Journal of Petroleum Science and Engineering 180 (2019) 504–517

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Journal of Petroleum Science and Engineering

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An experimental investigation into the effect of pore size distribution on the T

acid-rock reaction in carbonate acidizing
Hyunsang Yooa,1, Jiwon Parka,1, Youngsoo Leeb,**, Jeonghwan Leea,∗
a
Department of Energy and Resources Engineering, College of Engineering, Chonnam National University, 77, Yongbong-ro, Buk-gu, Gwangju, 61186, South Korea
b
Department of Mineral Resources and Energy Engineering, College of Engineering, Chonbuk National University, 567 Baekje-daero, Deokjin-gu, Jeonju-si, 54896, Republic
of Korea

ARTICLE INFO ABSTRACT

Keywords: This study presents the correlation analysis between pore size distribution and diffusion coefficient based on the
Carbonate acidizing experimental results to evaluate the effect of pore size distribution on the acid-rock reaction in carbonate
Diffusion coefficient acidizing. The mercury injection capillary pressure (MICP) was used to analyze the pore size distribution of four
Pore size distribution limestone samples. Also, the acid-rock reaction experiments were conducted to measure diffusion coefficients
Correlation analysis
using rotating disk apparatus (RDA). In the experimental results, micropore dominated rock samples have lower
dissolution rate and diffusion coefficient than macropore dominated rock samples. It is obviously revealed that
the dissolution rate and diffusion coefficient for limestone samples with similar mineral compositions are quite
different due to various pore size distribution. In the result of correlation analysis, it is revealed that neither
porosity nor permeability exhibits a strong correlation with diffusion coefficient compared with pore size dis-
tribution. Therefore, it can imply that the petro-physical properties such as porosity and permeability have a
lower relevance to the acid-rock reaction kinetics than pore size distribution. To investigate the effect of pore
size distribution on matrix acidizing, optimum injection rates were derived by the experimental results. As a
result, the optimum injection rates increase with the mean and median pore size, and the micropore dominated
rock samples show lower optimum injection rate than the macropore dominated rock samples. Although the
pore size distribution shows a strong correlations with matrix acidizing, the optimum injection rate has been
estimated without ample considerations of pore size distribution. Therefore, the effect of pore size distribution
on diffusion coefficient should be considered to design the optimum injection conditions in carbonate acidizing
job.

1. Introduction wormhole, an acidizing efficiency is controlled by the structure of the

Carbonate reservoirs comprise an approximately half of global hy-
drocarbon reserves. The majority of these are located in Middle East
and North America. At the end of secondary recovery, a massive
amount of oil (40–60% original oil in place (OOIP)) still exists behind
the reservoir due to many factors including heterogeneity of carbonate
rocks (Chen et al., 2018). Well stimulation methods can be employed to
enhance well production. Matrix acidizing is one of commonly used
methods in carbonate reservoirs due to high solubility of rocks. During
matrix acidizing, an acid dissolves the carbonate rock and causes im-
provement of permeability near wellbore by creating wormholes that
can act as high-conductivity pathways for hydrocarbon (Dubetz et al.,
2016). Because the enhanced flow of hydrocarbon occurs through the
wormhole (Hoefner et al., 1987). The structure of the wormhole can
change dramatically depending on the injection rate and diffusion
coefficient of acid (Economides et al., 2012). The injection rate can be
easily obtained from job execution whereas the diffusion coefficient is
intrinsically an uncertain parameter of the acid and rock. Thus it is
essential to measure the diffusion coefficient through acid-rock reaction
experiment (Qiu et al., 2015; Yoo et al., 2018). The various researches
to analyze acid-rock reaction kinetics and diffusion coefficients have
been conducted to accomplish successful matrix acidizing (Lund et al.,
1973; Lund et al., 1975; Busenberg and Plummer, 1982; Anderson,
1991; Fredd and Fogler, 1998; Taylor and Nasr-El-Din, 2004; Taylor
et al., 2006).
The spending rate and diffusion coefficient of the acid in carbonate

∗
Corresponding author.
∗∗
Corresponding author.
E-mail address: jhwan@jnu.ac.kr (J. Lee).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.petrol.2019.05.061
Received 29 January 2019; Received in revised form 23 March 2019; Accepted 26 May 2019
Available online 30 May 2019
0920-4105/ © 2019 Elsevier B.V. All rights reserved.
H. Yoo, et al. Journal of Petroleum Science and Engineering 180 (2019) 504–517

