SPE 150899

Acidizing Sandstone Reservoirs Using HF and Formic Acids

F. Yang, SPE, H.A. Nasr-El-Din, SPE, Texas A&M University; B. Al-Harbi, SPE, Saudi Aramco

Copyright 2012, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE International Symposium and Exhibition on Formation Damage Control held in Lafayette, Louisiana, USA, 1517 February 2012.
This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
Mud acid, which is composed of HCl and HF, is commonly used to remove the formation damage in sandstone
reservoirs. However, many problems are associated with HCl acid, especially at high temperatures.
In this study, formic acid was used to remove carbonate minerals as a preflush and with the main HF stage. A
series of formic acid and HF mixtures with different ratios and concentrations were tested. Sandstone cores
featured by different minerologies with dimensions of 1.5 in. 6 in. were used in the coreflood experiments, which
were run at a flow rate of 5 cm3/min and temperatures from 77 to 350oF. The cores were analyzed by CT scan
before and after the acidizing to investigate the effect of the acid. The core effluent samples were analyzed to
determine concentrations of Ca, Mg, Fe, Si, and Al by ICP. 19F NMR was utilized to follow the reaction kinetics
and products. Zeta potentials of clay particles (kaolinite, illite, and chlorite) were measured in various acid
solutions
Formic acid (9 wt%) damaged sandstone cores. Zeta potential measurements indicated that formic acid can
trigger fines flocculation. Addition of 5 wt% ammonium chloride helps to shield negative charges on clay surface.
Analysis of core effluent samples indicated that there was CaF2 precipitate in the core when a small volume of
preflush was used. Coreflood tests highlighted that formic acid/HF caused loss of core permeability. This paper
will discuss the detailed chemical reactions occurred within cores and were followed by chemical analysis of core
effluent samples and 19F NMR. Secondary reaction between clay minerals and HF became faster at higher
temperature, and decreased the ratio of Si/Al. It was also found that different clay minerals react with HF offering
very different concentrations of Al and Si in spent acid.
Introduction
Stimulation of sandstone reservoirs is aimed at removing the formation damage caused by drilling, workover, or
completion processes, thus to restore the original permeability of the formation. Three main steps are involved,
including preflush, main flush, and post flush. In the main stage, mixtures of mud acid (HCl-HF) have been
extensively employed in the field (Smith and Hendrickson 1965; Gidley 1985). In mud acid, the role of
hydrofluoric acid (HF) is to dissolve aluminosilicates and silica, while hydrochloric acid (HCl) helps to keep
reaction products soluble in spent acid.
Field reports showed variable success rates of the treatments using mud acid and formation damage was even
formed in some cases (Simon and Anderson 1990). These unsatisfying results were attributed to many drawbacks
of this conventional system. First, in the zones which are not adequately covered by preflush, there is a high risk of
secondary and tertiary precipitate. Second, HCl-senstive clays (e.g., illite) can cause formation damage and
decrease the permeability. Third, the high reaction rate and corrosion rate also cause many problems (Simon and
Anderson 1990; Gdanski and Shuchart 1996; Thomas et al. 2002). These problems can be worse at high
bottomhole temperatures, due to the accelerated reaction rates and higher corrosivity of the acid system.
To overcome the problems associated with mud acid, organic-HF acids have been used as an alternative to
mud acid (Abrams et al. 1983; Shuchart et al. 1996; Taylor et al. 2005; Al-Harbi et al. 2011). Among them, formic
and acetic acids are most commonly used to substitute for HCl. Formic acid, which is stronger than acetic acid,
offers better results in the prevention of aluminum fluoride precipitation (Shuchart 1997). In our research,

