Journal of Natural Gas Science and Engineering 34 (2016) 792e802

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Journal of Natural Gas Science and Engineering

journal homepage: www.elsevier.com/locate/jngse

Kinetic mechanics of the reactions between HCl/HF acid mixtures and

sandstone minerals
Nianyin Li a, *, Fanhua (Bill) Zeng b, Jun Li a, Qian Zhang a, c, Yanlin Feng a, Pingli Liu a
a
State Key Lab of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, 610500, Sichuan, China
b
Petroleum Systems Engineering, Faculty of Engineering and Applied Science, University of Regina, Regina, SK, S4S 0A2, Canada
c
Research Institute of Natural Gas Technology, PetroChina Southwest Oil & Gas Field Company, Chengdu, 610213, Sichuan, China

a r t i c l e i n f o a b s t r a c t

Article history: Due to the complex mineral composition and structure of sandstone rock as well as the diversity and
Received 1 March 2016 randomness of acid-rock heterogeneous reactions, the acid-rock reaction mechanisms of sandstone
Received in revised form acidizing are not well understood. A model that can be used to describe the kinetic reactions that occur
15 July 2016
during sandstone acidizing is needed. Based on theoretical analysis and laboratory experiments, this
Accepted 16 July 2016
Available online 19 July 2016
paper reveals the main reaction forms of hydrofluoric acid and sandstone mineral in sandstone acidizing,
demonstrates that hydrochloric acid catalytic action occurs during HCl/HF mixture acid dissolving
sandstone mineral, and analyzes the pattern of hydrochloric acid catalytic action. In addition, an acid-
Keywords:
Sandstone
rock reaction rate mechanism model was developed using Freundlich adsorption theory. The model
Acidizing takes into account the combined effects of two parallel reaction processes in the reaction of mud acid
Acid-rock reaction dissolving sandstone mineral: (1) hydrofluoric acid directly reacting with the minerals' lattice bond and
Reaction kinetics (2) hydrochloric acid adsorbed on mineral lattice surfaces and then serving as a catalyst in the reaction
between hydrofluoric acid and sandstone minerals. Furthermore, kinetic experiments of HCl/HF mixture
acid fluid reacting with an actual reservoir sandstone core under various formation temperatures,
pressure levels, and acid shear flow conditions were carried out using a rotating disk instrument. The
mapping method was used to determine the kinetic reaction parameters, and the developed acid-rock
reaction rate mechanism model was used to identify the acid-rock kinetic reaction equations of sand-
stone formation.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction mechanism between HF acid and siliceous minerals have been

Since the 1930s, acidizing has been used extensively to improve
the productivity of oil and gas production wells as well as the
injectivity of injection wells (Williams et al., 1979; Lund et al., 1976).
In acidizing, mixtures of hydrofluoric acid (HF) and hydrochloric
acid (HCl) are usually used in sandstone reservoirs. The mixtures of
HF and HCl are also called mud acid. Hydrofluoric acid in the
mixtures dissolves siliceous minerals. However, due to the complex
compositions of sandstone minerals, the mechanisms of acid-rock
reactions are complicated. The aim of this work is to provide a
better understanding of the basic chemical and physical principles
involved in the reactions between HF and sandstone minerals.
Two different opinions regarding the chemical reaction
* Corresponding author.
E-mail address: lnyswpu@163.com (N. Li).
presented in the literature. HF solution contains a variety of reac-
tion forms, including Hþ, F, HF, and HF 2 . One opinion is that the
first reaction form of HF during the dissolution of siliceous minerals
is F chemisorption (Hartman et al., 2006; Hekim and Fogler, 1980).
The other opinion is that the first reaction form of HF is HF mole-
cules rather than F (Kline and Fogler, 1981). No work has been
conducted to identify the reaction mechanism based on both
experimental and theoretical studies.
Extensive studies have been conducted on the chemical re-
actions between single minerals in sandstone and mud acid, and
kinetic equations for the corresponding acid-rock reaction have
been presented. The reactions examined in these studies include
the reactions between quartz and HF (Hill et al., 1981), the reactions
between aluminosilicates and HF/HCl (Labrid, 1975; Al-harbi et al.,
2012), and the reactions between feldspar and HF/HCl acid (Fogler
et al., 1976). It has been widely accepted that hydrochloric acid can
significantly increase the reaction rate between hydrofluoric acid

http://dx.doi.org/10.1016/j.jngse.2016.07.044
1875-5100/© 2016 Elsevier B.V. All rights reserved.
 N. Li et al. / Journal of Natural Gas Science and Engineering 34 (2016) 792e802 793

and sandstone minerals because of the catalytic action of HCl on the

 
reactions between HF and sandstone minerals. Moreover, the DHn 1 1
Kn ðTÞ ¼ Kn exp  ; n ¼ 1; 2 (2)
concentration of HF molecules do not affect the reaction rate for a R 298 T
given hydrofluoric acid concentration.
By measuring the concentrations of metal ions in the chemical Because hydrofluoric acid has ionization and association prop-
reactions between single sandstone minerals and mud acid, the erties, and hydrofluoric acid solution contains various fluoride
reaction mechanisms and the corresponding kinetic reaction rates forms such as F, HF, and HF
2 , the mole number of fluoride forms in