acidizing are dependent on many factors including pressure, tempera-

ture, acid type and concentration, formation composition (chemical and
physical), and so on. Among these factors, heterogeneity of chemical
and rock physical properties can promote a selective acid reaction in
rock formation. Especially, pore size distribution and pore shapes can
contribute to decisive differences in acid-rock reactions (Chilingarian
et al., 1992). Despite the importance of pore size distribution, only a
few studies have been conducted about the effect of pore size dis-
tribution on matrix acidizing.
Dubetz et al. (2016) have characterized pore size distribution of
different carbonate rocks using micro-CT (computer tomography) and
analyzed the impact of pore size distribution on pore volume to
breakthrough (PVBT) and optimum interstitial velocity. They found
that pore size distribution showed a better correlation with PVBT and
optimum interstitial velocity than porosity or permeability alone.
However, the correlation between pore size distribution and diffusion Fig. 1. The picture of four types of limestones.
coefficient has not been reported yet. Dong et al. (2017) suggested a
new model to calculate PVBT and optimum interstitial velocity using 2.2. Diffusion coefficient in acid-rock reaction
the mode size pore, which was the largest frequency in a pore size
distribution, as the optimal conditions. They assumed that larger The general formula for the reaction of HCl (hydrochloric acid) with
amounts of acids would flow into the mode size pores at any particular calcite is given in Eq. (1):
time and position because the mode size pores were more than any
other size of pores. However, this assumption was proven only using the CaCO3 + 2HCl CaCl2 + H2 O + CO2 (1)
mode size without other pore sizes, and the diffusion coefficient of Lund et al. (1973) reported the dependence of surface reaction on
carbonate was assumed to be a single value to apply to the new model. concentration using the power law equation that can be described with
The diffusion coefficient and pore size distribution are significantly Eq. (2):
important in acid-rock reaction during carbonate acidizing, but the
studies regarding effects of pore size distribution on the diffusion RH + = k Csn (2)
coefficient are scanty requiring more vigorous investigations, which where, RH + is the surface reaction rate in gmoles / s cm2 ,
k is the specific
provided primary impetus to the current work. In this study, the pore reaction rate in gmoles / s cm2 or (gmol/cm3) n , Cs is the concentration of
size distributions of four limestone samples are characterized, and acid- H+ on the surface of rock in gmol/ cm3 , and n is the reaction order in
rock reaction experiments are carried out using rotating disk apparatus dimensionless unit. The reaction rate constant, k , can be expressed as
(RDA) to derive the diffusion coefficients of rock samples. Based on the the temperature by the Arrhenius equation:
experimental results, correlation analyses are performed to ascertain
the effect of pore size distribution on diffusion coefficient in acid-rock k = ko exp
Ea
reaction. Furthermore, optimum injection rates are individually derived RT o (3)
with four samples to investigate the influence of pore size distribution
where, ko is the pre-exponential factor or frequency factor in
on matrix acidizing. gmol(1 m) cm(3m 2) s 1, Ea is the reaction activation energy in kcal/ gmol ,
R is the gas constant, and T is the absolute temperature. The mass
transfer rate is represented by the diffusivity of H+ given in Eq. (4):
2. Theoretical background
Jmt = kmt (Cb Cs ) (4)
2.1. Acid-rock reaction mechanism +
In Eq. (4), Jmt is the mass transfer rate of H from the bulk acid
solution to the surface of rock in gmoles / s cm2 , kmt is the mass transfer
Acid-rock reaction kinetics can be classified into three steps in the
coefficient in cm / s , and Cb is the concentration of H+ in the bulk acid
following sequence: acid diffusion to the interface, surface reaction, and
solution in gmoles / cm3 .
diffusion of reactants from the interface. More detailed descriptions are
For a mass transfer limited regime, it can be assumed that the
shown below: (1) the transfer of H+ ions from the bulk of acid solution
concentration of the acid on the surface is negligible compared to the
to the surface of carbonate rock; (2) the reaction between H+ and
bulk concentration because the reaction at the surface of rock is very
carbonate at the surface of carbonate rock; (3) the transfer of reaction
rapid, thus Eq. (4) can be reduced to Eq. (5):
products from the surface of carbonate rock into the bulk of acid so-
lution (Levich, 1962; Lund et al., 1973). The overall reaction kinetics Jmt = kmt (Cb) (5)
can be determined by the slowest step among these three steps, and it is
Newman (1966) introduced a formula to determine the mass
referred to as the rate determining step. If the slowest step is the surface
transfer coefficient using RDA given in Eq. (6).
reaction itself, the reaction is categorized as surface reaction limited
regime. On the other hand, if the slowest step is the transfer of H+ or 0.62048 Sc
2
3 ( )
1
2
reaction products to and from the surface, then the reaction is con- kmt =
(6)
1 2
1 + 0.2980 Sc 3 + 0.1451 Sc 3
sidered as mass transfer limited regime (Taylor and Nasr-El-Din, 2009).
The diffusivity of H+ from the acid solution to the surface of carbonate where, Sc is the Schmidt number in dimensionless, / D , is the kine-
plays an important role in understanding the rate of dissolution of matic viscosity in cm2 / s , D is the diffusion coefficient in cm2 / s , and is
carbonate reactions. Therefore, reaction kinetics should be studies to the disk rotational speed in rad / s . At steady state condition, the flux of
determine the dissolution rate and diffusion coefficient of an acid that H+ to the surface of the rock disk is equal to twice the flux of Ca2+ ions
are critical to improve the design of acidizing in carbonate reservoirs leaving the surface (Eq. (7)).
(Sayed et al., 2018). RDA is widely used as a method to identify dis- Jmt = 2 JCa2 + (7)
solution rate and diffusion coefficient (Taylor et al., 2004).
Hence, combining Eqs. (5)–(7), the mass transfer rate of calcium can

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Fig. 2. XRD results of (a) Edward white, (b) Indiana limestone-A, (c) Indiana limestone-B, and (d) Indiana limestone-C.

