Understanding Sandstone Acidizing
Leads to Improved Field Practices
Christopher M. Shaughnessy, SPE, Exxon Production Research Co.
Kenneth R. Kunze, Exxon Production Research Co.
Summary
A design criterion based on type and depth of
damage is proposed to replace laboratory design
curves that may have been distorted by CO 2
evolution. Furthermore, sandstone acidizing ex-
periments have provided evidence that
reprecipitation of dissolved silica from spent HF can
be a real limitation to acidizing success if operational
precautions are not taken. Finally, the potential for
iron precipitation from spent HCI acidizing solutions
is seen to be dependent on certain conditions such as
iron oxidation state and the presence of carbonates.
Introduction
Over the years, many field practices have been
devised to maximize the success of conventional
sandstone acidizing techniques. Much of this
technology has been developed by field ex-
perimentation supported by only a limited amount of
scientific data. A comprehensive examination of
sandstone acidizing chemistry has revealed sound
technical reasons for many of the common field
acidizing operations. Other practices have been
shown by experiment to be groundless. By em-
phasizing this technical basis, we hope to reinforce
good acidizing practices and discourage poor ones.
Through experimental laboratory work, three
important concepts of sandstone acidizing have
emerged:
1. Hydrofluoric acid (HF) begins to increase rock
permeability as soon as it is injected, provided the
rock has been preflushed properly with HCl to
remove carbonates.
2. Silica precipitation from spent hydrofluoric
acid can be very damaging to rock permeability.
3. Sandstone formations containing iron-bearing
minerals can be acidized successfully.
These three concepts are important to the suc-
0149·2136/81/0007·9388$00.25
Copyright 1981 Society of Petroleum Engineers of AIME
1196
cessful design of hydrofluoric acid stimulation
treatments in the field.
Permeability Increase Caused by HF
The phenomenon of initial permeability decline
during laboratory acidization of cores is of particular
interest because of its influence on many acidizing
procedures. One of the earliest reports of this
phenomenon appeared almost 15 years ago, 1 and
numerous others have followed. 2-5 These ob-
servations have been incorporated into general field
guidelines that frequently call for large acid volumes
just to overcome the damage caused by initial acid
injection.
Various theories have attributed this initial damage
to fines plugging, precipitation of insoluble
fluosilicates, and precipitation of silica. However,
recent laboratory experiments have convincingly
demonstrated that the initial damage in laboratory
cores is caused primarily by CO 2 gas saturation.
CO 2 Damage in Cores
Most sandstones contain various amounts of car-
bonate minerals. When contacted with acid, car-
bonate minerals will react to generate CO 2 and a
corresponding salt. If this CO 2 is liberated as a
gaseous phase within the pore structure, the rock will
appear damaged. However, this phenomenon is not
true damage because the absolute permeability of the
rock is not decreased. Instead, the development of a
CO 2 gas saturation temporarily lowers the relative
permeability of the aqueous phase.
Solubility of CO 2 in Spent Acid
When 15070 hydrochloric acid is reacted totally with
carbonate minerals, the spent acid is very similar to a
20070 calcium chloride (CaCI 2 ) solution. Likewise,
the spending of 5070 HCl produces a solution similar
to 7.5070 CaCI 2 . Fig. 1 plots the solubility of CO 2 in
7.5070 and 20070 CaCl 2 vs. pressure. Amounts of CO 2
JOURNAL OF PETROLEUM TECHNOLOGY
 TABLE 1 - MAXIMUM PERCENT PERMEABILITY LOSS DURING HCI ACIDIZING

HCI
Temperature, Concentration Flow Rate 0.69 MPa 2.07 MPa 3.45 MPa 4.82 MPa 6.89 MPa 10.3 MPa
°C(OF) (%) mUmin. (100 psi) (300 psi) (500 psi) (700 psi) (1,000 psi) (1,500 psi)
22(72) 15 5 88.2 67.9 39.1 23.0 15.6 16.0
66(150) 5 5 88.6 83.4 70.2 7.4 10.9
66(150) 15 5 93.4 92.3 90.4 89.4 86.0 68.3

o 25~--------------------------------'
liberated from the total spending of 5OJo and 15OJo
HCl on carbonates are shown for comparison. It is
~
-'
readily apparent from these data that the CO 2 ~
a:
2.0
CO, FROM
SPENT 15% Hel
generated by totally spending 15OJo HCl far exceeds ~

if>
the solubility limits over the entire range of CO 2 ~ 15
z COzFROM
pressures. In contrast, the CO 2 produced by com- -' { SPENT 5% HC!