can be better understood. Hartman et al. obtained the kinetic pa- the solution is constant. Therefore,
rameters of the dissolution reactions between mud acid and zeolite,
chlorite, and illite by comparing the concentrations of metal ions in CHF0 ¼ CHF þ CF  þ 2CHF2 (3)
the reaction of kaolinite and mud acid under the same conditions
(Hartman et al., 2003). Based on the study of Hartman et al. on the where
kinetic mechanics of mud acid and the fluosilicic acid reaction with
aluminosilicates, Gdanski found that the chemical reaction be- K1 ðTÞ$CHF
CF  ¼ (4)
tween hydrofluoric acid and aluminum silicate is a three-stage CHþ
chemical reaction (Gdanski, 1998, 1999, 2000).
The abovementioned studies have provided valuable informa- 2
K2 ðTÞ$CHF
tion on the reaction mechanisms of the chemical reactions between CHF2 ¼ (5)
acid and single minerals in sandstone acidizing. However, further CHþ
study is strongly needed to understand the complexity of the The equations can be simplified as
chemical reactions between the mixture sandstone minerals and
mud acid. Because multicomponent minerals influence acid-rock 8 qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
>
> ðK ðTÞ þ þÞ þ K1 ðTÞ þ C 2Hþ þ 8K2 ðTÞ$CHþ $CHF0
reactions and reaction products can react competitively with re- >
> 1 C H
>
> CHF ¼
actants, the results obtained from single minerals may not be >
> 4K2 ðTÞ
>
>
directly used in sandstone acidizing design. In this study, the main <
K1 ðTÞ$CHF
reaction forms of HF and sandstone minerals were primarily > CF  ¼
> CH þ
investigated based on theoretical analyses and experimental study. >
>
>
>
>
> K ðTÞ$CHF 2
The catalytic action and reactions involved in the dissolution re- >
>
action of sandstone minerals and mud acid were also analyzed. : CHF2 ¼ 2
CH þ
Then, a model describing the effects of HCl catalysis on the acid-
(6)
rock reaction rate of sandstone acidizing was developed and
applied. Acid-rock reaction kinetic experiments were conducted We define a distribution coefficient d (which is the ratio of the
using sandstone cores to obtain the acid-rock reaction kinetic pa- concentrations of a particular reaction form in a hydrofluoric acid
rameters for multicomponent minerals. Furthermore, because solution at equilibrium to the initial HF concentration of that so-
previous work was mainly conducted at room temperature, the lution) to accurately describe the distribution of the various fluo-
experimental work in this study was conducted at reservoir tem- rine reaction forms within the solution. The distribution
peratures. Thus, the results can be applied directly in sandstone coefficients of the fluorine reaction forms HF, F, and HF 2 can be
acidizing design. expressed as
8
>
> C
>
> dHF ¼ HF
>
> CHF0
>
>
2. Theoretical analysis and modeling >
< C 
dF  ¼ F (7)
2.1. Distribution of the reaction forms of hydrofluoric acid during >
> C HF0
>
>
sandstone acidizing >
>
> C
> d  ¼ HF2
>
: HF2
CHF0
At low concentration, hydrofluoric acid is a weak acid, but at
high concentrations, the HF molecules in hydrofluoric acid solution Given a certain temperature and the initial HF concentration,
associate to form nHF molecules via hydrogen bonds. Thus, a HF using Eq. (7), the relationships between the distribution co-
solution can become a strong acid (Ryss, 1960; Gordievskii et al., efficients of the various reaction forms and the pH of the solution
1963). can be determined. The relationship between the pH of the solution
and the distribution coefficients of the fluorine reaction forms at an
nHF4Hþ þ Hn1 Fn (1) initial HF concentration of 3% and a temperature of 75  C is shown
in Fig. 1.
where, at 25  C, when n equals 1 or 2, the equilibrium constants are Fig. 1 indicates that (1) when pH < 1, the main component in the
K1 ¼ 6.6  104 and K2 ¼ 2.2  103. The values of the higher-order hydrofluoric acid solution is HF molecules, and as the pH value
equilibrium constants are not known, but these equilibria only increases, the concentration of HF molecules decreases and the
become important at HF concentrations greater than 17.4% by concentrations of F and HF 2 increase; and (2) when pH > 3.4 (i.e.,
weight. In fact, the concentration of HF is normally less than 3%. the concentrations of F and HF 2 are larger than the concentration
Therefore, n > 3 when equilibrium constants cannot be considered. of HF), the solution contains a very low concentration of HF mol-
The value of the standard enthalpy of reaction DHn ecules and the main fluoride forms in hydrofluoric acid fluid are F
(DH1 ¼ 3210 Cal/mol, DH2 ¼ 4160 Cal/mol) can be obtained from and HF 2 . The foregoing analysis suggests that the pH value has a
the literature (Hekim and Fogler, 1977). The equilibrium constants significant effect on chemical reaction forms and chemical reaction
K1 and K2 at different temperatures can be calculated using the rates. The states of the chemical equilibrium and reaction forms
Van't Hoff equation. change with the pH value.
794 N. Li et al. / Journal of Natural Gas Science and Engineering 34 (2016) 792e802
2.2. Reaction mechanisms of HCl/HF acid mixtures and sandstone
The main purpose of introducing hydrochloric acid in sandstone
acidizing is to dissolve carbonate minerals in sandstone reservoirs
and thereby reduce hydrofluoric acid waste and inhibit the for-
mation of sediments (McLeod, 1984). In addition, HCl has a catalytic
effect on the reaction between hydrofluoric acid and siliceous
minerals and can significantly strengthen the dissolution capacity
of HF (Blumberg and Stavrinou, 1960). Essentially, chemical re-
actions result in bond cleavages and the formation of new lattice
bonds of reaction products. The reactions that occur between HCl/
HF and the lattice bonds of sandstone as well as the catalytic action
of HCl during HF-silicate reactions are not well understood.
The covalent bonds in sandstone mainly include SieO, SieOH,
AleO, and AleOH bonds, whereas the ionic bonds in sandstone
mainly include Kþ, Ca2þ, Mg2þ, and Naþ bonds. Some minerals in
sandstone, such as feldspar and clay, react rapidly with HF, whereas
others, such as quartz, react slowly with HF. The main structural
units of feldspar and clay include (SieO) tetrahedrons and (AleO)
octahedrons. These basic structural units possess significant water
adsorption capabilities. In addition, the ions in these structural
units are exchangeable. Therefore, hydroxylation occurs at the
surface of mineral lattices in acid solutions, as shown in Eq. (8).
Mineral interior Mineral interior
M M
M M M M
H2O / H+ O O
O O O O O O OH OH
Mineral surface Mineral surface
In this equation, denotes the lattice bonds on
the surface of a sandstone mineral involved in the acid-rock reac-
tion process and M denotes Si or Al lattice atoms. Both covalent
bonds, similar to M-O and M-OH, and ionic bonds in sandstone
minerals react with hydrofluoric acid. Generally, covalent bonds are
stronger than ionic bonds. The quartz in the sandstone, which
contains covalent bonds M-O, has the slowest dissolution rate,
which indicates that the cleavages of the covalent bonds M-O play a
key role in HF and siliceous mineral surface reactions.
2.2.1. Reaction mechanisms of HF and the lattice bonds of silica
minerals without HCl catalysis
The reactions between HF molecules and lattice bonds on
sandstone surfaces are associated nucleophilic chemical adsorp-
tion, which entails the nucleophilic attack of fluorine and the
protonation of lattice bonds. Because the F and H components of HF
simultaneously react with the lattice bonds of the sandstone sur-
face minerals, the SieO and AleO bonds are weakened, which
means that old chemical bonds are replaced by new chemical
bonds (shown in Eq. (9)).
(9)
2.2.2. Effects of HCl catalysis on the action mechanisms of HF and
the lattice bonds of silica minerals
When adding hydrochloric acid to the hydrofluoric acid solu-
tion, the HCl acts as a catalyst during the dissolution of the sand-
stone minerals. In dissolution kinetic experiments, Fogler et al.
found that, compared with potash feldspar and hydrofluoric acid,
hydrochloric acid increased the reaction rate between hydrofluoric
acid and sandstone minerals (Fogler et al., 1976). This effect
occurred because the Hþ in the hydrochloric acid reacted with
mineral lattice bonds, resulting in the formation of an unstable,
M M
O O
(8)
OH OH
hydroxylation
inactivated intermediate substance (shown in Eq. (10)).
(10)
Due to the absence of electrons, the Hþ ions can easily react with
the oxygen particles in the mineral lattice bonds, which results in
the formation of an intermediate substance. In addition, because
Hþ is characterized by strong electric field polarization, the Hþ ions
can increase the activity of the intermediate substance, which en-
ables the reaction between the intermediate substance and HF
molecules to occur more easily.
The catalytic action of the hydrochloric acid primarily affects the
protonation reaction pathways of the lattice bonds on the surfaces
of the sandstone minerals. When the reaction is not affected by HCl
catalysis, the HF molecules become the only source of protons. In
contrast, the introduction of Hþ onto the surfaces of the sandstone
minerals leads to the protonation of their bond lattices (shown in
Eq. (11)).
 N. Li et al. / Journal of Natural Gas Science and Engineering 34 (2016) 792e802 795

