid contains no aluminum.
Ca(fD=O, tD)=O . ................................. (3)

Because no aluminum leaching occurs at any given position in the

medium until acid arrives there, we require that
Cs(fD~tD,tD)=CsO

............................... (4a)

andR(fD~tD,tD)=O,

.............................. (4b)

where Cso = initial aluminum concentration in the solid phase.

Some further observations will simplify the forms of R discussed
below. If ~e product twR is small and the injected HCI concentration, Ch+' is high, then to a good approximation, Ch+ advances
through the medium at the same velocity as the fluid. In this case,
aluminum leaching at an arbitrary position fD begins at time
tD=fD , and we have
R>O for tD>fD . .................................. (5)
Furthermore, after HCl breakthrough-Le., for tD> I-the concentration of HCl within the medium is nearly constant, and to a
good approximation
CH+=CA+ forfD<tD' ............................ (6)

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)

Copyright 1990 Society 01 Petroleum Engineers

SPE Production Engineering, November 1990

if no minerals precipitate.
455

HCIIAluminosilicate Kinetics. By choosing an explicit expression

for R, we can solve Eqs. 1 and 2 for the effluent aluminum concentration history. The kinetics of the aqueous-phase reaction with
aluminosilicates has been .studied in connection with mineral
weathering l6 17 and aluminum extraction processes. II IS The kinetics falls into two categories 16: interface- and diffusioncontrolled. In an interface-controlled reaction, the rate-limiting step
is the breaking/forming of chemical bonds at the solution/mineral
interface. In a diffusion-controlled reaction, the rate-limiting step
is the physical transfer of reactant/product species between bulk
phases.

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

1 and 2 from boundary conditions (Eqs. 3 through 5) and letting

1, tD) denote the effluent aluminum concentration,
we obtain for the various rate expressions
ceff =Ca(iD =

ceff =twkp[(CsO -Csnc ) 1-p +twkp (l-p)(I-tD)]pl(l-p)

for tD> 1, p* 1 (power law), ........................ (13)

ceff =twk1 (Cso -Csnc)exp[twkl (I-tD)]

for tD> 1, p=I (power law), ........................ (14)

Ceff =twkd/(tD -1) 'h

for tD> 1 (parabolic), ........... (15)

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

R=kAforiD<tD, ........................... : ..... (8)

where A =effective mineral surface area per unit PV and k=rate

constant that incorporates the injected HCl concentration. We invoke a power-law relationship between effective surface area and
mineral concentration:
Ao:(Cs-Csnc)P, .................................. (9)

where p depends on the geometry of the mineral particles. Csnc ,

"noncontacting" or "noncontributing" mineral concentration, corrects the overall concentration for mineral surfaces not exposed to
pore fluids. Prediction of C snc a priori is difficult because many
factors influence the distribution of minerals within a rock. We
regard C snc as a matching parameter in the analysis of our
corefloods and assume that it remains constant during acid injection.
Combining Eqs. 8 and 9 yields

and R=kss

for tc<tD,

where tc=iD-(l/twkl)[ln(Csc-Csnc)-ln(Cso-Csnc)] is the time

when the critical solid concentration is reached at position iD' The
effluent aluminum concentration will be Eq. 14 for Iss> tD and Eq.
16 for tss < tD [where tss =tc(iD = 1)]. In other words, the effluent
concentration declines exponentially until the steady-state leached
layer is established throughout the medium, after which the effluent
concentration is constant.

Experimental Procedure
Materials. Cores from two sandstone formations were used in this

Diffusion Control. The classic example of a diffusion-controlled

study. Birchover gritstone, an outcrop sandstone from a quarry in

Derbyshire, contained feldspar (12%), authigenic kaolinite (10%),
and minor amounts of other authigenic species, including quartz
and illite. Material from one of our North Sea fields was also tested.
It contained more feldspar (18%) but less clay: 3% kaolinite and
2% illite.
Birchover gritstone was used for the initial tests, but interpreting
the acid effluent histories proved difficult because of the complicated rock mineralogy. To avoid this complication, a novel resinbonded sandpack was developed into which known concentrations
of one or more minerals could be incorporated. The physical and
chemical characteristics of the synthetic core were investigated
thoroughly and were similar enough to reservoir material to be suitable for use in this research. Because insufficient authigenic material
was available, detrital clays were used in this study.

surface reaction rate expression is 16,20 R=k/t'h. For a linear coreflood, we must modify this expression to

Method. Table 1 summarizes the range of core material and ex-

R=kp(Cs-Csnc)P for iD<tD (power law) ............ (10)

for the interface-controlled dissolution rate of aluminosilicates in

porous media subjected to strong HCl.
The development of Eq. 10 was motivated by rate expressions
applicable to natural (pH~O) aqueous/aluminosilicate systems.
Nucleation-rate expressions are often used 10 describe interfacecontrolled dissolution under much harsher conditions. II . 15 ,IS,19
These expressions lead to rate equations of the same form as Eq.
10, as shown in the Appendix.