SPE 150899

stimulation of sandstone reservoirs employing formic-HF acids is investigated. The main objectives are to: 1)
evaluate the influence of ammonium chloride on clay stabilization in formic acid solution based on zeta potential
analysis; 2) investigate the effectiveness of formic acid in removing carbonates in sandstone reservoirs at various
temperatures; and 3) study the effect of composition and volume of main flush on the permeability of sandstone
cores.
It is known that when organic acid is used as the preflush, 5 wt% ammonium chloride (NH4Cl) should be
included (Coulter and Jenning 1999; Wang et al. 2000). This conclusion was based on a flow test using 10 wt%
acetic acid at 75oF (Gdanski 1995). In this flow test, a sand column containing 10 wt% bentonite was continually
flushed by 5 wt% NaCl solution, followed by 10 wt% acetic acid and then 5 wt% NaCl solution again. Ion
concentrations of the effluent samples were measured and it was found that acetic acid was so weak that ion
exchange between H+ and Na+ on bentonite clay could not happen. It was then concluded that 10 wt% acetic acid
could cause swelling of bentonite and 5 wt% NH4Cl was recommended to add to the acetic acid solution during
preflush.
However, no direct evidence showed that formic acid, which is stronger than acetic acid, would behave in the
same way as acetic acid does. Also, no research results indicated that formic acid could cause formation damage,
not to mention that the addition of 5 wt% NH4Cl could prevent this damage.
Zeta potential is an indicator of a suspensions stability. Higher absolute zeta potential value indicates stronger
repulsion between clay particles, which leads to a more dispersed suspension. As a result, zeta potential analysis
has been used in research to decide the stability of clays and effectiveness of clay stabilizers (El-Monier and NasrEl-Din 2010). By incorporating this technique, the impact of formic acid on fines flocculation can then be assessed
directly.
The main purpose of preflush is to remove carbonates. The reaction between formic acid and calcite at high
pressure is given in Eq. 1 (Chatelain et al. 1976).
k
+
2+
2H (aq) + CaCO3 Ca (aq) + H2O +CO2 (aq)....... (1)
Formic acid is a weak acid, and the dissociation equation and the dissociation constant are given in Eq. 2 (AlHarbi et al. 2011).
HCOOH H+ + HCOO- (pKa, FA = 3.75) .............................................................................. (2)
When weak acid reacts on the surface of calcite, the consumption of H+ can drive the acid dissociation to the
right of Eq. 2. Undissociated acids are transported to the surface by diffusion, and then the H+ ions were generated
in situ through dissociation (Eq. 2). When pH is less than 4, the backward reaction can be ignored, and the forward
reaction rate depends on both H+ concentration, and the reaction constant (k) (Buijse et al. 2004).
Though research has been done regarding the organic-acid/carbonates system (Chatelain et al. 1976; Buijse et
al. 2004; Chang et al 2008), none of it was targeted at the carbonates in sandstone reservoirs. One paper reported
that when 14 wt% formic acid was used as preflush on a Muzza sandstone core at 400oF, calcium concentration
started to decrease after 8 PV (Scheuerman 1988). Nowadays, it is known that formic acid is often used at a
concentration of 9 wt% in the field, because calcium formate can precipitate at higher concentrations (Blake and
Walter 1999). But there is no study to show the effectiveness of 9 wt% formic acid in removing carbonates in
sandstone reservoirs at various temperatures.
Many aspects also need to be studied regarding the main acid flush. In this stage, HF acid dissolves
aluminosilicates, and formic acid helps to maintain the low pH, which is necessary to keep reaction products
soluble. Just like formic acid, HF is a weak acid. Its dissociation equation and dissociation constant at room
temperature are given in Eq. 3 (Perrin 1981).
HF H+ + F- (pKa, HF = 3.17) .... (3)