Table 1 be written as follows by Eq. (8):

XRF result of rock samples. 2 1
0.31024 Sc 3 ( ) 2
Components Values (%) Jca2 + = Cb
(8)
1 2
1 + 0.2980 Sc 3 + 0.1451 Sc 3
Edward Indiana Indiana Indiana
white limestone-A limestone-B limestone-C The mass transfer rate of HCl ( Jmt ) is equal to the dissolution rate
under the mass transfer limited regime. While RDA experiments are
SiO2 0.22 0.36 0.46 0.30 performed, diluted samples are taken at a constant time interval, and
Al2O3 0.08 0.10 0.12 0.07
Fe2O3 0.08 0.11 0.14 0.08
the amount of calcium ions in samples are measured. The amount of
MgO 0.32 0.51 0.50 0.49 calcium ions is plotted over time, and the points are then fitted to the
CaO 60.33 60.31 59.94 60.72 best straight line. The slope of the line means the rate of change in
SrO 0.04 0.03 0.03 0.03 calcium with time. The dissolution rate is then obtained by dividing the
Na2O 0.56 0.08 – 0.34
slope of the line by the initial surface of the reaction area on the disk.
K2O 0.03 0.09 0.07 0.07
CO2 39.21 38.84 39.21 38.48 The dissolution rate can be presented by Eq. (9).
Total 100.86 100.43 100.47 100.57
1 d [Ca ]
RDh + =
A0 dt (9)

Table 2 where, RDh + is the dissolution rate of calcite in s , and A0 is

gmoles / cm2
Porosity and permeability of rock samples. the initial surface of the reaction area on the disk as a volume fraction
as shown in Eq. (10).
Parameters Porosity (%) Permeability (md)
Ac
Edward white 24.9 15.1 A0 =
Indiana limestone-A 17.5 2.1
(1 ) (10)
Indiana limestone-B 19.1 10.8
Indiana limestone-C 16.2 48.0
where, Ac is the cross-sectional area of disk, and is the porosity of
rock. The diffusion coefficient can be determined by Eq. (8), because
the rate of consumption of H+ equals the rate of mass transfer, Jmt
(Taylor and Nasr-El-Din, 2004).

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Fig. 3. Flow chart of the experimental procedure.

3. Experimental preparation and procedure (XRF) analyses are conducted using Empyrean and Axios Minerals of
PANalytical LTd. Fig. 2 shows the XRD results of each rock sample. The
3.1. Characteristics of rock samples highest peak at two theta angle near 29° and some small low peaks for
quartz are observed. The values of XRF analysis for each rock sample
The pore size distribution of carbonate rock is often analyzed using are summarized in Table 1. The result shows that all of the core samples
MICP. However, the pore size distribution analyzed in previous studies have over 97% purity of calcite content with less than 3% of impurities,
was simply used to characterize carbonate rock type. MICP is suitable to which are not expected to affect the results of acid-rock reaction.
analyze the pore size distribution of carbonate rock with a small pore
size (Ronaldo and Bernardo, 2018), unlike Micro CT with a limitation to
3.1.2. Porosity and permeability measurements
difficulty of detecting a small size pore (Nayef et al., 2016). On the
Porosity and permeability are measured using a helium porosimeter
other hand, factors other than pore size distribution may affect the
and a coreflooding system (Coretest System Inc.), respectively. The
results if we use carbonate samples that have different mineral com-
porosity measurements are repeated for a total of five times with dif-
position. Therefore, the four limestones with very similar mineralogy
ferent numbers of reference cells, and the average value is used. The
were carefully selected as among some reference carbonate samples. In
permeability is measured using nitrogen gas as a conveying fluid, when
this study, four types of limestones from Kocurek Industries in the
the flow rate is stable. Table 2 shows the measured porosity and per-
United States (U.S.) were used as shown in Fig. 1, the Edward white was
meability of the rock samples.
collected in south-central Texas, the U.S., and all Indiana limestones
were collected from Lawrence counties in Indiana, the U.S.
3.2. Experimental procedure

3.1.1. XRD and XRF measurements 3.2.1. Pretreatment process

To identify the purity of rock samples and measure the elemental Fig. 3 presents a flow chart of the experimental procedure. Before
composition of mineral, X-ray diffraction (XRD) and X-ray fluorescence the experiments, a pretreatment process is conducted to minimize the

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Fig. 4. A schematic of rotating disk apparatus.