(11)

2.3. Acid-rock reaction mechanism model that considers molecules and ions in the liquid are adsorbed by multiple active
hydrochloric catalytic action centers on the surface of solid minerals. Freundlich adsorption
isotherm equations were used to describe the acid-rock reaction
In general, due to the adsorption of acid-rock substances, reactions process, including the adsorption process of reactant molecules and
occur on the surface of rocks. The reaction steps are as follows: ions before the acid-rock reaction. Based on the Freundlich
adsorption isotherm equations, in the Appendix, we derive the
1) Diffusion of reactant molecules and ions on the surfaces of acid-rock reaction rates with and without HCl catalysis. The overall
minerals. acid-rock reaction rate equation can be written as a summary of the
2) Adsorption of those reactant molecules and ions on the mineral acid-rock reaction rates with and without HCl catalysis.
surfaces. The acid-rock reaction rate without HCl catalysis can be written as
3) Reactions among the adsorption state molecules and ions on the !m
mineral surfaces. 1=n
GMax1 $KF1 $CHF
4) Desorption of reaction products from the mineral surfaces, and J1 ¼ k 1=n
(12)
1 þ KF1 $CHF
5) Diffusion of the reaction products back into solution.
The acid-rock reaction rate with HCl catalysis can be written as
In most cases, the mass transfer rate of one of these steps is
significantly lower than the mass transfer rates of the other steps. 1=n
!m 0 1=n
1m0
GMax1 $KF1 $CHF G
$@ A
0
Therefore, only the step with the slowest mass transfer rate should J2 ¼ k $
Max2 $KF22 $CHþ
(13)
1=n 1=n
be considered (Fu, 2006; Economides and Hill, 1994). Among the 1 þ KF1 $CHF 1 þ KF22 $CHþ
five steps, the adsorption of the reactant molecules and ions on the
mineral surfaces (Step 2) is the slowest. In other words, surface The overall acid-rock reaction rate equation can be written as
adsorption is the controlling step in the overall process and thus
 