SPE 150899

Primary, secondary, and tertiary reactions have all been reported between aluminosilicates and HF (Gdanski
1998, 1999, 2000), and are briefly described below.
Primary reaction between HF and aluminosilicates can be generally written in form of Eq. 4 (Gdanski 2000).
(5+x) HF + M-Al-Si + (3-x+1) H+ HSiF5 + AlFx(3-x) + M+ + H2O ..... (4)
Where: x= number of fluorides required to dissolve each Al; M = other cations, such as Na.
Kinetics of this reaction is dominated by mass-transfer effect and is faster at higher temperatures (Gdanski
2000).
The secondary reaction between HF and aluminosilicates is the reaction of fluosilicic acid with
aluminosilicates (Eq. 5) (Gdanski 1999).
x/5 HSiF5 + M-Al-Si + (3-x+1)H+ + H2O AlFx(3-x) + M+ + silica gel . (5)
The reaction rate constant was found to be very sensitive to temperature. Below 125oF, this reaction was very
slow, but the speed above 125oF was very fast and quickly went to completion (Gdanski 1999).
The tertiary reaction between HF and aluminosilicates was reported in general form of Eq. 6 (Shuchart and
Buster 1995).
y AlFx3-x + (x-y) Al-Si + 3(x-y) H+ x AlFy3-y + (x-y) silica gel ........ (6)
Where: y = number of fluorides coordinated with Al after tertiary reaction, y < x.
The rate constant was determined under various temperatures and the reaction with clay was found to be very
slow below 200oF (Gdanski 1998).
In our study, zeta potential data was first analyzed, to evaluate the effect of NH4Cl on clay stabilization in
formic acid solution. Then 19F NMR was applied to study the reaction extent and products. The influences of
temperature, ratio between formic-HF acids were investigated based on results from coreflood experiments,
chemical analysis of effluent samples, and X-ray computed tomography (CT) of sandstone cores.
Experimental Studies
Materials
Formic acid and hydrochloric acid were purchased from Sigma-Aldrich with concentrations of 96 wt% and 36.5
wt%, respectively. Ammonium chloride was obtained from Sigma with an assay of more than 99.5 wt%.
Ammonium bifluoride was supplied by Alfa Aesar, and the purity was 95 wt%. Corrosion inhibitor was obtained
from a service company. HF acid was prepared using ammonium bifluoride and HCl based on Eq. 7 (Thomas et al.
2001).
HCl + NH4HF2 NH4Cl + 2HF ... (7)
Core plugs were cut from Berea or Bandera sandstone blocks and the core size was 1.5 in. 6 in. The
mineralogy of the Berea and Bandera sandstone cores are given in Table 1. Clays (kaolinite, illite, and chlorite)
were purchased from Wards company. All solutions were prepared using deionized water with a resistivity of 18.2
.cm at room temperature.
Zeta Potential
There are three clay minerals in Berea and Bandera sandstone cores: kaolinite, chlorite, and illite. Zeta potential
was performed on these three clay minerals. The suspensions were prepared by mixing 15 mg of clay (kaolinite,
chlorite, or illite) with 10 cm3 of solution in a plastic tube at room temperature. The content of each solution is
shown in Table 2. Samples were left for 24 hours to reach equilibrium, and then zeta potential was measured using
ZetaPALs software (Brookhaven Company). Measurements were also taken at room temperature. Each sample was
measured 10 times, and then the highest and lowest values were deleted. The remaining values were averaged to
give the final result.