Table 3 Table 5
Experimental conditions of acid-rock reaction. Raw data of MICP for the Edward white.
Parameters Conditions Pressure (psia) Pore diameter (μm) Incremental intrusion (μl/g)

Type of acid HCl 0.5219 346.5714 0

Pressure 1000 psig 2.0021 90.3385 1.4551
Temperature 25 °C 3.0002 60.2846 0.39977
Disk rotational speed 600 rpm 4.0006 45.2092 0.28783
Acid concentration 10% 5.4983 32.8947 0.32781
5.9975 30.1565 0.07995
7.4940 24.1346 0.32781
8.4917 21.299 0.15191
Table 4
10.4845 17.2506 0.23986
Pore size classification by pore throat diameter (Bennion and Bachu, 2006). 12.9797 13.9344 0.27184
Sample Micropore Mesopore Macropore 15.9679 11.3267 0.24785
20.0012 9.0426 0.28783
Pore throat diameter < 1 μm 1–3 μm > 3 μm 24.9860 7.2386 0.38378
29.9664 6.0355 0.3438
39.5773 4.5699 0.37955
49.3130 3.6677 0.58447
experimental errors that may affect the accuracy of the results. In case 62.6225 2.8882 0.71718
of MICP analysis, each core sample is cut to the volume of about 3 cm3, 72.8999 2.481 1.0654
and dehydrated for approximately 24 h at 60 °C prior to measuring its 92.5848 1.9535 2.0109
weight. 120.6214 1.4994 3.3618
135.3871 1.3359 2.7904
For RDA experiment, each core sample is cut to disk with a diameter
178.4180 1.0137 5.4296
of 1.5 inch and a thickness of 0.78 inch. The surface of the disks is 226.1544 0.7997 7.1639
firstly polished using a sand paper to remove its roughness because the 269.4404 0.67126 6.1960
cross-sectional area of the disk as one of the parameters to calculate the 328.4863 0.5506 5.2649
dissolution rate, should be correctly estimated. The polished disks are 420.6158 0.43 5.4815

soaked in 0.1 N HCl for 40 min to remove impurities on the disk surface.
The disks are then thoroughly rinsed with deionized water and dried.
3.2.2. Pore size distribution analysis
Lastly, the disk is mounted on the rotating shaft using a heat-shrinkage
Pore size distribution is characterized using an Autopore Ⅲ por-
Teflon tube, which covers the perimeter of the disk to allow only the
osimeter 9500 (mercury injection capillary pressure, MICP). The pres-
bottom of the disk to be exposed to acid.
sure is set within the range of 0–60,000 psi to measure all pore sizes. A

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Fig. 5. Pore size distribution of the Edward white.
triple distilled mercury is used in this analysis, which has a surface
tension and a contact angle of 480 dyn/cm and 130°, respectively
(Salimifard and Ruth, 2015). The injection pressure, effectively the
differential across the mercury/vacuum interface, is increased in sev-
eral pressure levels to force mercury enter to the rock sample. The
volume of mercury, which has entered pores at each pressure, and the
proportion of the filled pore space can be calculated during mercury
injection. This process is repeatedly continued until the rock sample is
filled with mercury or the injection pressure reaches to pre-determined
value. Using the pressure and volume data, a mercury injection curve
can be drawn (Giesche, 2006). Lastly, from the curve, it is possible to
calculate the average size of pores making up a stated fraction of the
total pore space. This procedure will be specifically described in section
‘4.1. Determination of pore size distribution’.
Fig. 6. A histogram of pore size distribution for the Edward white.
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Journal of Petroleum Science and Engineering 180 (2019) 504–517
The experimental procedure of the MICP is as follows:
1 Limestone sample is evacuated for a space.
2 Mercury is injected while the system remains evacuated.
3 Atmospheric pressure is applied to the system allowing the mercury
to enter larger pores (macropores).
4 Pressure is raised to 60,000 psi allowing mercury to progressively
enter smaller pores (micropores).
5 The drop in the mercury level gives the volume of pores saturated
with mercury at each pressure level.
3.2.3. Acid-rock reaction analysis
Fig. 4 shows a schematic of the experimental apparatus used for
measuring dissolution rate and diffusion coefficient. It comprises a re-
actor, a sampling port, an exhaust port, and a data acquisition system.
The inner parts of all components are made of Hastelloy-C material for
corrosion resistance. The experimental conditions of the acid-rock re-
action are presented in Table 3. In carbonate acidizing, HCl is com-
monly used as the primary treatment fluid due to its strong dissolving
power and low cost. In addition, its reaction products do not precipitate
as they are usually soluble in water (Buijse et al., 2004). A pressure
greater than 1000 psig is necessary in the reactor to keep evolved CO2
in solution, so that it will not affect the hydrodynamics of the solution
(Rabie and Nasr-El-Din, 2011).
Lund et al. (1975) have verified that the dissolution of limestone
with HCl is mass transfer limited at temperatures over 25 °C. Taylor
et al. (2004) have shown the effect of disk rotational speed on the
dissolution rate of calcite at 25 °C. They reported that the dissolution
rate increased with disk rotational speed until 1000 rpm indicating that
reaction was mass transfer limited regime. Therefore, the temperature
and disk rotational speed are set to be 25 °C and 600 rpm, respectively,
as appropriate conditions to describe the mass transfer limited regime.
To observe the only effect of pore size distribution on diffusion
coefficient, an acid concentration is set to be 10% for all experiments as
HCl concentration varies from 5% to 35% in the field (Rajeev et al.,
2012). To prepare the acid solution, HCl (ACS reagent grade, 37 wt%) is
diluted with deionized water.
The experimental procedure of the RDA experiment is as follows:
1 The rock disk is mounted on the rotating shaft of the magnetic drive,
H. Yoo, et al. Journal of Petroleum Science and Engineering 180 (2019) 504–517

Fig. 7. A histogram of pore size distribution for the Indiana limestone-A.