pletely spending 5OJo HCl can be kept in solution by ~ 1.0

o
~
maintaining a pressure greater than 5 MPa (about
_ _ _:---25"C
700 psi). ::::~~~~____---7~C
'"'3
8
Acidizing Laboratory Cores With HCI 0" 10 12 14 16 MPa
o I I I
If gas evolution is indeed responsible for all or part 500 . 1000 1500 2000 2500 PSI
COz PRESSURE
of the initial permeability damage observed during
acidizing, then the damage should be apparent when Fig. 1 - Solubility of CO2 in spent acidizing solutions.
plain HCl is injected and should exhibit a strong
pressure dependence. To test this prediction, several
BACK PRESSURE
3.8 cm (1.5 in.) in diameter by 5 cm (2 in.) long Berea MP. (PSI) 5 MUMIN
sandstone cores were acidized in Hassler-type cells
with 5OJo and 15OJo HCl using different back pressures
and temperatures.
Successive cores were acidized at the same tem-
perature, flow rate, and HCl concentration, but with
0
w
z
~
f-
w
a:
100
-
b-ll~0~.3J(.u15:.20~0);;;;;;_ _ _-::----!!!!!!!!!"-------~100

increasing pressure inside the core. Two series were >-

f-
conducted with 15OJo HCl, one at 22°C (72°F) and :i
iii
the other at 66°C (150°F). A single series was per- <l:
UJ
formed with 5OJo HCl at 66°C (150°F). The data, :;:
a:
summarized in Table 1, show the maximum per- UJ
Q.

meability loss observed during each experiment. It is *-

apparent from these data that the induced damage is
a strong function of pressure; lower pressures yield o 2 4
PORE VOLUMES HCI INJECTED
more damage while higher pressures give less. Figs. 2
and 3 further illustrate the pressure dependent nature Fig. 2 - Berea cores acidized with 15% HCI at 22°C (72°F).
of the initial permeability loss from acid contact. The
pressure dependence of this phenomenon is evidence
for a gas-related mechanism. BACK PRESSURE
The data of Fig. 1 predict that for a pressure near 5 MP. (PSII

MPa (725 psi) the CO 2 generated from spending 5OJo

HCl would remain completely dissolved and never 0
w
form a separate gas phase. Data in Table 1 for 5OJo Z
<l:
HCl show a dramatic drop in the maximum per- f-
UJ
meability loss from 70.2OJo at 4.82 MPa (700 psi) to a:
>-
only 7.4OJo at 6.89 MPa (1,000 psi). Again, the f-

correlation between core permeability behavior and ~

!Xl
100
<l:
CO 2 solubility data strongly supports the gas- UJ
:;:
saturation damage mechanism. a:
UJ
Q.

