Journal of Petroleum Science and Engineering 203 (2021) 108593

Contents lists available at ScienceDirect

Journal of Petroleum Science and Engineering

journal homepage: http://www.elsevier.com/locate/petrol

Acid stimulation in carbonates: A laboratory test of a wormhole model

based on Damköhler and Péclet numbers
H. Al-Arji, A. Al-Azman, F. Le-Hussain, K. Regenauer-Lieb *
University of New South Wales, Sydney, Australia

A R T I C L E I N F O A B S T R A C T

Keywords: Acid stimulation has been used worldwide as a stimulation technique either by matrix acidizing to remove the
Carbonate acidizing near-wellbore permeability impairment which is referred to as formation damage or acid fracturing to enhance
Wormhole the connectivity between wells and reservoirs. Carbonate acid stimulation improves the near-wellbore perme­
Dimensionless numbers
ability through the creation of deeply penetrating fluid pathways referred to as wormholes. The stimulation
Damköhler
Péclet
success depends on the length and width of these wormholes. Here, we test the results of a theoretical study
Acidic core flooding which suggests that the effect of acid flow in a reactive porous medium can be fully defined by just two sig­
HCl injection nificant dimensionless numbers, the non-dimensional Damköhler and Péclet numbers. The approach was vali­
dated in an idealized numerical study and is here tested in a systematically controlled laboratory experiment for
real carbonate rocks. In order to obtain statistically meaningful results, we pushed the envelope by testing the
prediction of the critical point for the wormholing phenomenon in a difficult domain, where sufficient randomly
distributed pathways exist such that the wormholing domain is rarely achieved. The result confirmed that for a
randomly-structured highly porous media, the critical point for dissolution pattern formation including the
wormholing phenomenon can be fully captured by a domain diagram of inverse Damköhler versus Péclet number
as predicted by the theoretical model. The model also holds for moderately tight formations, however, breaks
down when the natural permeability drops well below 100 mDarcy. We conclude that the result of this research
can be applied to reliably predict the wormholes initiation and various dissolution structures under various
injection rate and HCl-concentration.

1. Introduction length- and time-scales encapsulated in a system of partial differential

It is believed that carbonate reservoirs represent more than half the
world’s oil reserves. About half of the world’s proven oil reserves are in
the Middle East area, where about 70% of that oil reserves found to be in
fractured carbonate reservoirs (Statistical Review of World Energy).
Carbonate rocks are known for their high level of heterogeneity and
randomly distributed pathways (Masalmeh et al., 2014). Naturally, most
of the carbonate reservoirs consist of a wide range of permeability that
can be either high permeability represented by fractures and low
permeability represented by the matrix. This variation in permeability
further increases the challenge for predicting the outcome of acid in­
jection (Pal et al., 2017). In this contribution, we aim at improving the
accuracy of carbonate acid treatment through testing a theoretical
model proposed by Szymczak and Ladd (2004). This physics-based
model is based on a forward prediction of the onset of the wormhole
phenomenon, based on a choice of physical processes, the critical
reaction-diffusion-advection equations. The theory has been validated
by numerical implementations but an experimental assessment was still
outstanding (Szymczak & Ladd, 2009). A laboratory test of the proposed
physics-based model is the objective of this contribution. We present
here a systematic analysis of core-flood acidizing tests of a variety of
naturally permeable carbonate samples.
Carbonate acidizing is a well-established empirically-based practice
in well stimulation operations to reduce formation damage due to dril­
ling or completion operations and improve near-well connectivity
among the wellbore and formation. The acid in carbonate stimulation is
used to dissolve the solid rock and create deep conductive flow pathways
“wormholes” which connect the virgin formation in the reservoirs to the
wellbore to enhance the oil flow (Hoefner et al., 1987). The connectivity
enrichment following the acid treatment strongly relies on the depth of
created wormholes away from the wellbore. The deeper the wormholes
can penetrate the formation, the better the stimulation outcome is, as a