Emuent Histories for DitTerent Rate Expressions. For simplic-

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.

ity, we consider cores containing only one leachable mineral and

assume that the leaching kinetics do not undergo a transition. Thus,
we substitute only one rate expression (Eq. 10, 11, or 12) at a time
into the conservation equations (Eqs. 1 and 2). Integrating Eqs.

Discussion of Results
In all experiments, the effluent silicon concentration after HCI breakthrough was constant and equal to the silicon concentration in equi-

R=kd/(tD-iD)'h for iD<tD (parabolic) .............. (11)

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

SPE Production Engineering, November 1990

TABLE 1-SUMMARY OF EXPERIMENTAL CONDITIONS

Treatment
Test
--

1
2
3
4
5

6
7
8
9

Core PV
(cm 3)

Acid Flow Rate

(10 -3 cm3/s)

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

Synthetic core; 5 wt% illite

Synthetic core; 5 wt%
kaolinite + 5 wt% calcite
Synthetic core; 3 wt%
montmorillonite + 5 wt%
calcite
North Sea reservoir

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.

Iibrium with amorphous silica (-0.05 kg/m 3). This observation

is consistent with formation of a silicon-rich leached layer on aluminosilicate surfaces, which controls the aqueous silicon concentration in the core. This applies particularly to the synthetic core
experiments, in which aluminosilicates were the only source of aqueous silicon, because the resin coating prevents matrix sand grains
from contacting pore fluids.
We now compare coreflood effluent aluminum histories to the
predictions of Eqs. 13 through 16. Fig. 1 shows that effluent aluminum from core containing only illite (Experiment 6) follows flrstorder power-law kinetics (twk1 =0.16, Csne = 14 kg/m3 PV in Eq.
14) quite well up to time tD = 13 PV. The diffusion-controlled parabolic model, Eq. 15, cannot fit the data during this period. As the
logarithmic scale in Fig. 1 makes clear, however, the power-law
model predicts a continual exponential decline in concentration,
whereas the observed concentration attains a constant value after
tD = 13 PV. Indeed, the steady-state model (twkss =0.55 kg/m3 in
Eq. 16) fits the data nicely for tD > 13 PV. Thus, the aluminum
history flts a transition model of the form of Eqs. 14 and 16 with
tss = 13. This behavior is consistent with the HClIillite reaction initially being interface-controlled, then becoming diffusion-controlled
as a leached layer forms and attains a steady-state thickness.
Fig. 2 shows the effluent calcium and aluminum concentrations
from a core initially containing both calcite and kaolinite (Experiment 7). The HCI reacts so rapidly with calcite that local equilibrium applies and a calcite dissolution wave forms. The aqueous phase
downstream of this wave consists of acid completely spent on calcite. Spending 15% HCI on calcite yields a solution 4 containing
about 88 kg/m3 calcium. The observed calcium concentration attains this saturation value between tD = 1 and 3 PV, supporting the
local eqUilibrium prediction. During the same time interval, the effluent aluminum concentration is negligible, indicating that the
kaolinite has not yet been attacked.
Upstream of the calcite dissolution wave, all calcite has been dissolved, so the HCI there contacts only kaolinite. Consequently, the
pH'upstream of the dissolution wave is nearly the injected pH (cf.
Eq. 6), and the arrival of the calcite dissolution wave at the core
outlet coincides with HCI breakthrough. The initial calcite concentration in Experiment 7 is 3.8 mol/L PV, so Eq. 7 predicts HCI
breakthrough at tb=2.7 PV. At tD=3 PV in Fig. 2, the observed
calcium concentration drops and the observed aluminum concentration increases, both consistent with the predicted HCI breakthrough. Following HCI breakthrough, the aluminum concentration
attains a plateau almost immediately, consistent with the
HClIkaolinite reaction quickly reaching a diffusion-limited steady
state (Eq. 16). This experiment shows that the HClIaluminosiliSPE Production Engineering, November 1990