Analysis of acid effluent concentrations emerging *- 100

from the cores was conducted to determine the
degree of spending. At 66°C (150°F), between 75 and 0
0 2 4 6 8 10
85OJo of the acid was spent on the rock sample. PORE VOLUMES HCI INJECTED
However, at the lower temperature of 22° C, only 40
to 45OJo of the acid was spent. This partial spending Fig. 3 - Berea cores acidized with 15% HCI at 66°C (150° F).
explains the ability of pressures above 4.82 MPa (700
JULY 1981 1197
 10 MUMIN
66°C (150°F)
300
>-
!:::
..J
Ol
<l:
UJ
::;;
c::
~ 200
..J
<l:
Z "-
r.:J
c::
o o
*
100
15.2 CM (6 IN) CORE
35 ML PORE VOLUME
o 10 20 30
PORE VOLUMES 3% HF - 10% HCI INJECTED
Fig. 4 - Acid response curve of Berea core.
psi) to suppress damage in cores acidized with 15070
HCI at 22°C (72°F).
Recovery From Damage
If the generation of a CO 2 gas saturation is
responsible for the initial loss in permeability, then
removal of the gas should restore the rock to its
original permeability. Figs. 2 and 3 clearly show that
continued injection of HCI restores the permeability
to a value equal to or greater than that of the un-
treated rock. Because CO 2 is soluble in HCI, con-
tinued acid injection dissolves and removes the gas
saturation, thereby increasing the relative per-
meability to the aqueous phase.
Acidizing Laboratory Cores With HF
If HF is injected into a core previously acidized with
HCI, the permeability will begin to rise immediately,
without exhibiting a period of initial damage. To
demonstrate this behavior, a Berea core 3.8 cm (1.5
in.) in diameter by 15.2 cm (6 in.) long was mounted
in a Hassler-type cell at 66°C (150°F) with 6.89 MPa
(1,000 psi) back pressure. The core then was acidized
with 3070 HCI followed by 15070 HCI to achieve
complete removal of carbonate minerals.
The core was acidized next with 1,000 mL (28 PV)
of 3070 HF/1007o HCI pumped at 10 mLimin. The
acid response curve was recorded during injection
and is reproduced in Fig. 4. The permeability of the
rock began to increase immediately when HF was
injected. No initial damage of the type reported by
previous investigators was observed. Identical
behavior from tests on a wide variety of other core
material supports the general validity of this ob-
servation.
Permeability Profile After Acidizing With HF
To determine the permeability profile for a core
acidized with HF, a 76.2-cm (30-in.) Berea core was
acidized with 3070 HF/1007o HCI under conditions
identical to those of the acid response curve. This
experiment used a single core long enough to measure
1198
6oo,--------------------,
• BRINE
500 o FRESH WATER
"L1VE" HF
PENETRATION
400
o
::;;
::;; 300
a:
w
RESPONSE TO HC!
200
100
- -----INtTIAL--- - PERM.---- - - - - - - -
•
°OL--l~0-~20~~3~0--4~0-~50~~6~0--7~0-~ C~
( I I I I I I I
o 4 8 12 16 20 24 28 IN
DISTANCE FROM INJECTION FACE
Fig. 5- Permeability of a Berea core acidized with 3%
HF/10% HClat66°C(150°F).
directly the entire permeability profile. There was no
reliance on the mathematical extrapolation of short-
core acid response data.
After 2500 cm 3 (14 PV) of acid had been injected,
the core was cut into 15 5-cm (2-in.) sections. Each
section was tested for brine permeability and
freshwater sensitivity. Fig. 5 shows that even with
this large acid volume, net stimulation occurred only
within the first 30 cm (12 in.) of the input face. The
first 10 cm (4 in.) of core, which had experienced
about 100 PV of HF, was unconsolidated.
Although net stimulation only occurred out to 30
cm, it is significant that freshwater sensitivity was
removed from the entire core. Freshwater per-
meabilities taken after brine are similar to those
taken with brine. In other words, the clays in the
entire core were rendered insensitive to fresh water.
Design of Field Sandstone Acidizing Treatments
By using the information presented on how for-
mation rock responds to acid injection, acid treat-
ments for field application can be designed with
confidence. First, it is recommended that the acid
volume be chosen to match the type and depth of
formation damage in each candidate well. This
perspective on the acid design procedure eliminates
the concept of a large minimum acid volume. It
further allows the flexibility to use large acid volumes
when damage is extensive, and small volumes when
damage is limited. Indeed, many successful sand-
stone acidizing treatments have been performed
recently with small acid volumes.
The foregoing recommendation applies to the
majority of wells being acidized today. However, two
important exceptions exist: (1) sands with a very high
nonquartz content, and (2) wells with a very high
bottomhole temperature. When acidizing with either
of these conditions present, some initial permeability
loss may occur as a result of silica precipitation
(discussed in the next section). A reduction in the HF
concentration or a modification to the acidizing
procedure is required to achieve successful results.
JOURNAL OF PETROLEUM TECHNOLOGY
 EARLY TIME DATA EARLY TIME DATA