SPE 150899

NMR Analysis
At room temperature, 4 g of clay minerals (kaolinite, chlorite, or illite) were added to 20 g of 9 wt% formic acid
and 0.5 wt% HF mixture, to ensure enough clay for acids to react. After agitating for 0.5 hour, the suspension was
filtered, and then analyzed by 19F NMR, using Oxford NMR spectrometer tuned to 300 MHz. The chemical shifts
are reported relative to trichloro-fluoro-methane (CFCl3). The concentrations of Al and Si were analyzed by
inductively coupled plasma (ICP) analysis using Optima 7000 DV ICP-OES system and WinLab 32TM software.
Samples were diluted to make sure the concentrations of each ions were below 30 mg/l.
Coreflood Experiments
The cores were first dried at 250oF for 5 hours, and then saturated with 5 wt% ammonium chloride for 2 hours
under vacuum. The pore volume of the core was determined by dividing the weight difference of the saturated core
and the dry core by the density of brine.
After the core was loaded into the core holder, the back pressure was adjusted to 1000 psi, while the
overburden pressure was 1500 psi. The injection rate was 5 cm3/min in all experiments.
In all the core flood experiments, 5 wt% ammonium chloride was injected at room temperature as preflush
and post flush until the pressure drop was stablized. Then the permeabilities of the cores were calculated using
Darcys equation. So the effect of the acids on permeability can be evaluated. The compositions and volumes of
acids used and temperatures of all the coreflood experiments on Berea sandstone cores are listed in Table 3. The
experiment condition of coreflood experiment on Bandera core was the same as in coreflood experiment #3.
The cores were scanned by X-ray computed tomography (CT) both before and after the coreflood
experiments, and the CT results were analyzed utilizing ImageJ software. The core effluent samples were collected
in all coreflood experiments and analyzed to determine the concentrations of Ca, Mg, Fe, Al, and Si by inductively
coupled plasma (ICP) analysis using Optima 7000 DV ICP-OES system and WinLab 32TM software. Samples were
diluted to make sure the concentrations of each ions were below 30 mg/l.
Results and Discussion
Zeta Potential
Zeta potential test results are shown in Fig. 1. Zeta potentials of kaolinite, chlorite, and illite in deionized water
were -36.7, -29.3, and -27.1 mV, respectively, which were very close to literature reported values (Hussain 1996).
Zeta potential jumped to almost 0 mV with only 1 wt% formic acid, and kept stabilized with the increase of
concentration until 9 wt%. This indicates that the clay particles flocculated readily in formic acid solutions. With
the addition of 5 wt% NH4Cl to the 9 wt% formic acid solution, zeta potential of clays increased to around 10 mV.
This is because NH4Cl helps to shield the negative charges on clay surface, and acts as clay stabilizer in formic
acid solution .
NMR Analysis
F NMR spectra of 9 wt% formic acid 0.5 wt% HF after reaction with kaolinite, illite, and chlorite are shown in
Figs. 2 through 4. As mentioned before, CFCl3 was used as a reference, which means its chemical shift is 0 ppm in
these spectra. To compare our results with literature reported values, we calculated the chemical shifts using
trifluoro acetic acid (CF3COOH) as a reference first. CF3COOH has a chemical shift of -76.55 ppm relative to
CFCl3. So the chemical shifts in our spectra should +76.55 ppm to be the chemical shifts relative to CF3COOH.
In the 19F NMR spectrum of 9 wt% formic acid 0.5 wt% HF after reaction with kaolinite (Fig. 2), there are
two groups of signals in the spectrum, one is around -132 ppm, and the other one is around -158 ppm. The
chemical shifts of our spent acids should be around -55.45 and -81.45 ppm respectively if we use CF3COOH as a
reference. These values are very close to the values reported by Shuchart and Buster (1995). In their paper, they
assigned the group of peaks around -55 ppm as silicon fluoride species, while those around -80 ppm as aluminum
fluoride species. They also found that HF had a chemical shift at -85.5 ppm. But there is no peak in that region in
our spectrum. In our experiment, it is also found that the acid solution contains high concentrations of Si and Al
(Table 4). So it can be concluded that when the ratio between clay and 9 wt% formic-0.5 wt% HF acids is 1:5, HF
was completely consumed, and both aluminum fluoride species and silicon fluoride species were produced.
In the 19F NMR spectra of 9 wt% formic acid 0.5 wt% HF after reaction with illite and chlorite (Figs. 3 and
4), the major peaks are around -55 ppm. These indicate that most of the fluoride ions are coordinated with silicon.
High concentration of Si was found in the solution, with very low amount of Al (Table 4). This could explain why
there is no obvious peak in the region of aluminum fluoride in the 19F NMR spectra. Also, no HF peak is observed,
19