cate reaction is negligible as long as other minerals that consume

HCI rapidly are present. Once these minerals are depleted, however, HCI immediately begins to extract aluminum.
Fig. 3 shows the calcium and aluminum effluent from a core containing calcite and montmorillonite (Experiment 8). As in Fig. 2,
a plateau of acid spent on calcite precedes HCl breakthrough. After breakthrough, the aluminum concentration shows a peak followed by a gradual decline into a plateau beginning at tD = 8 PV.
The behavior after HCI breakthrough qualitatively matches the
HCl/illite effluent (Fig. 1), suggesting that montmorillonite also
undergoes a transition from interface-controlled to diffusion-limited
kinetics.
Montmorillonite has a large speciflc cation exchange capacity
(CEC) that arises from charge deflciencies in the clay layers. 12
These deficiencies are caused by isomorphous substitution by trivalent cations, chiefly Al +3, in the tetrahedral clay layers and by
divalent cations in the octahedral clay layers. Because aluminum
extraction by HCI gradually destroys the octahedral layers and removes any aluminum from the tetrahedral layers, 14 a side effect
of HCI injection should be to decrease the core's CEC. Experiment 5 tested this prediction. The synthetic core containing montmorillonite was saturated with KCI brine. When CaCl 2 brine
displaced the KCI, cation exchange delayed calcium breakthrough
for 4 PV. But after the flrst stage of HCI (see Table 1), a similar
sequence of brines produced no delay in divalent ion breakthrough.
This indicates that the core's CEC had been reduced to zero, a result consistent with the mechanism of HCI attack.
Figs. 1 through 3 demonstrate that injecting HCI through synthetic cores under reservoir conditions extracts aluminum from clay
minerals contained in the cores. We have observed qualitatively
identical aluminum histories after injecting HCI into both outcrop
and reservoir sandstones containing clays and feldspars, as has Bertaux. 21 In each case, the aluminum history eventually attains a
plateau, consistent with the establishment of a leached layer of
steady-state thickness.
Physical Effects ofHCIIAhiminosilicate Attack. The HCl/aluminosilicate reaction has two important physical effects. First, the
extraction of aluminum from an aluminosilicate mineral weakens
its structure, making it susceptible to physical fragmentation. Fluid
flow past the mineral and stress differences within the rock may
exert sufficient force to cause disintegration of the mineral particle.
Second, the fact that the leached layer on a particle surface attains a steady-state thickness implies that the layer's outer edge is
being destroyed at the same rate that the inner edge advances into
the mineral. Because the leached layer is largely amorphous silica,
457

Theoretical predictions vs. Expt. Data

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)

Fig. 1-HCllllilte reaction exhibits transition from Interfaceto diffusion-controlled kinetics.

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...

Fig. 2-When calcite Is present, HCllkaollnlte reaction Is

delayed until calcite Is dissolved from the core and then ex
hlblts dlffuslonllmlted kinetics.

[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

TABLE 2-CONCENTRATION OF FINES

IN EFFLUENT DURING EXPERIMENT 7
Injected Fluid
Brine before Hel
15% Hel
Brine after Hel
15% Hel

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

SPE Production Engineering, November 1990

......

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

Original permeability (md)

Fig. 4-Ratlo of permeability of core plugs after HCllnJectlon

to original permeability.

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

Ac = cross-sectional area of porous medium, cm 2

ceff = aqueous aluminum concentration in core effluent,
kg/m 3
Ca = total aqueous-phase concentration of aluminum,
kg/m3 PV
CH + = concentration of HCl in porous medium, mollL
CJ+ = injected HCI concentration, mol/L
Cj = initial calcite concentration in porous medium,
mol/L PV
C s = total solid-phase concentration of aluminum, kg/m3 PV
Csc = solid-phase aluminum concentration at which
reaction becomes diffusion-limited, kg/m3 PV
C snc = concentration of mineral in porous medium that does
not contact pore fluid, kg/m3 PV
SPE Production Engineering, November 1990

<t

20

40

Time, hrs after production resumed

Fig. 5-Alumlnum concentration In returns from HCI cleanup
treatment on a North Sea well demonstrates HCI attack on
formation aluminosilicates.