0.12 0.24 AI, Si, 0, (OHI,

0.10 0.20
...J ...J
W 0.16
~ 0.08 ...J
o o
::;; ::;;
<.i 0.06 Si u 0.12 AI
z z
o
8
~_~Si
0.04 AI u 0.08
_ __
0.02 0.04

o 30 90 120 150 180 o

TIME. MINUTES TIME. MINUTES

LATE TIME DATA LATE TIME DATA

0.12
0.24 [ - - - - - - = = = = = = = A = I :::::::;;:;;;;;:;;;;;;;-~
0.10 0.20
...J ...J
W W
...J 0.08 AI ...J 0.16
o o
::;; ::;;
~ 0.06 . " . So z
u
o
u 0.04 u 0.08

0.02 0.04~
o o 4 20 24
TIME. HOURS TIME. HOURS

Fig. 6- Reaction of kaolinite with 0.4 mol/L HF/1.0M HCI at Fig. 7- Reaction of kaolinite with 0.4 mol/L HF/1.0M HCI at
22'C(72'F). 66'C (150'F).

The second major sandstone acidizing design
consideration is recognition of the shallow depth of
permeability increase resulting from HF injection.
The maximum practical penetration distance at-
tainable with conventional HF/HCI mixtures has
been shown to be approximately 30 cm (12 in.). The
penetration distance actually achieved in the field
will depend on the acid volume, injection rate, and
temperature, but also will depend heavily on the
concentration of nonquartz constituents in the
reservoir rock. 6 Excessively large HF volumes will
not increase the penetration distance significantly but
instead will unconsolidate the reservoir near the
points of injection.
structural units, a silica sheet and an alumina sheet. 7
The manner in which these sheets are stacked plus the
degree of substitution by other elements determines
the type of clay.
Clay reacts with HF to form silicon and aluminum
fluorides according to the simplified reaction
AI 2 Si 2 0 S (OH)4 + 18HF-2H 2 SiF 6
+2AIF3 +9H 2 0.
However, in an actual spent acid, a distribution of
reaction products exists. 4,8,9 The silicon fluorides
exist as
SiF 4 , SiFs ~ ,and SiF 6 = ,

Spent HF Precipitates Silica while the aluminum fluorides exist as

Having restored flexibility to the sandstone acidizing
design procedure, attention may be focused on the
most serious problem associated with sandstone
acidizing - silica precipitation.
In studies of alumino-silicate mineral (clay and
feldspar) dissolution, Labrid 4 concluded that HF
uniformly attacks the clay structure solubilizing both
silicon and aluminum. However, in the latter stages
of reaction, aluminum dissolution continues while
silicon is precipitated from solution in the form of
colloidal silica. This sequence suggests that per-
meability damage from precipitated silica may limit
the success of sandstone acidizing treatments.
Dissolution of Clay Minerals by HF
In the majority of field applications, clay dissolution
dominates the response of the formation rock toward
HF. Clays have a layered structure composed of two
JULY 1981
Al + + + , AIF + + , AIF 2 + . . . AIF 6 '" .
Clay Dissolution in a Stirred Reactor
Of the clays studied, kaolinite most readily illustrates
the silica precipitation phenomenon. The kaolinite
was dissolved with 0.4 moUL HF and 1.0 moUL HCI
(about 1070 HF and 4% HCI) in a stirred reactor. The
low HF concentration permitted a large excess of clay
to be present while maintaining the reactor contents
as a flowable slurry. Experience has shown that HF
can be spent sufficiently to observe the important
secondary precipitation reactions only when enough
aluminum is available to yield an AI:F ratio of ap-
proximately 1:2. This criterion was met by using 40 g
of kaolinite per 1,000 mL of HF IHCI mixture.
Figs. 6 and 7 present the time dependence of
kaolinite dissolutions at 22°C (72°F) and 66°C
(150°F). The initial attack by HF results in the
1199
 160 CALCULATED 2 HR SHUT· IN
INPUT F 66'C 11 50'F)
1.4 ------------------ ____ _ LIMIT OF HF
PENETRATION
F TOT
1.2 140