Fig. 8. A histogram of pore size distribution for the Indiana limestone-B.

and then 10% HCl is filled into the reactor.
2 The reactor is pressurized to the desired pressure (1000 psig) and
maintained constant with nitrogen.
3 The rock disk starts to rotate, and a stable amount (10 ml) of sample
is collected every 2 min precisely during 10 min of reaction process.
4 The collected samples are filtered using 45 µm PTFE (polytetra-
fluoroethylene) membrane filters to remove insoluble precipita-
tions, and diluted by deionized water.
5 The concentration of calcium ions in each diluted sample is mea-
sured using inductively coupled plasma optical emission spectro-
meter (ICP-OES) manufactured by Ametek Spectro Genesis.
4. Results and discussion
4.1. Determination of pore size distribution
A total of four types of limestones were analyzed with the MICP
experiments to figure out pore size distribution. All pore sizes varied in
the range of 0.003–346 μm. Based on the results of MICP, the pore sizes
were classified as three categories referring to Bennion and Bachu
(2006): micropores, mesopores, and macropores as presented in
Table 4.
To analyze the pore size distribution of rock samples, a histogram of
pore size distribution was constructed after processing of the raw data
from MICP results. The whole procedure of the data processing will be

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Fig. 9. A histogram of pore size distribution for the Indiana limestone-C.

Table 6 divided into a 0.01 μm interval of bin, and then the number of values,
Pore size distribution (%) of rock samples. which fell into each bin, was counted. This is called the frequency.
Sample Edward white Indiana Indiana Indiana Next, the volume of mercury was divided by the number of bins, and
limestone-A limestone-B limestone-C then the divided values were assigned to the respective bin. In the case
of above example, the mercury volume of 1.4551 μl/g means injected
Micropore (%) 63.67 59.7 47.61 37.1
volume into the 90.3385 μm–346.5714 μm. Thus the number of bin was
Mesopore (%) 25.54 21.72 13.12 6.54
Macropore (%) 10.79 18.58 39.27 56.36
25,623 ((346.5714 μm–90.3385 μm)/0.01 μm). The volume of
Dominated Pore Micropore Micropore Micropore Macropore 1.4551 μl/g was divided with 25,623 and the divided value was given
Macropore to each bin. The histogram was then normalized to display relative
frequencies showing the proportion of each bin in percentage (%).
The histograms of pore size distribution in each core sample are
Table 7 constructed by using the above specified method as shown in Figs. 6–9.
Representative values of pore size distribution for rock samples. The histograms are presented in both semi-log and log-log plots in (a)
Sample Edward Indiana Indiana Indiana and (b). The semi-log plots with the x-axis being the logarithmic scale
white limestone-A limestone-B limestone-C emphasize the shape of the distribution along the area of most fre-
quently occurring pore size, while log-log plots that encompass the
Mean (μm) 7.81 7.39 12.47 24.44
Median (μm) 0.77 0.74 1.16 7.26 entire distribution of pore sizes within the sample clearly show larger
Mode (μm) 0.73 0.065 0.065 0.065 pores with low-frequency of occurrence (Dubetz et al., 2016). Also, a
cumulative frequency curve is plotted on the log-log plot.
Fig. 6 (a) shows that the Edward white has a high distribution of
discussed for only the Edward white. The same procedure was respec- micropores (less than 1 μm), with macropores (above 3 μm) less than
tively conducted for other three core samples. Table 5 presents the raw 10%. The Indiana limestone-A is composed of a high distribution of
data of Edward white representing mercury intrusion volume at each micropores and mesopores within the range of 0.03–3 μm (Fig. 7).
pressure and pore diameter. Fig. 5 shows the pore size distribution of Therefore, the dominated pores of the Edward white and Indiana
the Edward white using the raw data. In Table 5, when the pore dia- limestone-A are determined as micropores, which comprise over 50% in
meter was 90.3385 μm, the volume of mercury intruded was 1.4551 μl/ the structure. The Edward white and Indiana limestone-A have re-
g. This means that the pressure increases from 0.5219 to 2.0021 psia markably similar distributions, despite the differences in porosity and
during the mercury injecting into smaller pore such as from permeability. The Indiana limestone-B mainly comprises the pore
346.5714 μm of pore diameter to the 90.3385 μm, when the injected ranges of less than 1 μm and greater than 3 μm. However, the dis-
mercury volume is 1.4551 μl/g. That is, the 1.4551 μl/g of mercury was tribution of macropores is frequently included in the histogram struc-
injected into the pores which had the diameter of ture compared to the Edward white and Indiana limestone-A. In addi-
90.3385 μm–346.5714 μm. However, this analytical method can only tion, the Indiana limestone-B has a relatively high percentage of
classify pore size range (micropore, mesopore, macropore) of a rock macropores, which are analogous to mesopore size (Fig. 8). Thus, the
sample, because the distribution of each pore size cannot be precisely dominated pores of the Indiana limestone-B can be determined as mi-
estimated as shown above. For example, the volume of mercury in- cropores and macropores. The Indiana limestone-C primarily comprises
jected into the pore diameter of 90.3385 μm can be regarded as 0 or macropores greater than 10 μm (Fig. 9), so that the dominated pores of
1.4551 μl/g. Indiana limestone-C are categorized as macropores. Table 6 presents
Therefore, a histogram of pore size distribution should be con- the percentage of mircopores, mesopores, and macropores for each rock
structed to eliminate the above error and calculate a representative sample.
value of pore size distribution. First, the entire range of pore sizes was To figure out the effect of pore size distribution on diffusion