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
1. Mcleod, H. Jr.: "Matrix Acidizing," JPT (Dec. 1984) 2055-69.
2. Crowe, C.: "Prevention of Undesirable Precipitates From Acid Treating
Fluids," paper SPE 14090 presented at the 1986 SPE Intl. Meeting
on Petroleum Engineering, Beijing, March 17-20.
3. Walsh, M., Lake, L., and Schechter, R.: "A Description of Chemical
Precipitation Mechanisms and Their Role in Formation Damage During Stimulation by Hydrofluoric Acid," paper SPE 10625 presented
at the 1982 SPE Inti. Symposium on Oilfield and Geothermal Chemistry, Dallas, Jan. 25-27.
4. Williams, B., Gidley, J., and Schechter, R.: Acidizing Fundamentals,
Monograph Series, SPE, Richardson, TX (1979) 6, 1-3, 77-79.
5. Lievaart, L. and Davis, D.: "The Role of Fines During Acidizing Treatments," Marine Pet. Geol. (1987) 4, 127-31.
6. Mungan. N.: "Permeability Reduction Through Changes in pH and
Salinity." JPT (Dec. 1965) 1449-53; Trans., AIME, 234.
7. Gidley, J.: "Acidizing Sandstone Formations: A Detailed Examination of Recent Experience," paper SPE 14164 presented at the 1985
SPE Annual Technical Conference and Exhibition, Las Vegas, Sept.
22-25.
8. Shaughnessy, C. and Kunze, K.: "Understanding Sandstone Acidizing Leads to Improved Field Practices," JPT (July 1981) 1196-1202.

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.
9. Gdanski, R. and Peavy, M.: "Well Return Analysis Causes ReEvaluation ofHCI Theories," paper SPE 14825 presented at the 1986
SPE Symposium on Formation Damage Control, Lafayette, LA, Feb.
26-27.
10. Thomas, C., Hickey, J., and Stecker, G.: "Chemistry of Clay Cracking Catalysts," lrul. & Eng. Chem. (1950) 42, 866-71.
11. Hulbert, S. and Huff, D.: "Kinetics of Alumina Removal From a Calcined Kaolin With Nitric, Sulphuric and Hydrochloric Acids," Clay
Minerals (1970) 8, 337-45.
12. Stumm, W. and Morgan, J.: Aquatic Chemistry, second edition, John
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
par l'acide chlorhydrique," Bull., Soc. chim. Fr. (1960) 1, 60-70.
16. Lasaga, A.: "Chemical Kinetics of Water-Rock Interactions," J. Geophys. Res. (1984) 89, 4009-25.
17. Dibble, W. Jr. and Tiller, W.: "Non-Equilibrium Water/Rock
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.
19. Franke, M., Ernst, W., and Myerson, A.: "Kinetics of Dissolution
of Alumina in Acidic Solution," AIChE J. (1987) 33, 267-73.
20. Paces, T.: "Steady-State Kinetics and Equilibrium Between Ground
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.
22. Sharma, M. and Yortsos, Y.: "Fines Migration in Porous Media,"
AIChE J. (1987) 33, 1654-62.
23. Rege, S. and Fogler, H.: "Network Model for Straining Dominated
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)

where E=extent ofthe reaction, or E= I-CsICso . Thus, the rate

R=dCsldtD takes the form

/J-I l(dfldE) =k't/J-I l(dfldE) .

R=nkCsot~t

.......... (A-2)

The form of the function f depends on the effective surface area

and chemical driving force, among other things. II One form II is
f(E) = -In(I-E), which leads to the rate expression
R=k't/J-I (l-E)=k't/J-I CsICso . .................. (A-3)
In the special case n = 1, Eq. A-3 is of the same form as Eq. 10.
Hofmann and Schoenbom l8 take n=1 in Eq. A-I and derive
f(E) and k for particular particle geometries and acid/mineral
stoichiometries. Their approach amounts to using a geometrical
function V(r)=clr ml to relate particle volume, V, to some particle
dimension r, and a stoichiometrical function U(r) =c2rm2 to
describe acid concentration at the particle surface. This approach
leads to functions f of the form
f(E)=I-(I-E)-N, ............................. (A-4)

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.

51 Metric Conversion Factors

OF
gal
in.
Ibm
psi

(OF-32)/1.8

x
x
x
x

'Converslon factor is exact.

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.

SPE Production Engineering, November 1990