~ o PERM. AFTER
z 1.0 ::;; HCI ACIDIZING
Q
>- 66'C 11 50'FI ~ 120
<t .8 ill
a: 0.
>-
z
ill
U 100
Z
0
u .4
S;
80
10 CM
AI
I I
o 2000 o 8 12 16 20 24 28 IN
VOLUME OF HFHCI INJECTED, ML DISTANCE FROM INJECTION FACE'

Fig. 8 - Effluent profiles from 3% HF/10% HCI stimulation. Fig. 9 - Permeability profile of a core shut in after injecting
0.5 PV HF/HCI.

uniform (stoichiometric) dissolution of the clay
structure. The Si:Al ratio in solution is identical to,
the 1.1: 1 measured spectrographically for the bulk
kaolinite. The later phases of the dissolution process
are characterized by a continued increase in the
aluminum concentration and a simultaneous
decrease in the silicon concentration. Comparison of
Figs. 6 and 7 show both the dissolution and
precipitation reactions are greatly accelerated by
increases in temperature.
Cause of Silica Precipitation
Silica precipitates from spent acid when the con-
centration of remaining HF becomes very low. The
reaction that dissolves silicate minerals by consuming
HF when the HF concentration is high,
ffi0 2 +6HF-H 2 ffiF 6 +2H 2 0
reverses itself to regenerate HF and precipitate silica
as the HF concentration drops:
H 2 SiF 6 +4H 2 0-Si(OH)4 +6HF.
However, this silica precipitates as a voluminous
hydrated colloid [5i(OH)4 ·nH 2 0j that is damaging
to rock permeability.
The driving force that lowers the HF concentration
is the continued removal of aluminum from the clay
minerals. Aluminum has greater affinity for fluorine
than does silicon. As aluminum dissolves, it com-
bines with the available fluorine thereby reducing the
HF to the level where Si(OH)4 precipitates. The
following table relates the predominant species of
aluminum and silicon fluorides to the level of free
fluoride (F -) in solution. Our measurements show
that somewhere at or below 10 - 5 moUL free
fluoride, silica is precipitated.
Free Fluoride Predominant Species
(moUL) Aluminum Silicon
10- 4 AlF 3 ,AlF z + SiF 6 - , SiF 5
10- 5 AlF z + , AlF+ + SiF 5 - , SiF4
10- 6 AlF+ + Si(OH)4
Chemical E"idence for Silica Damage in Cores
A 3.8 cm (1.5 in.) X 76.2 cm (30 in.) Berea sandstone
core was acidized initially with HCl and then treated
1200
with 3070 HF/10070 HC!. The test temperature was
66°C (150°F), and the flow rate was 13.3 mLimin. A
total of 2500 mL (13.5 PV) of HF/HCl was injected;
however, midway into the treatment, injection was
ceased for 2 hours.
The spent acid effluent from the core test was
analyzed for aluminum, silicon, and total fluorine.
The data are plotted in Fig. 8. During the first 1000
mL of injection, the Si:Al ratio ranged from 0.2: 1 to
0.5: 1. This ratio is much lower than the 1.2: 1 Si:Al
ratio measured for the natural clays and indicates
that the effluent acid already has reached the silica
precipitation stage. The acid uniformly dissolves clay
at the front of the core, but during its 13-minute
residence time in the rock, the spent acid is exposed
to sufficient aluminum-bearing minerals that silica
precipitation begins to occur.
Illite clay was detected in the core, making it
possible that precipitation occurred as potassium
fluosilicate (K 2 SiF 6) instead of silica [Si(OH)4j·
However, effluent analysis for total fluorine shows
that over 90070 of the injected fluorine exits the core;
hence, only a very small fraction of the missing
silicon can be accounted for by K2 SiF 6'
Following the 2-hour shut-in, the effluent profile
in Fig. 8 is characterized by a sharply rising
aluminum concentration along with a nearly zero
silicon content. The silicon in solution just before
shut-in has totally precipitated. This data illustrates
the hazards of allowing spent HF to remain in the
formation rock, even for a few hours.
Permeability Evidence for Silica Damage in Cores
In another experiment, a 76.2-cm (30-in.) Berea core
was acidized initially with HCl and then acidized
partially with 3070 HF/10070 HCl at 66°C (150°F).
The HF/HCl acid front was allowed to advance only
halfway into the core. Following a 2-hour shut-in