k 
0  0
determines the total reaction rate of acid-rock reactions. The 1=n m 1=n m
J ¼ k GMax1 $KF1 $CHF $ 1 þ $ GMax2 $KF22 $CHþ (14)
equilibrium approximation is used to characterize the reaction k
mechanisms during the acid-rock surface reaction process. In this
approximation, it is assumed that the reactant molecules and ions or
are adsorbed by the surface of the sandstone minerals, equilibrium h i
a 1 þ k $C b
J ¼ k1 $CHF (15)
is achieved instantaneously, and then the reactant molecules and 2 Hþ
ions react with the lattice bonds on the surface of the sandstone.
0 0 0
The adsorption process in the acid-rock surface reaction process where k1 ¼ k$Gm m k m m '
Max1 $KF1 , k2 ¼ k $GMax2 $KF22 , and a¼m/n, b¼m /n.
can be represented by the adsorption isotherm equation. Various
adsorption isotherm equations that represent different adsorption 3. Experiment
mechanisms and characteristics have been developed. In this work,
Freundlich adsorption isotherm equations were used to develop an Using the weight loss method, the primary functional forms in
acid-rock reaction rate equation for sandstone reservoirs. The acid- HF solution during the dissolution of sandstone minerals as well as
rock reactions occurred along two parallel pathways. In one the catalytic effects of hydrochloric acid were investigated in this
pathway, HF directly corroded the mineral surfaces. In the other work. Under various formation temperatures, pressure levels, and
pathway, Hþ was adsorbed onto the mineral surfaces, and HF shear flow conditions, acid-rock reaction kinetic experiments were
reacted with the minerals adsorbed with Hþ (Fogler et al., 1975; conducted using a rotating disk instrument (Li et al., 2015; Rabie
Zhang and Ren, 1996). During the adsorption process, the et al., 2010; Rabie and Nasr-El-Din, 2011). The kinetic parameters
of the reactions between the HF/HCl acid mixtures and sandstone
minerals were measured. Based on the developed acid-rock reac-
tion mechanism model, an acid-rock kinetic equation with variable
formation temperatures and pressure values was developed to
describe the sandstone acidizing process.

3.1. Experimental apparatus

As shown in Fig. 2, a rotating disk instrument has four main

Fig. 1. Relationship between the distribution coefficients of the fluorine reaction forms
and pH.
components: (1) a computer-based controller, (2) a preheater (with
a maximum volume of 1100 ml), (3) a high-pressure and high-
temperature reactor (with a maximum volume of 1000 ml, a
maximum operation temperature of 250  C and a maximum
pressure of 35 MPa), and (4) a rotating speed control system (with a
rotating speed of 100e2000 rpm).
796 N. Li et al. / Journal of Natural Gas Science and Engineering 34 (2016) 792e802
Fig. 2. Diagram of the rotating disk instrument.
3.2. Sample preparation
Sample preparation involved four steps:
(1) An X-ray diffraction test was conducted to measure compo-
nents of the core minerals. The results are shown in Table 1.
(2) Prepare rock powder. The rock powder samples were pre-
pared by milling and drying the sandstone. The prepared
rock powder was used to perform rock dissolution experi-
ments to measure dissolubility.
(3) Prepare rock disks. Cylindrical rock disks with a length of
3 cm and a diameter of approximately 3.8 cm were polished
to ensure surface smoothness. They were subsequently
dried. The prepared rock disks were used for the experi-
mental study of reaction kinetics.
(4) Prepare acid fluid. During sandstone acidizing treatment,
the most common acids used are mixtures of 5 wt%~15 wt%
HCl solution and 0.5 wt%~3 wt% HF solution. A number of
acid solutions with different weight percentages of HCl and
HF in the abovementioned concentration ranges were pre-
pared. To eliminate the effects of the acid additives on the
acid-rock reaction, only corrosion inhibitors were added to
the experimental acid solutions to protect the experimental
devices.
3.3. Experimental method and data processing
(1) Measuring effective hydrofluoric acid concentration
Various methods can be used to measure the fluoride concen-
tration in solutions (Gao and Gu, 2009; Niu et al., 2004; Li and Li,
Table 1
Mineral content of the sandstone core determined via X-ray diffraction.
Total amount of clay Quartz Potassium feldspar
Mineral percentage of rock, %
14.3 23.2 5.8
Illite Montmorillonite
Relative contents of the clay minerals, %
6.9 10
2001). In this work, the fluoride ion selection electrode method
was used. Compared with other methods, such as the colorimetric
method, atomic absorption spectrometry, spectrophotometry, and
ion chromatography, the fluoride ion selection electrode method
can generate more reliable results and is easy to implement. In this
method, a buffered solution was added to the solution to prevent
ionic disruption. The fluoride electrode then acted as an electro-
chemical sensor. Within a certain range of data, the values obtained
by the fluorine electrode and the logarithm of the fluoride ion ac-
tivity in the solution were linearly correlated. Thus, the ionic con-
centration of the measuring solution was obtained based on the
known ion concentration of the solution. Although fluoride elec-
trodes display inherently good selectivity, ionic interference was
prevented by controlling the pH of the solution. Any additional
ionic interference was eliminated by adjusting the ionic strength
using miscellaneous reagents.
(2) Measuring and calculating dissolution ratio
Under a given reaction temperature, 10 g of rock powder was
poured into a beaker, which was filled with 10 ml of acid solution.
After a certain period, the undissolved rock powder was filtered
from the acid solution, dried, and weighed. The dissolution ratio of
the rock powder, which is the ratio of the weight of dissolved rock
powder to the weight of initial rock powder, was calculated.
(3) Measuring acid-rock reaction kinetics
In the test conducted to measure acid-rock reaction kinetics,
acid (approximately 1000 ml) was first poured into the preheater
and then heated to the experimental temperature. Once a prepared
rock disk was mounted in the reactor with Teflon, the reactor was
Anorthose Calcite Dolomite Pyrite
49.8 5.2 1.7 14.3
Illite smectite Kaolinite Chlorite
0.2 30 52.9
 N. Li et al. / Journal of Natural Gas Science and Engineering 34 (2016) 792e802 797

preheated to the experimental temperature, and the preheated acid

was injected into the reactor and pressurized by a hydraulic pump
to the experimental pressure. The rock disks were each rotated
under different designated rotating speeds. Samples of the reacted
acid were taken at a fixed time interval for concentration mea-
surement. The experiments were conducted at different tempera-
tures, pressure levels, and rotating speeds.
(4) Calculating kinetic parameters
lgJ ¼ lgðk0 C m Þ  ðEa =2:303RÞ$ð1=TÞ (22)
According to Eq. (22), when the acid concentration is constant,
lgJ is linearly correlated with 1/T with a slope of (Ea/2.303R) and
an intercept of lg(k0Cm). A regression analysis was applied to the
relationship after measuring the reaction rate constant k1 at
different temperatures. The reaction activation energy Ea and the
frequency factor k0 during the acid-rock reaction process were thus
obtained.