SPE 150899

which means that HF was completely consumed. It can be concluded that HF was completely consumed, and
silicon fluoride species were the major products. This result is different from the reaction with kaolinite, in which
significant amounts of aluminum fluoride was produced. The difference can be explained by examining the
structures of these three minerals. Kaolinite has 1:1 layered structure, which makes the aluminum sheet contact
with acid. Illite and chlorite both have 2:1 layed structure, which contain the aluminum sheet in between two
silicon sheets. This structure makes it harder for acid to contact the aluminum sheet. Thus less Al was dissolved in
the acid solutions (Al-Harbi et al. 2011).
Coreflood Experiments
Coreflood experiments were conducted with various acid compositions, volumes, and under different temperatures
(Table 3). The influences of these factors are discussed below.
Acid Preflush
Coreflood experiments #1 and #2 were conducted to investigate the effect of formic acid solution on sandstone
cores and the influence of temperature in the acid preflush stage. In coreflood experiment #1, 10 PV of 9 wt%
formic acid were injected to the Berea sandstone core at room temperature. The pressure drop across the core
increased at first, and then decreased very slowly. Eventually, the permeability of the core decreased from 60 to 56
md (Fig. 5). These results indicated that formic acid itself can damage the core.
The ICP analysis of coreflood experiment #1 is shown in Fig. 6. At room temperature, large amounts of Ca,
Fe, and Mg were removed by formic acid. The concentrations of Ca, Fe, and Mg kept on increasing with the
injection of acid, and reached their highest after 6 PV of acid, and then started to drop very slowly. When 10 PV of
acid were injected, the concentrations of Ca, Fe, and Mg were 2,500, 1,400, and 600 mg/l respectively, which were
still very high. Therefore, it can be concluded that a large volume of formic acid is needed to remove carbonates
from Berea sandstone at room temperature.
In coreflood experiment #2, 10 PV of 9 wt% formic acid was injected into the Berea sandstone core at 250oF.
Pressure drop increased at the beginning of the injection of acid, and then decreased more rapidly than in coreflood
experiment #1. The permeability increased from 56 to 58 md (Fig. 7). Much higher concentrations of metal ions
than at room temperature were observed. Also, it was noticed that the concentrations of these ions started to drop
rapidly only after 3 PV of acid preflush (Fig. 8). All of these indicate the improved effectiveness of formic acid in
removing carbonates at higher temperatures.
Besides, Al concentrations in coreflood experiments #1 and #2 were both low during the whole process (Figs.
6 and 8). These indicate that formic acid is not effective in leaching aluminum from clays present in Berea
sandstone cores up to 250oF.
Acid Main flush
To investigate the impact of HF concentration, coreflood experiments #3 and #4 were conducted. The fluid
compositions and sequences were almost the same, except for the concentrations of HF in the main stage. In
coreflood experiment #3, 1 wt% HF with 9 wt% formic acid were used in the main flush, and the concentration of
Ca suddenly dropped when the formic-HF acids were injected (Fig. 11). This indicated that Ca precipitated during
this stage, and caused the permeability to decrease from 55 to 50 md (Fig. 9). On the other hand, the highest
concentrations of Si and Al were 1,300 and 600 mg/l, respectively (Fig. 11), and these came from the reaction of
aluminosilicates with HF, which produced soluble silicon and aluminum fluorides (Eq. 4).
In coreflood experiment #4, 2 wt% HF and 9 wt% formic acid were used in the main flush. The highest
concentrations of Si and Al were 3,500 and 1,700 mg/l respectively, which were both much higher than in
coreflood experiment #3 (Fig. 14). So it can be concluded that a higher concentration of HF is more effective in
removing the aluminosilicates. As in experiment #3, the concentration of Ca decreased significantly during this
stage. Meanwhile, more severe permeability loss was observed at the same time, from 54 to 43 md (Fig. 12). CT
number increases were observed both in coreflood experiments #3 and #4 (Figs. 10 and 13). The CT number is
related to bulk density as shown in Eq. 8 (Izgec 2009).
bulk = aCTN + b .(8)
Where bulk is the bulk density, CTN represents the CT number, a is the slope, and b is the intercept of the
linear relation between CTN and the bulk density.