period, flow was reversed and the spent acid was
flushed out with 3070 NH4 Cl brine. The core was cut
into 5-cm (2-in.) sections, and the permeability of
each was measured. Three distinct permeability
regions are visible in Fig. 9.
First, immediately adjacent to the injection face,
the core shows a substantial gain in permeability
from the removal of both carbonates (by HCl) and
JOURNAL OF PETROLEUM TECHNOLOGY
 TABLE 2 -IRON CONTENTS OF CORES
FROM VARIOUS GEOLOGIC SETTINGS
Iron Iron (II) Iron (III)
Core Source (wt%) (wt%)
A siderite 2.20 0.01
B siderite 4.51 0.01
C chlorite 1.20 0.20
D chlorite 1.40 0.60
E siderite 0.83 0.01
clay minerals (by HF). Second, a low permeabilty
region lies between 5 and 45 cm (2 and 17 in.) from
the injection face. This is the region penetrated by the
spent HF/HCl. Precipitation of silica caused by
contact of spent acid with aluminum-bearing
minerals reduced the permeabilty to less than the
HCl acidized value. The amount of permeability loss
is indicated by the shaded region in Fig. 9. Finally,
between 45 and 76 cm (17 and 30 in.) lies a region
acidized by HCl but not reached by the HF. A
modest gain in permeability over the initial value was
obtained from the removal of carbonate minerals.
Preventing Silica Precipitation in Field Operations
The precipitation of silica can limit significantly the
success of sandstone acidizing treatments in field
operations. Through the years, two important
operational techniques have been developed to
improve the success rate of sandstone acidizing
treatments: (1) use a sizeable afterflush and (2) return
the well to production immediately. We believe these
practices enhance acidizing success by preventing
silica precipitation.
Afterflushing a sandstone acidizing treatment with
either diesel oil, nitrogen, HCl, or ammonium-
chloride brine displaces the spent acid from the
critical region very close to the well. Any
precipitation of silica that occurs will be far enough
away from the well bore that the resulting damage
will have only a small effect on flow capacity. The
after flushing process should occur immediately after
acid injection so there is no delay in displacing the
spent acid.
Aqueous (HCl or NH4 Cl) afterflushes are the
most effective in displacing spent acid from the near-
wellbore region. They also serve to dilute the acid,
thereby reducing the precipitation tendency. In many
cases, however, other well problems prevent the use
of an aqueous afterflush, thus necessitating that
diesel or nitrogen be used. These cases occur when
low reservoir permeability requires re-establishment
of an oil or gas saturation around the well to allow
rapid cleanup or when low reservoir pressure requires
swabbing to lift large aqueous volumes to the sur-
face.
Obviously, the best solution to the silica
precipitation problem is to produce the spent acid
from the well as quickly as possible. How quickly
production must be started depends primarily on the
reservoir temperature. Our data indicates that 1 to 2
hours may be adequate for low temperature reser-
. voirs, but as the temperature reaches or exceeds 66°C
(150°F), this time is reduced to 30 minutes or less.
JULY 1981
To some extent, there is a trade-off between af-
terflush volume and time to initiate production. In
cases where it is impossible to initiate production in
an appropriately short time following treatment,
large aqueous after flush volumes have been suc-
cessful in pushing the spent acid far from the
wellbore. In other situations where the entire acid
treatment could be produced into the well bore within
60 to 90 minutes following the treatment, success has
been achieved with minimal after flush volumes.
High-temperature wells above 95°C (200°F)
deserve special attention because of the speed of the
HF reaction at these temperatures. The extremely
rapid HF reaction makes it impossible to return the
well to production before precipitation is complete,
and even the afterflush may not displace the reaction