The acid-rock reaction rate can be described as acid consump-

4. Results and discussion
tion per unit time. According to the mass balance law, the chemical
reaction rate is proportional to the effective mass of the reactants.
4.1. The HF molecule is the main reaction form when hydrofluoric
When the temperature and pressure remain unchanged, the reac-
acid dissolves sandstone minerals
tion rate is positively correlated with the m-th power of the con-
centration of various reactants. Because the reaction is
Fig. 3 presents the variation of the dissolution ratio with reac-
heterogeneous, the concentration of rocks can be considered con-
tion time under different pH values at a temperature of 75  C and an
stant. Thus, the acid-rock reaction rate can be expressed as
initial HF mass concentration of 3%. By adding a different per-
centage of HCl, different pH values were obtained for different acid
vC
J¼ ¼ kC m (16) solutions. The experimental results indicate that the HF dissolution
vt
ratio increases with decreasing pH values. Over time, the difference
Taking the logarithms of both sides of Eq. (16), in the dissolution ratio caused by different pH values increases and
then becomes constant. As indicated above, the primary fluoride
lgJ ¼ lgk þ mlgC (17) form in hydrofluoric acid solution is HF molecules at low pH values.
The reaction rate constant K and the reaction order m are con- As the pH value increases, the concentrations of F and HF 2 grad-

stant under a given condition. Thus, the curve relating lgJ to lgC is a ually increase and the species become the main fluoride forms in
straight line with a slope of m and an intercept of lgK. Once the acid solutions (as shown in Fig. 1). Therefore, the primary fluoride
reaction rate constant K and the reaction order m are determined, form of dissolved sandstone mineral is the HF molecule in sand-
the reaction kinetics equation between acid and rock can be stone acidizing.
established. To understand whether HF or F is reacting with sandstone
For the HF acid-rock reaction, we assume that the reaction order minerals, HF and NaF were used to react with the rock powder,
is a and the reaction rate constant is k1. If we assume that the respectively. The experimental results are shown in Fig. 4. As shown
sandstone minerals react with only the HF and the acid-rock re-
action rate J and the HF concentration CHF are known, the HF re-
action order a and the reaction rate constant k1 can be obtained
based on Eq. (17).
By substituting the values of a and k1 into the previously
established acid-rock reaction rate model in Eq. (15), the following
equation can be obtained:

J b
a  1 ¼ k2 ðCHCl Þ
k1 CHF
(18)

0 0
Let k CJ a  1 ¼ J .J is the quasi acid-rock reaction rate, and Eq.
1 HF
(18) can be simplified as follows:

0
J ¼ k2 ðCHCl Þb (19)
By taking the logarithms of both sides of Eq. (19) and plotting Fig. 3. Variation of the dissolution ratio with reaction time under different pH values.
the linear relationship between lgJ0 and lgCHCl, the hydrochloric
acid reaction order b and the reaction rate constant k2 can be ob-
tained. Then, the obtained values of a, b, k1, and k2 are substituted
into Eq. (15), and the overall kinetic equation of the acid-rock re-
action can be obtained.
Another kinetic parameter is the activation energy. The activa-
tion energy is usually described by the Arrhenius equation:
 
Ea
k1 ¼ k0 exp  (20)
RT
By substituting Eq. (20) into Eq. (16), we can obtain
 
Ea
J ¼ k0 $exp  $C m (21)
RT
By taking the logarithm of both sides of Eq. (21), we have Fig. 4. Dissolution ratios of equal concentrations of HF and NaF fluid over time.
798 N. Li et al. / Journal of Natural Gas Science and Engineering 34 (2016) 792e802
Fig. 5. Comparison of the dissolution ratios of rock powder in HF acid fluid and HCl
acid fluid.
Fig. 6. Effects of pH on the dissolution ratio of rock powder.
Table 2
Effects of HF and HCl acid concentrations on the reaction rate. (Temperature: 75  C; Pressure: 7 MPa; Rock Plate Rotation Speed: 300 r/min).
HF concentration
HF acid concentration mol/L Acid-rock reaction rate  108 mol/(cm2$s)
0.5315 1.10
0.8411 1.61
1.3775 3.72
1.9432 4.86
in the figure, under the same conditions, the dissolution ratio of HF
was significantly higher than the dissolution ratio of NaF. Thus, F
did not significantly contribute to the dissolution of the sandstone
minerals.
In the hydrofluoric acid-sandstone mineral reaction, Hþ is
another possible reaction form that may react with the lattices of
sandstone minerals. Hþ primarily originates from HCl ionization.
The effects of HF and HCl on the sandstone dissolution ratio are
shown in Fig. 5. As shown in the figure, the dissolution ratio of
sandstone rock powder in hydrochloric acid is higher than the
dissolution ratio in hydrofluoric acid. In a previous study, Bryant
found that eluviation occurs during the reaction between hydro-
chloric acid and aluminosilicate minerals (Bryant and Buller, 1990).
In another study, Fogler et al. compared the dissolution rates of
potash feldspar in hydrochloric acid and mud acid (hydrofluoric-
hydrochloric acid mixtures) (Fogler et al., 1975). The results indi-
cated that the dissolution rate of the mud acid was 20 times greater
than that of the hydrochloric acid.
In conclusion, the primary reaction form of the reaction be-
tween hydrofluoric acid and sandstone minerals is HF molecules,
rather than F, HF þ
2 , and H molecules.
4.2. Catalysis of hydrochloric acid enhances the reaction between
hydrofluoric acid and sandstone minerals
The dissolution ratio of sandstone rock powder in mud acid
fluid, hydrofluoric acid fluid, and hydrochloric acid fluid are pre-
sented in Fig. 6. As shown in the figure, under the same experi-
mental conditions, the dissolution ratio of sandstone rock powder
in mud acid fluid is not only much higher than it is in hydrofluoric
acid fluid and hydrochloric acid fluid, but it is also higher than the
sum of the ratios in hydrofluoric acid fluid and hydrochloric acid
fluid. The experimental results show that, although hydrofluoric
acid makes a dominant contribution to the dissolution ratio of mud
acid dissolving sandstone minerals, hydrochloric acid among mud
acid catalyzes the reaction between hydrofluoric acid and sand-
stone minerals and increases the dissolution ratio of sandstone rock
powder in mud acid fluid.
4.3. Kinetic equation of the acid-rock reaction
Acid reaction rates under different acid concentrations were
measured to investigate the effects of the variation in concentration
on the reaction rate. The results are shown in Table 2.
The curve relating the reaction rate and HF acid concentration is
shown on a log-log coordinate system in Fig. 7(a). The straight slope
and intercept of the linear relationship are obtained to determine
the HF reaction order a ¼ 1.215 as well as the HF reaction rate
constant k1 ¼ 2.25  108. The relationship between lgJ0 and lgCHCl
is determined using Eq. (19). Using the straight slope and intercept
of the relationship shown in Fig. 7(b), the HCl reaction order
b ¼ 0.59 and HCl reaction rate constant k2 ¼ 0.29 are determined.
The findings show that, because the HF reaction order is greater
HCl concentration
HCL acid concentration mol/L Acid-rock reaction rate mol/(cm2$s)
1.9813 0.43
2.6378 0.49
3.1794 0.59
3.9631 0.63
than 1, the HF acid and rock reaction follows a first-order rate law,
and the acid-rock reaction rate is proportional to the HF concen-
tration. In addition, because the HCl reaction order is approxi-
mately 0.59, the HCl concentration slightly affects the reaction rate.
By substituting the values of a, b, k1, and k2 into Eq. (15), the
comprehensive kinetic equation of the mud acid-sandstone reac-
tion can be obtained:
 