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Fig. 10. Comparison of the rock disk in before and after reaction.
coefficient, the mean, median and mode pore sizes were derived. The
mean pore size is the sum of values calculated by multiplying the pore
size by the relative frequency for each bin. The median pore size is the
middle value, which is found by ordering all data points and picking out
the one in the middle. For a distribution, the median is the value such
that the number is equally likely to fall above or below it. Because of
this, the median pore size can be determined by the point of 50% in
cumulative frequency distribution graph. A mode pore size is the most
frequently observed data among the distribution. The mode pore size
can be determined by the highest relative frequency in the histogram of
pore size.
Table 7 presents the values of mean, median, and mode pore sizes of
each rock sample. Even though micropores are dominated in both the
Edward white and Indiana limestone A, the mean pore sizes are dif-
ferent, because the Indiana limestone-A is composed of higher portion
of small pores (< 0.1 μm) than the Edward white. Furthermore the
mode sizes of the Indiana limestones are the same.
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4.2. Determination of the dissolution rate and diffusion coefficient
Acid-rock reaction experiments were conducted with four different
limestones at the same conditions to determine the dissolution rate and
diffusion coefficient. Fig. 10 shows the pictures of rock disks before and
after acid-rock reaction experiments. The most dissolved rock disk is the
Indiana limestone-C. It means that the macropore dominated rock
sample makes stronger reaction than other cases because of its larger
contact area between rock and acid.
The concentrations of calcium ions as the main component of
limestone, were measured for all the cases using ICP-OES. The con-
centrations of calcium ions in each sample are plotted by reaction time
as shown in Fig. 11. In all experiments, the concentrations of calcium
ion are gradually increased with reaction time. This means that rock
disks are continuously dissolved over the reaction time, thus the reac-
tion experiments are well performed.
Table 8 shows the gradients of ion concentration graphs for each
H. Yoo, et al. Journal of Petroleum Science and Engineering 180 (2019) 504–517

Fig. 11. Ca2+ ion concentrations over reaction time.

Table 8 Table 9
Gradients of the ion concentration graph. Initial surface of the reaction area on the rock disk.
Sample Gradient of the ion concentration graph ( gmole/ s ) Sample r (cm ) A c (cm2 ) A 0 (cm2 )

Edward white 5.77 × 10−4 Edward white 1.905 11.4 15.16

Indiana limestone-A 6.08 × 10−4 Indiana limestone-A 13.82
Indiana limestone-B 6.64 × 10−4 Indiana limestone-B 14.09
Indiana limestone-C 7.69 × 10−4 Indiana limestone-C 13.61

rock sample. As one of the procedures to calculate the dissolution rate,
the gradients of the best-fit straight line in Fig. 11 are presented. The
dissolution rate can be obtained by dividing the gradient of the best-fit
straight line in the ion concentration graph by the initial surface of the
reaction area. The initial surface of the reaction area on the disk is
determined by Eq. (10). Table 9 presents the radius of the disks and the
initial surface of the reaction area, which are used in this study.
Table 10 shows the dissolution rates of each rock sample. The dis-
solution rate of the Edward white is 7.62 × 10−5 gmoles / cm2 s , which is
the lowest value among the rock samples. For the Indiana limestone A,

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Table 10
Dissolution rates of rock samples.
Sample Dissolution rate ( gmoles/ cm2 s )

Edward white 7.62 × 10−5

Indiana limestone-A 8.79 × 10−5
Indiana limestone-B 9.43 × 10−5
Indiana limestone-C 1.13 × 10−4

Table 11
Fluid properties for acid.
Acid concentration ( g / cm3 ) µ ( g / cm s ) (cm2 /s ) Cb ( gmoles/ cm3 )
(%)

10 1.0456 1.109 × 10−2 1.04 × 10−2 2.86 × 10−3

Table 12
Diffusion coefficients of rock samples.
Sample Diffusion coefficient (cm2 /s )

Edward white 1.42 × 10−4 Fig. 13. The diffusion coefficient plotted against mean pore size.
Indiana limestone-A 1.78 × 10−4
Indiana limestone-B 1.99 × 10−4
Indiana limestone-C 2.64 × 10−4

Fig. 12. Comparison of dissolution rate and diffusion coefficient for the lime-
stone samples. Fig. 14. The diffusion coefficient plotted against median pore size.