* Corresponding author.
E-mail addresses: h.alarji@student.unsw.edu.au (H. Al-Arji), klaus@unsw.edu.au (K. Regenauer-Lieb).

https://doi.org/10.1016/j.petrol.2021.108593
Received 29 November 2020; Received in revised form 22 February 2021; Accepted 24 February 2021
Available online 27 February 2021
0920-4105/© 2021 Elsevier B.V. All rights reserved.
H. Al-Arji et al.
lowered skin is attained. In carbonates, acid treatment is performed by
the injection of reactive fluids most often hydrochloric acid (HCl) owing
to its availability, cost, and high rock dissolving power with calcitic and
dolomitic rocks. The significance of using HCl acid in carbonate reser­
voirs stimulation goes back to the late 19th century (Frasch, 1896).
Since plain HCl is very corrosive, it was unpreferable to the industry at
that time. However, after introducing corrosion inhibitors, the HCl was
the focus of researchers giving to the high dissolution rate power (Fredd
and Fogler, 1996); Fredd and Fogler, 1998; Frenier et al. (1988). It is
worth mentioning that additives quantity needs to be added carefully as
they affect the HCl dissolving efficiency. Experiments performed with
pure HCl have been conducted to consider the spent acid effect in
dolomitic carbonates (Yoo et al., 2018). The authors found that spent
acid has a greater dissolving effect on dolomite disks than fresh acid.
Additionally, spent acid resulted in a higher dissolution rate compared
to fresh acid. The reason owes to the long contact time which makes the
rock/acid reaction stronger at the surface of the dolomite rock. The
wormholes dissolution structure was suggested to be mostly affected by
the injection rates. As the wormhole propagates more in the rock matrix,
the wormhole tip gradually progresses as a result of the spent acid effect.
To study the effect of wormholes and define the related parameters,
lab experiments on core specimens are required by testing injecting acid
into the core sample face until wormholes breakthrough. These experi­
ments have enabled the extensive study of the dependence of acidizing
efficiency on treatment design parameters, such as flow rate (Frick et al.,
1994; Hoefner and Fogler 1989), acid type (Gomaa and Nasr-El-Din,
2010; Hoefner and Fogler, 1989; Zakaria and Nasr-El-Din, 2015) and
fluid properties (Hoefner and Fogler, 1989; Mostofizadeh and Econo­
mides, 1994). Breakthrough curves from coreflood testing are also
incorporated directly into semi-empirical models (Buijse and Glasber­
gen, 2005; Fredd, 2000; Furui et al., 2012; Tan et al., 2016), which
upscale the core test data to predict wormhole growth in open-hole
reservoirs.
Several researchers (Hoefner et al., 1987; Daccord and Lenormand
1993; Frick et al., 1994; Fredd and Fogler 1998, 1999) have recognized
the significance of wormhole formation and investigated the parameters
that affect the rock dissolution phenomenon. These observations have
shed light on basic mechanisms of wormhole formation which resulted
in developing models that rely on Damköhler and Péclet numbers to
estimate the wormhole structure, the rate of wormhole growth and the
optimum condition for wormhole formation. Both Damköhler and Péclet
numbers count on the effective diffusion coefficient and are conven­
tionally used to predict wormhole creation for different rock structures
and mineralogy (Fredd et al., 2017; Szymczak & Ladd, 2009). It is sur­
prising that just two non-dimensional numbers should be so efficient in
capturing the phenomenon of wormhole formation as there are many
factors that affect the wormhole initiation. The two numbers effectively
imply that the extent to which wormholes form depends primarily on the
injection rate and HCl-concentration. If this is true, it comes as a striking
observation that microstructural diversity can be described by just these
two numbers. In this paper, diluted hydrochloric acid (1–5 wt% HCl) is
injected into carbonate rocks, namely Mount Gambier limestone, to
study the effect of different parameters such as acid concentrations and
injection rates that will result in initiating the wormholes. Damköhler
and Péclet dimensionless numbers are calculated and plotted to provide
a complete physical description of wormholes and hence identify the
wormhole formation region. In this study, we will validate the numerical
model proposed by Szymczak and Ladd (2009) and test the method of
predicting wormholes formation and other dissolution structures under
different injection rate and HCl concentration.
2. Literature review
2.1. Acid stimulation
There has been intense interest in the industry to understand the
2
Journal of Petroleum Science and Engineering 203 (2021) 108593
physics behind carbonate acidization to optimize stimulation treatment
jobs that would result in effective outcomes at minimal costs. In car­
bonate acidizing, the success of the treatment depends on the length and