products in time. In these situations, we recommend
a third technique for avoiding silica precipitation-
reducing the concentration of HF. A reduced HF
concentration slows down the dissolution reactions
and lowers the concentration of the dissolved species,
which slows down the precipitation reactions.
Although field results with this technique are not
numerous, preliminary results are encouraging.
Acidizing Iron-Bearing
Sandstone Formations
Iron is an important constituent in several commonly
encountered minerals; hence, most geologic for-
mations contain iron. Theoretically, iron can
precipitate from spent acid solutions to yield an
amorphous gel. It is important to understand the
conditions under which this precipitation takes place
so that acidizing fluids and field practices can be
designed correctly.
Iron Content of Sandstone Formations
The iron-bearing minerals commonly occuring in
sandstone reservoirs are the carbonates siderite and
ankerite, the sulfide pyrite, and the clay chlorite. All
of these minerals contain iron in the + 2 oxidation
state [Fe(II)]. In addition, chlorite also contains a
small percentage of iron in the + 3 oxidation state
[Fe(III)] - the exact ratio of Fe(II) to Fe(III) being
dependent on the origin of the chlorite. 7
Several cores from producing wells in different
geologic settings have been analyzed for relative
amounts of Fe(II) and Fe(III). A permanganate
titration coupled with atomic absorption was used to
identify the two oxidation states. As seen in Table 2,
most of the iron was in the + 2 oxidation state.
Dissolution of Iron Minerals by HCI
All of the iron-containing minerals will react with
HCl to generate soluble iron. The carbonates siderite
and ankerite dissolve rapidly in HCl to release Fe + +
into solution and produce CO 2 as a by-product. The
reaction proceeds until the acid is consumed and
equilibrium with the minerals is reached. No
precipitation will occur.
Iron pyrite decomposes very slowly in HCl to yield
soluble Fe + + and H2 S. As with carbonates, the iron
pyrite comes to equilibrium with the HCl with no
precipitates forming.
1201
 Chlorite minerals, unlike carbonates, do not
dissolve completely in HC!. Instead, the iron,
aluminum, and magnesium components are leached
from the clay, leaving a hydrated silica residue. Iron
is leached from chlorite minerals by HCI at different
rates depending on the chemical composition and
crystallinity. In general, however, this leaching is
very slow when compared with the reaction of HCI
with carbonates. It has been found that more than 2
hours of exposure to 70/0 HCI at 75°C (l6rF) was
required to remove 20% of the iron from a chlorite
sample. 11
Precipitation of Iron Compounds
Iron precipitation from spent HCI becomes a real
possibility only if there is another mineral in the
formation sand that will cause the HCI to spend
completely. That mineral is generally a form of
calcium carbonate (CaC0 3). CaC0 3 can cause the
pH of the spent acid to rise to a point where iron
minerals are precipitates. However, this necessitates
that sufficient CaC0 3 be present in the rock to
totally spend the HCl. This condition usually is
found in carbonate reservoirs but occurs less
frequently in sandstone reservoirs.
As the pH of the spent acid rises due to spending
on CaC0 3 , the region of Fe(II) precipitation is
approached. There is evidence that because of CO 2
liberated by the CaC0 3 dissolution reaction, the
precipitated mineral will be Fe(II) carbonate
(siderite, FeC0 3) and not Fe(II) hydroxide. 11 Fe (II)
carbonate is a crystalline precipitate likely to form a
scale on the pore walls. It is not a gel-like precipitate
that can clog pore throats. Permeability impairment
due to Fe(II) carbonate precipitation does not pose a
major problem.
On the other hand, Fe (III) begins to precipitate as
iron hydroxide [Fe(OHhl if the pH of the spent acid
rises above pH = 1. This precipitate' does have a
hydrated gel-like structure and can be very damaging