SPE 150899

The higher CT numbers after the acid treatment indicated that higher-density precipitate was formed inside the
core. It is known that CaF2, has a density of 3.18 g/cm3, which is much larger than that of sandstone (2.65 g/cm3)
(Perry, 2011). Besides, CaF2 has ever been reported as precipitation when HF was pumped down hole and mixed
with spent acid there, which has high concentration of Ca (Mohammad et al. 2011). Combining with the sudden
drop of Ca after injection of formic-HF acids, it can be inferred that Ca precipitated in the form of CaF2.
To further confirm the hypothesis of CaF2 precipitate, coreflood experiments #5 was conducted. It employed 1
PV of 9 wt% formic acid -0.5 wt% HF. Compared with coreflood experiment #3, the fluoride amount in this
experiment was much smaller, also the extent of mixing the spent acid containing Ca with the solution containing
fluoride ions were highly reduced. If the hypothesis regarding the CaF2 precipitate was true, less permeability loss
should be achieved. And this is the case in coreflood experiment #5, where the permeability only slightly
decreased from 62 to 60 md (Fig. 15). This proved that Ca did precipitate in the form of CaF2 when main acid was
injected, and 1 PV of 9 wt% formic acid-0.5 wt% HF could cause less damage to the core compared with 3 PV of 9
wt% formic acid -1 wt% HF. Also, this experiment condition was selected, and further investigated at high
temperatures.
Coreflood experiments #6, #7, and #8 were conducted at 150, 250, and 350oF, respectively. In coreflood
experiment #6, the permeability of the core increased from 56 to 58 md after the acid treatment (Fig. 17). In
coreflood experiment #7, the permeability of the core increased from 63 to 67 md (Fig. 20), and the permeability
increased from 60 to 64 md in coreflood experiment #8 (Fig. 22). These improvements can be attributed to small
amount of fluorides and effective removal of carbonates during preflush, which both leave less possibility for CaF2
to precipitate. These can be further proved by the decreased density after acid treatment (Fig. 19).
Overall, better permeability improvements were achieved at higher temperatures, when 1 PV of 9 wt% formic
acid and 0.5 wt% HF was used in the main stage.
The ratio of Si/Al was also investigated. At room temperature, the ratio of Si/Al was around 2:1 (Fig. 16).
However, Si/Al ratio decreased to 1:1 at 150oF (Fig. 18), and 1:2 at 250oF (Fig. 21). Si/Al ratio further dropped to
1:3 at 350oF (Fig. 23). This change can be explained by the secondary reaction of aluminosilicates with HF. When
temperature increased, the extent of secondary reaction increased as well. In the secondary reaction, fluosilicic acid
was consumed by aluminosilicates to generate more aluminum fluoride species, while Si transferred from
fluosilicic acid to silica gel. Thus, the concentration of Al in spent acid solution increased, while the concentration
of soluble Si decreased. As a result, the ratio of Si/Al decreased.
Mineralogy
Bandera sandstone core was also used to conduct coreflood experiment, to investigate the influence of mineralogy
on the outcome of acid treatment. Based on the pressure drop shown in Fig. 24, it can be calculated that the
permeability of Bandera sandstone core decreased from 4.0 to 2.6 md. This indicated that severe damage was
formed inside the core. The ICP analysis of five ions is shown in Fig. 25. Large amount of Ca was removed during
acid preflush, and the concentration of Ca dropped rapidly since the injection of main acid, but rose again during
post flush stage. This is attributed to the precipitation of CaF2 during the main stage.
Si concentration reached as high as 1,000 mg/l during main stage, while Al concentration was very low during
the whole experiment, even after HF was injected (Fig. 25). The observations regarding Al and Si concentrations in
Bandera sandstone core are very different from what we have seen in Berea sandstone cores. In Berea sandstone
cores, Al concentration went up together with Si concentration after the injection of HF. The difference in Al
concentration is attributed to the mineralogy. As shown in Table 1, Berea sandstone core has high percentage of
kaolinite (5%) and low percentages of illite (1%), while Bandera sandstone core has high percentage of illite (10%)
and relatively low amount of kaolinite (3%). It has been reported before that organic mud acids were much less
efficient to extract Al from illite than from kaolinite, and these low efficiencies were caused by the structure as
explained earlier.
Conclusions
The following conclusions can be drawn from this study:
1. At room temperature, formic acid solution damages sandstone core. Ammonium chloride can act as clay
stabilizer and alleviate the damage.
2. At room temperature, formic acid is not effective in removing carbonates in a sandstone reservoir. It
becomes more effective at higher temperatures.
3. More concentrated HF can remove more alluminosilicates, but can cause precipitate of calcium fluoride

SPE 150899

Acknowledgements
The authors would like to thank Saudi Aramco for funding this project and for permission to publish.
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Measurement Technique for Organic Acid Additives in Stimulation Fluids. SPEJ 10(2): 152-160.

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Thomas, R.L., Nasr-El-Din, H.A., Lynn, J.D. 2001. Precipitation During the Acidizing of a HT/HP Illitic Sandstone Reservoir
in Eastern Saudi Arabia: A Laboratory Study. Paper SPE 71690 presented at the SPE Annual Technical Conference
and Exhibition, New Orleans, Louisiana, September 30-October 3.
Thomas, R.L., Nasr-El-Din, H.A., Mehta, S. Hilab, V., Lynn, J.D. 2002. The Impact of HCl to HF Ratio on Hydrated Silica
Formation During the Acidizing of a High Temperature Sandstone Gas Reservoir in Saudi Arabia. Paper SPE 77370
presented at the SPE Annual Technical Conference and Exhibition, San Antonio, Texas, September 29- October 2.
Wang, B., Jiang, W., Liu, X., Feng, P. 2000. Acidizing High-Pressure Water Injection Wells Using a New Low-Damage
Acetic/HF Acid System. Paper SPE 64776 presented at the International Oil and Gas Conference and Exhibition in
China, Beijing, China, 7-10 November.