width of deep conductive flow pathways called “wormholes” created as
a result of the reaction of acidic fluids with carbonate rocks. The reaction
of carbonates with hydrochloric acid (HCl) creates water-soluble reac­
tion products described as (Nasr-El-Din et al., 2006):
CaCO3 + 2HCl→CaCl2 + CO2 + H2 O(Limestone) (1)
CaMg(CO3 )2 + 4HCl→CaCl2 + MgCl2 + 2CO2 + 2H2 O(Dolomite) (2)
The reaction of limestone rocks with HCl, as illustrated in the
chemical reaction (1), is fast, and therefore result in a mass transfer limit
regime at a temperature above 0 ̊C (Lund et al., 1975). In contrast, the
dolomitic rock dissolution by HCl, as described by equation (2) is re­
action rate limited under 50 ◦ C (Lund et al., 1973) as the reactant
transport is faster than the reaction rate. The reaction of acid-rock can be
defined by three steps as follows (Lund et al., 1973):
(1) The hydrogen ions transportation from the acid fluids to the
surface of the rock.
(2) The reaction at the surface of the rock.
(3) The reaction products transportation from the surface of the rock
to the acid fluids
There are many factors that distinct carbonate rocks such as depo­
sitional environment, rock structure, or diagenesis (Embry and Klovan,
1971). Diagenesis plays a major role in alternating the pore structure
and pathways for fluid to flow. In general, the porosities of carbonate
rocks are either connected porosity, vugs, or fracture porosity. For
effective well stimulation, it is essential to consider this variation in
porosities which constitute a complex pathway for the reactive fluid to
flow and ultimately affect the outcome of the acidizing flooding (Akbar
et al., 2000; Dasgupta and Mukherjee, 2020). Intensive research has
been conducted in the literature to define the parameters that affect acid
treatment and found to be mainly injection rate, acid concentration and
temperature. Mahmoud et al. (2017) performed experiments to study
the effect of changing the injection rate on the stimulation process. The
objective of his study was to identify the optimum injection rate by
assessing the wormholes’ configurations. Their study concluded that the
optimum injection rate resulted in dominant wormholes, which were
narrow combined with short lengths branches. The authors also
analyzed the temperature effect on the stimulation process. They found
that dominant wormholes require more stimulation fluids at low tem­
peratures. Their statement agrees with Cikes et al. (1990), who stated
that an increase in temperature will result in an increase in reaction rate
and hence a reduction in the required stimulation fluid for the wormhole
to breakthrough. Mahmoud et al. (2017) also analyzed the effect of
using various acid concentration on wormhole development. They
concluded that there is an optimum acidic concentration where
above/below that value more stimulation fluid is required for worm­
holes to breakthrough at the outlet face of the rock sample at the same
conditions.
2.2. Physics-based characterization of wormhole formation in carbonates
In fluid mechanics, physics-based characterization of fluids flow
through porous media is conveniently described by dimensionless
numbers. This approach has allowed accurate modelling of fundamental
regimes of fluid and heat flow in many engineering applications mini­
mizing the necessary degrees of freedom that are considered irrespective
of the type of porous medium considered. For reactive flow, the major
numbers that govern the reactive fluid flow throughout matrix acidizing
are expected to be the Damkhöler and Péclet numbers. Hoefner and
Fogler (1988) assessed the reaction of HCl with carbonate rocks and
concluded that the wormhole formation phenomenon is controlled by
H. Al-Arji et al.
Damkhöler ‘s number. Damkhöler number (Da) is defined as the ratio of
dissolution rate to the acid injection rate (Fredd and Scott Fogler, 1998):
L
Da = aDe 3 *( ) (3)
2
q
where L (cm) is the core sample length,
De is the effective diffusion coefficient (cm2 /s), q is the injection flow
rate (cm3/s), and a is a constant depends on the rock sample. Péclet
number (Pe) is defined as the ratio of the convection to the diffusion rate
of a specific fluid (Frick et al., 1994; Mahmoud et al., 2017) and can be
described by:
√̅̅̅
q k
Pe = (4)
ADe
where q is the injection flow rate (cm3/s), k is the rock permeability
(cm2), A is the rock cross-section area (cm2), and De is the effective
diffusion coefficient (cm2/s).
Hoefner et al. (1987) demonstrated that wormholes are being
created due to the quick, mass transfer limited and nearly entire disso­
lution of the minerals in the reactive fluid (HCl). Another factor of the
wormhole formation is the diversity of pore-scale flow rates induced by
carbonate rock heterogeneity, which causes some pores to encounter
larger acid volume and thus run into rapid dissolution. Fredd and Fogler