J ¼ 2:25  108 1 þ 0:29CHCl
0:59 1:22
CHF
¼ 2:25  108 CHF
1:22
þ 6:53  109 CHCl
0:59 1:22
CHF (23)
Based on a kinetic experiment involving mud acid reacting with
feldspar, Fogler et al. measured the reaction order and reaction rate
constant of hydrofluoric acid and hydrochloric acid (Fogler et al.,
1975). The experimental results are shown in Table 3. Compared
with the results in Table 3, the magnitude of reaction rate constants
obtained in this study are in line with the experimental results of
Fogler et al., and the reaction orders obtained in this study are
approximately equal to those associated with the reaction between
potash feldspar and mud acid.
 N. Li et al. / Journal of Natural Gas Science and Engineering 34 (2016) 792e802 799

Fig. 7. Logarithmic relationships between HF and HCl concentrations and acid-rock reaction rates.

Table 3 the reaction between the sandstone minerals and HF acid and the
The kinetic parameters of the reaction between mud acid and feldspar. activation energy Ea ¼ 30.94 kJ/mol and the frequency factor
Reaction HCl HF k0 ¼ 0.0030 of the reaction between the sandstone minerals and
This work a ¼ 1.215 b ¼ 0.59 mud acid. As shown in Fig. 8, the activation energy significantly
K1 ¼ 2.25  108 k2 ¼ 0.29 affected the acid-rock reaction. The reaction activation energy
Soda feldspar and mud acid a¼1 b¼1 represents the energy required for normal molecules to become
k1 ¼ 1.85  108 K2 ¼ 0.3 activation molecules. The activation energy of the mud acid-
Potash feldspar and mud acid a ¼ 0.4 b ¼ 1.2
sandstone mineral reaction was lower than the activation energy
k1 ¼ 3.4  108 K2 ¼ 0.7

Table 4
Reaction rates and reaction rate constants of HF acid and mud acid reacting with sandstone at different temperatures.

Acid type Temperature K HF concentration (mol/L) Reaction rate (mol/s.cm2) Reaction rate constant

Hydrofluoric acid 333 1.9321 2.25  108 1.04  108

348 1.9002 4.86  108 2.25  108
363 1.9348 7.37  108 3.42  108
378 1.9221 9.81  108 4.55  108
Mud acid 333 1.9527 6.95  108 4.90  108
348 1.9024 8.25  108 5.82  108
363 1.9257 1.40  107 9.91  108
378 1.9219 2.59  107 18.20  108

of the HF-sandstone mineral reaction. Thus, hydrochloric acid

promoted the reaction of hydrofluoric and sandstone minerals.