B, C, the dissolution rates are 1.78 × 10−5, 1.99 × 10−5, 2.64 × 10−5
gmoles / cm2 s , respectively, and tend to increase with permeability.
The diffusion coefficient of hydrogen ions from the bulk solution to
the rock surface is a key factor to understand the dissolution of car-
bonate rocks during acid-carbonate reaction (Qiu et al., 2015). Thus,
the diffusion coefficient is considered as the most important parameter
in the design of carbonate acidizing. In this study, diffusion coefficients
were derived by substituting the characteristics of acid fluid, rotating
disk speed, and the dissolution rate into Eq. (8). The density and dy-
namic viscosity of the acid solution were measured by Anton paar Lovis
2000M micro viscometer. Kinematic viscosity was calculated using the
density and dynamic viscosity. Table 11 shows the fluid properties for
acid solution used in this study.
Table 12 presents the diffusion coefficients of each rock sample. The
diffusion coefficients are obtained in the range of 1.42 × 10−4 to
2.64 × 10−4 cm2 / s . Similar to the results of dissolution rate, the dif-
fusion coefficient of the Edward white is the lowest values among the
limestones, and the diffusion coefficients tend to increase with the
permeability in the Indiana limestone cases. Therefore, it is regarded
that the micropore dominated rock samples (Edward white, Indiana
limestone-A) have lower diffusion coefficients than the macropore
dominated rock samples (Indiana limestone-B, Indiana limestone-C).
Fig. 12 compares the dissolution rate and diffusion coefficient of each
limestone. From the results, it is obviously revealed that the dissolution
rate and diffusion coefficient for limestone samples with similar mineral
compositions are quite different due to the various pore size distribu-
tion.
4.3. Correlation analysis between pore size distribution and diffusion
coefficient
Correlation analysis between the diffusion coefficients and the
characteristics of the pore size distribution was conducted to investigate
the effect of pore size distribution on diffusion coefficient. Fig. 13 shows
the relation between diffusion coefficients and mean pore size with the
best-fit straight line. The mean pore size increases with diffusion coef-
ficient, with a satisfactory R2 value of 0.9. From the result, a strong
correlation is observed between diffusion coefficient and mean pore

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Fig. 15. The diffusion coefficient plotted against mode pore size. Fig. 17. The diffusion coefficient plotted against permeability.

Table 13
The results of correlation analysis.
Result Properties of core sample

Porosity Permeability Pore size distribution (μm)

Mean Median Mode

R2 0.66 0.64 0.9 0.88 –

Trend Linear Linear Linear Log –
Direction Reverse (−) Forward (+) Forward (+) Forward (+) –

Fig. 16. The diffusion coefficient plotted against porosity.

size. In addition, the diffusion coefficient as a function of the median

pore size is plotted in Fig. 14, and the x-axis is converted in a log scale
for obtaining the best fit. It is clear that the diffusion coefficient in-
creases with median pore size as R2 value of 0.88. Similar to the mean
pore size, the median pore size also shows the strong correlation with
the diffusion coefficient. However, the plot of diffusion coefficient
versus mode pore size do not demonstrate any clear correlation com-
pared with the mean and median pore size. Furthermore, the mode sizes
of the Indiana limestones are same (Fig. 15). Therefore, it could be
deduced that the mode pore size is only related to the type of limestone. Fig. 18. Comparison of optimum injection rate with different pore size dis-
The petro-physical properties such as porosity and permeability are tribution.
also important to describe a fluid transport in reservoir, thus the cor-
relation between diffusion coefficient and petro-physical properties
summary of the results of correlation analysis.
should be analyzed. Figs. 16 and 17 show the diffusion coefficients
Optimum injection rates were derived to investigate the effect of
plotted by porosity and permeability, respectively, with best-fit straight
pore size distribution on matrix acidizing in carbonate reservoirs. The
line. The diffusion coefficient decreases with the porosity as R2 of 0.66,
optimum injection rate can be calculated by applying the diffusion
but increases with permeability as R2 of 0.64. Therefore, neither por-
coefficient to Damköhler number (Da) as shown in Eq. (11).
osity nor permeability exhibits a strong correlation with diffusion
coefficient compared to the pore size distribution. Table 13 presents the