(1998) described the wormhole formation progression throughout
acidizing treatment, where the reactive fluid favourably drifts to the
highest permeability districts. These early flow pathways are grown
through the accelerated matrix dissolution, triggering more flow to be
received by these regions. A dominant route rapidly establishes and
spreads during the contributed flow by other districts. Once established,
the wormhole pathways offer negligible flow resistance and effectively
import the entire injected fluid.
Several studies have revealed that the formation of wormholes pri­
marily depends on the reactive fluid concentration, injection rate,
temperature, and rock mineralogy (Fredd, 2000; Fredd et al., 2017).
Rock dissolution structures shaped during carbonate acidizing treatment
by the reactive fluid are illustrated by Fredd et al. (2017). Referring to
Fig. 1 in Fredd et al. (2017), the major types of rock dissolution struc­
tures can be summarized as face dissolution, conical wormhole, domi­
nant wormhole, ramified wormhole, and uniform dissolution. The rock
dissolution structures are highly affected by the injection rate. They vary
from face dissolution at low injection rate or high Damköhler number
(Da) to uniform dissolution at high injection rate or low Damköhler
number (Da). At a low injection rate, the acid is spent on the core sample
inlet surface, leading to face dissolution with minimal penetration
depth. At a moderate injection rate, the acid penetrates more and mostly
be spent on the wall of the pathways leading to the creation of a conical
wormhole. When increasing the injection rate to somewhat intermedi­
ate, the acid is carried toward the tip of the developing pathway, where
Fig. 1. Mount Gambier rock sample.
3
Journal of Petroleum Science and Engineering 203 (2021) 108593
the reaction elongates the length of the pathway and forms a single
dominated wormhole channel. At a high injection rate, the acid propa­
gates deeper into the smaller pore of the core sample, and the flow
channel results in more branched or ramified wormholes as the required
fluid volume is increased. At an extremely high injection rate, the acid is
carried to most pores in the core sample resulting in uniform dissolution
and insufficient carbonate stimulation.
The significance of acid stimulation was noted through a minimum
of injected pore volume required for wormhole breakthrough related to
variations in the Damköhler numbers (Hoefner and Fogler, 1988). The
type of rock dissolution structures controls the acid volume essential for
achieving a certain depth of channel penetration. There is an optimum
injection rate of all the fluids where a dominant wormhole channel
structures are created at minimum pore volumes. Consequently, there is
an ideal Damköhler number (Da) where minimal injected pore volumes
are needed for the dominant wormhole to breakthrough.
2.3. Rock dissolution structures as a function of Péclet and Damköhler
numbers
Szymczak and Ladd (2004) studied the dissolution of artificial frac­
tures numerically to examine the effect of flow rate described through
Péclet number, mineral dissolution rate described through Damköhler
number, and fracture geometrical properties. Moreover, Szymczak and
Ladd (2004) investigated the dissolution of the lower fracture surface
under a constant injection rate and pressure drop conditions for various
Péclet and Damköhler numbers. Fig. 6 in (Szymczak & Ladd, 2009)
shows a phase diagram that summarizes the outcomes of their numerical
model, which illustrates dissolution structures as a function of Péclet
and Damkhöler’s number. There are three regions in the phase diagram:
surface inundation (face dissolution) at the bottom, wormholes at the
middle, and uniform dissolution at the top. For small Péclet number and
large Damköhler number, the reactant fluid soaks the nearby injection
face. The reaction front spreads enormously slowly after a quick early
dissolution of the porous medium at the fluid inlet and results in face
dissolution. However, in the case of a high injection flow rate (Pe >
500), or low reaction rate (Da < 1/100), the reactant penetrates through
small pores, and the entire sample dissolves uniformly. Wormhole
structure is noted at intermediate values of Péclet and Damkhöler ‘s
number, approximately around Pe ~10 and Da > 1/100 (Szymczak &
Ladd, 2009).
Researchers have focused on achieving optimum conditions for
wormhole propagation based on the injection rate and minimum volume
required for a breakthrough without accounting for the physics aspect of
the wormhole phenomenon. However, a deeper understanding of the
physics beyond wormhole initiation and propagation is essential in
defining effective stimulation efficiency. To achieve that, we test a
numerically based idealized parameterization on just two non-
H. Al-Arji et al. Journal of Petroleum Science and Engineering 203 (2021) 108593