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TABLE 1MINERAL COMPOSITION FOR BEREA AND BANDERA

SANDSTONE CORES
Mineral

Berea

Bandera

Quartz

86

57

Dolomite

16

Calcite

Feldspar

12

Kaolinite

Illite

10

Chlorite

TABLE 2COMPOSITION AND CONCENTRATIONS OF VARIOUS

SOLUTIONS USED IN ZETA POTENTIAL TESTS
Composition

Concentration, wt%

Deionized water

--

Formic acid solution

Formic acid solution

Formic acid solution

Formic acid and NH4Cl solution

Formic acid, 9 + NH4Cl, 5

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TABLE 3COREFLOOD EXPERIMENTS ON BEREA SANDSTONE CORES

Coreflood
Experiment #

Acid Preflush

Acid Mainflush

Acid Overflush

Temperature,
o
F

10 PV of 9 wt% FA

--

--

75

10 PV of 9 wt% FA

--

--

250

7 PV of 9 wt% FA + 5
wt% NH4Cl

3 PV of 9 wt% FA +1 wt% HF

3 PV of 9 wt% FA + 5
wt% NH4Cl

75

3.5 PV of 9 wt% FA +
5 wt% NH4Cl

3 PV of 9 wt% FA +2 wt% HF

3 PV of 9 wt% FA + 5
wt% NH4Cl

75

7 PV of 9 wt% FA + 5
wt% NH4Cl

1 PV of 9 wt% FA +0.5 wt% HF

3 PV of 9 wt% FA + 5
wt% NH4Cl

75

7 PV of 9 wt% FA + 5
wt% NH4Cl

1 PV of 9 wt% FA +0.5 wt% HF

3 PV of 9 wt% FA + 5
wt% NH4Cl

150

7 PV of 9 wt% FA + 5
wt% NH4Cl

1 PV of 9 wt% FA +0.5 wt% HF

3 PV of 9 wt% FA + 5
wt% NH4Cl

250

7 PV of 9 wt% FA + 5
wt% NH4Cl

1 PV of 9 wt% FA +0.5 wt% HF

3 PV of 9 wt% FA + 5
wt% NH4Cl

350

TABLE 4CONCENTRATION OF METAL IONS IN ACID

SOLUTION AFTER 0.5 HOUR REACTION BETWEEN CLAYS
AND 0.9 wt% FORMIC -0.5 wt% HF

Kaolinite

Illite

Chlorite

Al, mg/l

1,025

171

24

Si, mg/L

1,083

638

579

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Fig. 1Zeta potential of 3 kaolinite, chlorite, and illite shows that addition of 5 wt% NH4Cl can help to
stabilize clay particles in 9 wt% formic acid solution

Fig. 219F NMR spectra of 9 wt% formic acid-0.5 wt% HF after reaction with kaolinite for 0.5 hour at
75oF

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Fig. 319F NMR spectra of 9 wt% formic acid-0.5 wt% HF after reaction with illite for 0.5 hour at 75oF

Fig. 419F NMR spectra of 9 wt% formic acid-0.5 wt% HF after reaction with chlorite for 0.5 hour at
75oF

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Fig. 5Pressure drop across the core using 9 wt% formic acid at 75oF and 5 cm3/min on Berea sandstone
core.

Fig. 6Analysis of coreflood effluent samples of Berea sandstone core treated by 9 wt% formic acid at
75oF and 5 cm3/min.

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Fig. 7Pressure drop across the core using 9 wt% formic acid at 250oF and 5 cm3/min on Berea
sandstone core.

Fig. 8Analysis of coreflood effluent samples of Berea sandstone core treated by 9 wt% formic acid at
250oF and 5 cm3/min.

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Fig. 9Pressure drop across the core using 9 wt% formic acid with 5 wt% ammonium chloride as
preflush and 3 PV of 9 wt% formic acid and 1 wt% HF as main flush at 75oF and 5 cm3/min on Berea
sandstone core.