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Table 14 rates and diffusion coefficients for limestone samples with similar
Optimum injection rates of rock samples. mineral compositions are quite different due to the various pore
Result L ( ft ) Diffusion coefficient Optimum injection rate size distribution.
(cm2 /s ) (cm3/min ) (3) The diffusion coefficient increases with the mean and median pore
size with R2 value of 0.9, 0.88 respectively, thus a strong correla-
Edward white 3 1.42 × 10−5 1.31 tion is observed between the diffusion coefficient and the mean,
Indiana limestone-A 1.78 × 10−5 1.66
median pore size. Also, the diffusion coefficient decreases with the
Indiana limestone-B 1.99 × 10−5 1.86
Indiana limestone-C 2.64 × 10−5 2.46 porosity as R2 of 0.66, but increases with permeability as R2 of 0.64.
Since porosity and permeability do not show a strong correlation
with diffusion coefficient, these parameters have a lower relevance
LD
2/3 to the acid-rock reaction kinetics than the pore size distribution.
Da = 6.33 (4) The optimum injection rate increases with the mean and median
q (11)
pore size, and the micropore dominated rock samples show lower
where, L is the wormhole length in cm , D is the diffusion coefficient, optimum injection rate than the macropore dominated rock sam-
and q is the optimum injection rate in cm3/min . ples. It is regarded that the optimum injection rate has a high re-
Damköhler number is defined as the ratio of the net rate of dis- levance to pore size distribution, because the optimum injection
solution to the rate of transport by convection, where the net rate of rate is derived by the diffusion coefficient, which has a strong
dissolution is the rate of mass transfer for mass transfer limited systems correlation with the pore size distribution.
(Fredd and Fogler, 1999). Hoefner and Fogler (1988) found that the (5) In conclusions, if the pore size distribution is not reflected in the
phenomenon of wormhole formation was governed by the Damköhler reaction of acid and rocks with similar mineral compositions, op-
number. In addition, the optimum Damköhler number was approxi- timum injection rate could be underestimated or overestimated due
mately 0.29 for all the fluid/mineral systems. Gdanski (1999) devel- to different pore size distributions. Therefore, the effect of pore size
oped a wormholing model during matrix acidizing in carbonates, which distribution on diffusion coefficient should be considered to design
showed that practical limits for effective penetration of HCl varied from the optimum injection conditions in carbonate acidizing job.
about 1 to 5 ft. Therefore, the Damköhler number and the length of the
wormhole were assumed as 0.29 and 3 ft, respectively, in this study. Acknowledgments
Fig. 18 and Table 14 present the optimum injection rate for each rock
sample. The optimum injection rate increases with diffusion coefficient. This work was supported by the Energy Efficiency & Resources of
The Edward white shows the lowest optimum injection rate while the the Korea Institute of Energy Technology Evaluation and Planning
Indiana limestone-C presents the highest optimum injection rate. It is (KETEP) grant, funded by the Korea government Ministry of Trade,
regarded that the micropore dominated rock samples have lower op- Industry & Energy (No. 20152510101980).
timum injection rate than the macropore dominated rock samples.
Based on the results, it is revealed that the optimum injection rate Appendix A. Supplementary data
has a high relevance to pore size distribution, because the optimum
injection rate is derived by the diffusion coefficient, which has very Supplementary data to this article can be found online at https://
strong correlation with the pore size distribution. Neither porosity nor doi.org/10.1016/j.petrol.2019.05.061.
permeability exhibits a strong correlation with diffusion coefficient
compared to the pore size distribution, it can imply that the petro- Nomenclature
physical properties are insufficient to describe the mechanism of acid-
rock reaction and wormhole propagation without considering pore size A0 initial surface of reaction area
distribution. In conclusions, if pore size distribution is not reflected in Ac cross-sectional area of disk
the reaction of acid and rocks, optimum injection rate could be un- Cb bulk acid concentration
derestimated or overestimated due to different pore size distributions. Cs surface acid concentration
Therefore, the effect of pore size distribution on diffusion coefficient Da Damköhler number
should be considered to design the optimum injection conditions, such D diffusion coefficient
as injection rate, volume, and pumping schedule in carbonate acidizing Ea reaction activation energy
job. Jmt mass transfer rate
JCa2 + mass transfer rate of Ca2+ ions
5. Conclusion k specific reaction rate
kmt mass transfer coefficient
In this study, the MICP and acid-rock reaction experiments have ko pre-exponential factor
been conducted with the four types of limestone core samples to draw L wormhole length
the correlations between diffusion coefficient and pore size distribution. q optimum injection rate
From the results, the following conclusions have been drawn: n reaction order
R gas constant
(1) The histograms of pore size distribution in each core sample were RDh + initial dissolution rate
constructed to characterize the dominated pore size and re- RH + surface reaction rate
presentative values of pore size distribution. The dominated pores Sc Schmidt number
were determined as micropores for the Edward white and Indiana T absolute temperature
limestone-A. The Indiana limestone-B mainly comprised of the v kinematic viscosity
micropores and macropores. The Indiana limestone-C was cate- porosity of rock
gorized by the macropore dominated rock. disk rotation speed
(2) The micropore dominated rock samples (Edward white, Indiana
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