dimensional numbers (Damköhler and Péclet) in a systematically Table 2

controlled laboratory experiment. In addition, to ensure the reliability of Elemental composition (in wt% oxides) of Mount
our approach, we tested the critical point of the wormhole initiation in a Gambier limestone using XRF.
difficult range such that the wormholing domain is rarely achieved. Chemical Formula Oxide wt%

SiO2 0.64
3. Methods TiO2 0.01
Al2O3 0.17
3.1. Core samples Fe2O3 0.24
Mn3O4 0.01
MgO 0.49
Mount Gambier limestone core samples with 2.5 cm in diameter and CaO 55.41
5 cm long were used in this study (Fig. 1). To test the hypothesis that the LOI 43.5
flow of acidized fluid in a porous medium can be characterized by just
two significant dimensionless numbers, a highly porous rock with an
drop across the core sample, an Omega pressure transducer was utilized.
average of 51% porosity and 1600 md was used. The rationale for using
The production section composes of a glass production outlet beaker to
extreme end-member porosity samples for testing the prediction of the
collect the produced effluent sample. All samples were saturated with
critical point of the wormholing phenomenon is to obtain repeatable
de-ionized water prior-to the acid stimulation and flooded with the de-
results in a safe domain for testing the postulated physics. Owing to the
ionized water to calculate the absolute permeability prior-to acid
high porosity, our tested limestone is far away from the percolation
flooding experiments.
threshold and sufficient randomly distributed pathways exist in the
sample. In terms of physical mechanisms, we, therefore, aim at testing
the hydro-chemical coupling without interference from hydro- 3.3. Procedure
mechanical effects which may require consideration of additional
physics. These hydro-mechanical couplings may appear during The effect of injection rates and HCl-concentrations on the wormhole
wormholing experiments for tighter samples that are closer to the formation was investigated using Mount Gambier limestone rocks. The
percolation threshold. An additional motivation was to obtain a high core flooding experiments were carried out at three HCl-concentrations;
sensitivity of detection critical points and test the model in conditions 1, 3, 5 wt% HCl. To identify the effect of flow rate on wormhole for­
where wormholing is rarely achieved. We, therefore, seek to verify/ mation, the injection rate was increased at each HCl-concentration until
falsify the hydro-chemical model for the extremely porous, highly a wormhole breakthrough is observed at the outlet face of the core
permeable end-members. This physics-based approach intends to pro­ sample. High-resolution microscopic images (up to 10μm) of the rock
vide the foundations for the application of additional experiments that samples’ outlet face were collected to confirm the wormhole develop­
closely replicate natural engineering applications under laboratory ment throughout the experiments (Fig. 3). All experiments were con­
conditions. Conventionally, physics-based models are only tested for the ducted using Mount Gambier limestone at ambient conditions. The
simplified conditions that they are designed and are not intended to normalized pressure drop was calculated by dividing the instant pres­
incorporate the complexity of a real specific engineering application. sure by the initial pressure drop, as described by equation (5):