Fig. 10CT number across the Berea sandstone core before and after the acid treatment using 9 wt%
formic acid with 5 wt% ammonium chloride as preslush and 3 PV of 9 wt% formic acid with 1 wt% HF
as main flush at 75oF and 5 cm3/min.

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Fig. 11Analysis of coreflood effluent samples for Berea sandstone core treated by 9 wt% formic acid
with 5 wt% ammonium chloride as preslush and 3 PV of 9 wt% formic acid with 1 wt% HF as main flush
at 75oF and 5 cm3/min.

Fig. 12Pressure drop across the core using 9 wt% formic acid with 5 wt% ammonium chloride as
preflush and 3 PV of 9 wt% formic acid and 2 wt% HF as main flush at 75oF and 5 cm3/min on Berea
sandstone core.

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Fig. 13CT number across the Berea sandstone core before and after the acid treatment using 9 wt%
formic acid with 5 wt% ammonium chloride as preslush and 3 PV of 9 wt% formic acid with 2 wt% HF
as main flush at 75oF and 5 cm3/min.

Fig. 14Analysis of coreflood effluent samples for Berea sandstone core treated by 9 wt% formic acid
with 5 wt% ammonium chloride as preslush and 3 PV of 9 wt% formic acid with 2 wt% HF as main flush
at 75oF and 5 cm3/min.

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SPE 150899

Fig. 15Pressure drop across the core using 9 wt% formic acid with 5 wt% ammonium chloride as
preflush and 1 PV of 9 wt% formic acid and 0.5 wt% HF as main flush at 75oF and 5 cm3/min on Berea
sandstone core.

Fig. 16Analysis of coreflood effluent samples for Berea sandstone core treated by 9 wt% formic acid
with 5 wt% ammonium chloride as preslush and 1 PV of 9 wt% formic acid with 0.5 wt% HF as main
flush at room temperature and 5 cm3/min.

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Fig. 17Pressure drop across the core using 9 wt% formic acid with 5 wt% ammonium chloride as
preflush and 1 PV of 9 wt% formic acid and 0.5 wt% HF as main flush at 150oF and 5 cm3/min on Berea
sandstone core.

Fig. 18Analysis of coreflood effluent samples for Berea sandstone core treated by 9 wt% formic acid
with 5 wt% ammonium chloride as preslush and 1 PV of 9 wt% formic acid with 0.5 wt% HF as main
flush at 150oF and 5 cm3/min.

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SPE 150899

Fig. 19CT number across the Berea sandstone core before and after the acid treatment using 9 wt%
formic acid with 5 wt% ammonium chloride as preslush and 1 PV of 9 wt% formic acid with 0.5 wt% HF
as main flush at 150oF and 5 cm3/min.

Fig. 20Pressure drop across the core using 9 wt% formic acid with 5 wt% ammonium chloride as
preflush and 1 PV of 9 wt% formic acid and 0.5 wt% HF as main flush at 250oF and 5 cm3/min on Berea
sandstone core.

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Fig. 21Analysis of coreflood effluent samples for Berea sandstone core treated by 9 wt% formic acid
with 5 wt% ammonium chloride as preslush and 1 PV of 9 wt% formic acid with 0.5 wt% HF as main
flush at 250oF and 5 cm3/min.

Fig. 22Pressure drop across the core using 9 wt% formic acid with 5 wt% ammonium chloride as
preflush and 1 PV of 9 wt% formic acid and 0.5 wt% HF as main flush at 350oF and 5 cm3/min on Berea
sandstone core.

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SPE 150899

Fig. 23Analysis of coreflood effluent samples for Berea sandstone core treated by 9 wt% formic acid
with 5 wt% ammonium chloride as preslush and 1 PV of 9 wt% formic acid with 0.5 wt% HF as main
flush at 350oF and 5 cm3/min.

Fig. 24Pressure drop across the core using 9 wt% formic acid with 5 wt% ammonium chloride as
preflush and 3 PV of 9 wt% formic acid and 1 wt% HF as main flush at 75oF and 5 cm3/min on Bandera
sandstone core.

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Fig. 25Analysis of coreflood effluent samples for Bandera sandstone core treated by 9 wt% formic acid
with 5 wt% ammonium chloride as preslush and 3 PV of 9 wt% formic acid with 1 wt% HF as main flush
at 75oF and 5 cm3/min.