5. Conclusions

(1) Hydrofluoric acid, which possesses ionization and associa-

(2) Hydrochloric acid can promote the reaction between hy-
Fig. 8. Effects of temperature on the reaction rate constants of HF and mud acid.
4.4. Activation energy of the acid-rock reaction process
As shown in Table 4, the reaction rate constant k1 was tested at
different temperatures (60  C, 75  C, 90  C, and 105  C), the same
(3) The Freundlich adsorption isotherm equation can be used to
pressure of 7 MPa, and the same rotation speed of 300 r/min. In
addition, as shown in Fig. 8, the linear relationship between lgk1
and 1/T was determined to obtain the acid-rock activation energy
Ea and the frequency factor k0.
Using the linear regression method, we calculated the activation
energy Ea ¼ 33.99 kJ/mol and the frequency factor k0 ¼ 0.0025 of
tion properties, has various reaction forms, such as Hþ, F,
HF, and HF2 . The primary reaction form of hydrofluoric acid
when it reacts with sandstone minerals is HF molecules,
rather than F, HF þ
2 , and H molecules.
drofluoric acid and sandstone via catalysis action. The addi-
tion of HCl significantly increased the solubility of
hydrofluoric acid. Because Hþ does not contain electrons, it
reacted easily with the oxygen in the mineral lattice bonds
and formed a highly reactive intermediate substance.
Consequently, the HF molecules reacted easily with the
mineral lattice bonds of the sandstone.
effectively describe the adsorption process before the
occurrence of acid-rock surface reactions. In response to the
controlling step of the reaction rate and reaction mecha-
nisms of the adsorbed reactant molecules and ions on the
surface of minerals, an acid-rock reaction rate mechanism
model was developed using Freundlich adsorption theory.
800 N. Li et al. / Journal of Natural Gas Science and Engineering 34 (2016) 792e802
This model considered the catabolic effect of the HCl adsor-
bed by the mineral lattices.
(4) A rotating disk apparatus was used to measure the kinetic
parameters of the HF/HCl acid reaction with sandstone
minerals and determine the kinetic equation of the reaction
under various formation temperatures, pressure levels, and
shear flow rate conditions. The reaction of hydrofluoric acid
and sandstone followed a first-order rate law. The reaction
rate was proportional to the HF concentration. However, it
was found that the HCl concentration only slightly affects the
reaction rate because the activation energy of the mud acid-
sandstone mineral reaction was lower than that of the HF-
sandstone mineral reaction. This result also indicated that
hydrochloric acid can promote the reaction between hydro-
fluoric acid and sandstone.
Acknowledgments
This work was supported by the Open Fund (PLN1519) of the
State Key Laboratory of Oil and Gas Reservoir Geology and Exploi-
tation (Southwest Petroleum University) as well as the National
Natural Science Foundation of China (51574197).
Nomenclature
CþH Hþ concentration, mol/L
CHF0 initial HF concentration, mol/L
CHF HF concentration, mol/L
CF Fconcentration, mol/L
CHF2 HF2 concentration, mol/L
CHCl HCl concentration, mol/L
Ea the acid-rock reaction activation energy, J/mol
J the overall acid-rock reaction rate, mol/(L$s)
J1 the acid-rock reaction rate without HCl catalysis, mol/
(L$s)
J2 the acid-rock reaction rate with HCl catalysis, mol/(L$s)
K the equilibrium constant
K1(T), K2(T) primary and secondary reaction equilibrium constants
at different temperatures
KF1 when the HF is not affected by HCl catalysis, the
adsorption equilibrium constant of the HF molecule on
the lattice surfaces of the sandstone minerals
KF21 the adsorption equilibrium constant of Hþ in the
adsorption activity center of SiteMO
KF22 the adsorption equilibrium constant of Hþ in the
adsorption activity center of SiteMOH
k the acid-rock reaction rate constant without HCl catalysis,
(mol/L)1m/s
k 0 the acid-rock reaction rate constant with HCl catalysis,
(mol/L)1m/s
k0 frequency factor
k1 the reaction rate constant of hydrofluoric acid,
(mol1a$La)/(cm (Lund et al., 1976)$s)
k2 the reaction rate constant of hydrochloric acid t, Lb/molb
m the reaction order, zero dimension
m0 the reaction order with HCl catalysis, zero dimension
R the molar gas constant, 8.314 J/(mol$K)
Site the adsorption activity center located on the lattice
surfaces of the sandstone minerals
SiteHF the adsorption-state HF molecules in the activity centers
SiteMO the activation centers formed by the metal ions of the
mineral surface with neutral dissociation
SiteMOH the activation center formed after the surface of minerals
lattice has undergone acid solution hydroxylation
SiteMOHþ the activation center after the protonation of the
2
minerals lattices, whose edges or mineral surfaces were
hydroxylated and then acquired Hþ from acid
T the thermodynamic temperature, K
a the reaction order of HF, zero dimension
b the reaction order of HCl, zero dimension
d the distribution coefficient of various fluoride reaction
forms
u the rotation speed of rock disk, r/min
DHn the reaction enthalpy change, KJ/mol
GSiteHF the amount of adsorbed HF located in an activity center
GMax1 the maximum adsorption capacity of the reaction system
without the effect of HCl catalysis
GMax2 the maximum adsorption capacity of the reaction system
with the effect of HCl catalysis
Appendix. Acid-rock reaction model of sandstone acidizing
with hydrochloric acid catalysis
The reaction between mud acid and sandstone minerals
occurred along two parallel pathways. In one pathway, the HF
molecules, which remained unaffected by the catalysis of Hþ,
directly reacted with the lattice bonds on the surfaces of the
sandstone minerals. In the other pathway, the Hþ that was adsor-
bed by the lattice bonds of the sandstone minerals could catalyze
the reaction of HF molecules and sandstone minerals. In response
to the control step of the reaction rate and reaction mechanisms of
the adsorbed reactant molecules and ions on the surface of min-
erals, an acid-rock reaction rate mechanism model was developed
based on Freundlich adsorption theory.
(1) Factors unaffected by HCl catalysis
HF dissolves sandstone minerals by directly reacting with their
lattice bonds. This phenomenon, which is not affected by HCl
catalysis, can be expressed as follows:
1
HF þ Site⇔ SiteHF ðAdsorption reaction; fastÞ (A-1)
n
SiteHF /P ðSurface reaction; slowÞ (A-2)
In Eq. (A-1) and (A-2), Site represents the adsorption activity
center located on the lattice surfaces of the sandstone minerals, n
represents the number of activity centers occupied by HF mole-
cules, KF1 represents the adsorption equilibrium constant, SiteHF
represents the adsorption-state HF molecules in the activity cen-
ters, and P represents the product of the acid-rock surface reaction.
Because the reaction of adsorption-state HF molecules on the sur-
face of the mineral lattices is a speed-controlled step, the following
relationship can be derived according to the surface mass action
law:
J1 ¼ k$Gm (A-3)
SiteHF
In this equation, GSiteHF represents the amount of adsorbed HF
located in an activity center. The Freundlich adsorption isotherm
equation can be used to represent the adsorption equilibrium of the
HF molecules on the mineral lattices:
1=n
GSiteHF ¼ GSite $KF1 $CHF (A-4)
According to Eq. (A-4),
 N. Li et al. / Journal of Natural Gas Science and Engineering 34 (2016) 792e802 801

constant can be confirmed to be

GSiteHF GSiteHF
KF1 ¼ 1=n
¼
1=n (A-5) GSiteMOH GSiteMOH
GSite CHF GMax1  GSiteHF $CHF KF21 ¼ ¼ 
GSiteMO $CH1=n
þ GMax2  GSiteMOH  GSiteMOHþ $CH1=n
þ
After simplification, we can obtain 2