to near-well bore permeability. However, the slow
rate of Fe(III) leaching from chlorite relative to the
rapid spending of HCI on calcium carbonate makes it
uncertain as to whether Fe(OH)3 ever could form in
a producing sandstone reservoir.
Dissolution of Iron Minerals by HF
Hydrofluoric acid will dissolve chlorite rapidly to
release essentially all of the iron into solution.
However, if the HF treatment has been properly
designed, an HCl pre flush can be used to dissolve
carbonates before the arrival of the HF. There
should be little chance of spending the acidity of an
HF/HCI mixture; hence, no Fe(OHh hydroxide will
precipitate.
Note also that the fluoride ion has a great affinity
for dissolved Fe(III). The strength of the iron
fluoride complex is sufficient to prevent hydroxide
formation until a pH near 5 or 6 is reached. 11 The
use of hydrofluoric acid presents no new problems in
acidizing iron-bearing minerals.
1202
Guidelines for Acidizing Iron-Bearing Sandstones
Based on the discussion of iron mineral dissolution
and precipitation, the following guidelines for
acidizing iron-bearing sandstones are recommended
for producing wells:
1. The presence of an iron mineral in the reservoir
does not necessarily mean that an iron precipitate
will form.
2. Information about the mineralogy and car-
bonate content are required to determine the iron
precipitation potential.
3. Properly designed HF acidizing treatments do
not increase the chances for iron precipitation
beyond that for plain HCl.
These guidelines are for application only to
producing wells. Wells that have been used for in-
jection service and which may contain large quan-
tities of Fe (III) corrosion products must be handled
differently. The possibility for Fe(OHh precipitation
in this case is increased greatly.
Acknowledgments
We gratefully acknowledge the valuable con-
tributions made by W.M. Salathiel as well as the
many hours of laboratory work performed by M.E.
Whiteley and M.V. Rowe during this project. We
also thank Exxon Production Research Co. for
permission to publish this paper.
References
L Smith, C.F. and Hendrickson, A.R.: "Hydrofluoric Acid
Stimulation of Sandstone Reservoirs," J. Pet. Tech. (Feb.
1965) 215-222.
2. Farley, J.T., Miller, B.M., and Schoettle, V.: "Design
Criteria for Matrix Stimulation with Hydrochloric-
Hydrofluoric Acid," J. Pet. Tech. (April 1970) 433-440.
3. Williams, B.B.: "Hydrofluoric Acid Reaction with Sandstone
Formation,' J. Eng. Indust. (Feb. 1975) 252-258; Trans.,
ASME,97.
4. Labrid, L.: "Thermodynamic and Kinetic Aspects of
Argillaceous Sandstone Acidizing," Soc. Pet. Eng. J. (April
1975) 117-128.
5. Lund, K., Fogler, H.S., and McCune, C.C.: "Predicting the
Flow and Reaction of HCI/HF Acid Mixtures in Porous
Sandstone Cores," Soc. Pet. Eng. J. (Oct. 1976) 248·259.
6. McCune, C.c., Ault, J.W., and Dunlap, R.G.: "Reservoir
Properties Affecting Matrix Acid S!imulation of Sand-
stones," J. Pet. Tech. (May 1975) 633-640.
7. Grim, R.E.: Clay Mineralogy, McGraw-Hili Book Co. Inc.,
New York City (1968) 51-57 and 581.
8. Borodin, P.M. and Zao, N .K.: "Study of Mobile Equilibria in
the HF-Si0z-HCI04-H20 System by the 'F NMR' Method,"
Russian J. Inorganic Chern. (1972) 17, 959-962.
9. Brosset, C. and Orring, J.: "Studies on the Consecutive
Formation of Aluminum Fluoride Complexes," Svensk
Kernisk Tidskrift ( 1943) 55,101-116.
10. Ross, G.J.: "Acid Dissolution of Chlorites: Release of
Magnesium, Iron, and Aluminum and Mode of Acid Attack,"
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1 L Kragten, J.: Atlas of Metal Ligand Equilibria in Aqueous
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JPT
Original manuscript received in Society of Petroleum Engineers office Aug.
12. 1980. Paper accepted for publication April 10, 1981. Revised manuscript
received May 27, 1981. Paper (SPE 9388) first presented at the SPE 55th Annual
Technical Conference and Exhibition, held in Dallas, Sept 21·24,1980.
JOURNAL OF PETROLEUM TECHNOLOGY