(A-9)
1=n
GMax1 $KF1 $CHF
GSiteHF ¼ 1=n
(A-6)
1 þ KF1 $CHF GSiteMOHþ GSiteMOHþ
KF22 ¼ 2
¼ 2

By substituting Eq. (A-6) into Eq. (A-3), the acid-rock reaction GSiteMOH $CH1=n
þ GMax2  GSiteMO  GSiteMOHþ $CH1=n
þ
rate equation without hydrochloric acid catalysis can be obtained: 2

(A-10)
1=n
!m
GMax1 $KF1 $CHF By simplifying Eqs. (A-9) and (A-10), we can obtain
J1 ¼ k 1=n
(A-7)
1 þ KF1 $CHF
GMax2
GSiteMO ¼   (A-11)
where GMax represents the maximum, or saturation, adsorption 1=n 1=n 2
1þ KF21 $CHþ þ KF21 $KF22 $ CHþ
capacity. The maximum adsorption capacity can be used to repre-
sent the adsorption equilibrium limit of a reaction system.
GMax2 $KF21 $CH1=n
þ
(2) Catalytic portion of the model GSiteMOH ¼   (A-12)
1=n 1=n 2
1 þ KF21 $CHþ þ KF21 $KF22 $ CHþ
The catalytic portion of the acid-rock reaction is related to the
surface concentrations of HF molecules and Hþ. Acid-rock surface  2
reactions become more complex compared with the condition GMax2 $KF21 $KF22 $ CH1=n
þ
without HCl catalysis. After HCl is adsorbed by the surfaces of the GSiteMOHþ ¼   (A-13)
1=n 1=n 2
lattice minerals, the reaction between hydrofluoric acid and sand- 2
1 þ KF21 $CHþ þ KF21 $KF22 $ CHþ
stone minerals is catalyzed by hydrochloric acid. Because various
1=n 1=n
activation centers can adsorb Hþ on the surfaces of the lattice In acid solution, KF21 $CHþ ð1 þ KF22 $CHþ Þ > 1; therefore, Eqs. (A-
minerals, Hþ can be affected in a variety of ways during the 11)e(A-13) can be simplified as follows:
adsorption process. Therefore, the activation centers that are most
likely to adsorb Hþ at the beginning of the adsorption process must GMax2
GSiteMO ¼   (A-14)
be confirmed to establish an accurate catalytic acid-rock reaction 1=n 1=n 2
KF21 $CHþ þ KF21 $KF22 $ CHþ
rate model.
Due to the lattice formations of feldspar and the clay compo-
nents of sandstone, after metal ion dissociation occurs, the lattices GMax2
form activation centers that can easily adsorb Hþ. Therefore, the GSiteMOH ¼ 1=n
(A-15)
1 þ KF22 $CHþ
lattice has hydroxylation properties. Fogler et al. proposed that the
surfaces of mineral lattices possess hydroxylation properties even
before sandstone acidizing begins (Fogler et al., 1975). Three types GMax2 $KF22 $CH1=n
þ
of activation centers on surfaces of mineral lattices can adsorb GSiteMOHþ ¼ 1=n
(A-16)
Hþ22: the activation centers formed by the metal ions of the min-
2 1 þ KF22 $CHþ
eral surface with neutral dissociation, denoted by SiteMO ; the Compared with the corresponding adsorption capacities at
activation center formed after the surface of mineral lattices has three types of activation centers that may adsorb Hþ with GMax2,
undergone acid solution hydroxylation, denoted as SiteMOH; and respectively, we find that the relationship of adsorption capacities
the activation center after the protonation of the mineral lattices at three types of activation centers is GSiteMOHþ > GSite
MOH
> GSiteMO and
whose edges or mineral surfaces were hydroxylated and then ac- 2
that GSiteMOHþ is the highest. Therefore, the reaction mechanisms of
quired Hþ from acid, denoted as SiteMOHþ . Therefore, the adsorp- 2
the hydrofluoric acid reacting with the surfaces of the mineral
2
tion equilibrium of Hþ on the surfaces of the mineral lattices can be lattices and absorbed by hydrochloric acid can be expressed as
expressed as
SiteHF þ SiteMOHþ /P ðSurface reaction; slowÞ (A-17)
2
8
>
> According to the law of surface mass action,
>
>
>
> 1 þ KF21
>
>
< H þ SiteMO ⇔SiteMOH 0
J2 ¼ k Gm m
0

n SiteHF GSite (A-18)

ðAdsorption reaction; fastÞ MOHþ
>1
> KF22
2

>
> þ
> nH þ SiteMOH ⇔SiteMOH2þ
>
>
By substituting Eqs. (A-6) and (A-16) into Eq. (A-18), the acid-
>
: rock reaction rate, which is catabolic, can be obtained as follows:

(A-8) 1=n
!m 0 1=n
1m0
GMax1 $KF1 $CHF G
$@ A
0 Max2 $KF22 $CHþ
J2 ¼ k $ 1=n 1=n
(A-19)
1 þ KF1 $CHF 1 þ KF22 $CHþ
According to Eq. (A-8), the Freundlich adsorption equilibrium
802 N. Li et al. / Journal of Natural Gas Science and Engineering 34 (2016) 792e802

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