They are often validated in similar idealized laboratory conditions or by P ins
numerical studies. The rationale for developing such physics-based NPD = (5)
P initial
models is an attempt to understand the main controlling factors for
critical point phenomena, such as the wormhole instability observed in NPD = Normalized pressure-drop.
nature. Engineering approaches come from a completely different angle P ins = instant pressure, psi.
and attempt at describing the phenomenon most accurately with the P initial = Initial pressure, psi.
tools of mathematics to capture the complexity of the behaviour of real Fig. 4 demonstrates the normalized pressure of the acidizing process
rocks. Both approaches together allow robust extrapolations for the for the samples that ended up with wormholes breaking through at their
postulated hydro-chemical processes. outlet face. Fig. 5 illustrates the normalized pressure for the samples
The mineral and element composition of Mount Gambier limestone where wormholes were not observed.
rock are shown in Table-1 and 2. The samples’ rock properties and
acidizing conditions are summarized in Table-3. 3.4. Experiments protocol

All experiments were conducted at ambient conditions (no back-

3.2. Experimental setup
pressure) to establish a baseline for the parameters that affect the
wormhole growth. We noticed in our experiments that there is an effect
Fig. 2 presents a schematic diagram of the experimental setup. In this
of back pressure on the acid distribution within the treated core. Most
method, the core-flooding configuration was designed to be compatible
importantly, back pressure has an effect on the bubble formation near
with hydrochloric acid solutions. A dual syringe pump with a dispensing
the outlet of the core, especially at low pressures. The objective of our
accuracy of ±1% was used to inject acid solutions. Two 60 ml syringes
work was to test the theoretical model of Szymczak and Ladd (2004)
were mounted on the dual pump. 1/16-inch Polyetheretherketone
which only considered single-phase flow. This two-phase flow problem
(PEEK) tubing was used as a flow line. A manual water pump was
was beyond the scope of the original work. We, therefore, chose to test
mounted to provide the necessary confining pressure. The confining
the model as a base-line without applying back pressure. The rationale
pressure applied in this research was 500 psi. To measure the pressure
for not suppressing the physics of bubble formation in a real case test
scenario was to falsify the original model by overlooking the potentially
Table 1 important physics of bubble formation. In future work discussed later
XRD result for Mount Gambier rock sample.
on, we propose to investigate the effect of bubble formation through
Rock Sample Mineral Composition comparison to experiments that apply systematically varying negative
Mount Gambier limestone 96.0%, Calcite (CaCO3) and positive back pressure (1000 psi). The investigation of phase tran­
2.3%, Quartz (SiO2) sitions and hydro-mechanical coupling, including the effect of bubble
1.2%, Magnesite (MgCO3) formation on the percolation of CO2 multiphase solutions are out of
0.4%, Magnetite (Fe3O4)
scope for this suite of experiments. The first set of experiments were

4
H. Al-Arji et al. Journal of Petroleum Science and Engineering 203 (2021) 108593

Table 3
Rock properties and acidizing conditions of the core samples.
SAMPLE # DIAMETER LENGTH DRY WEIGHT WET WEIGHT PORE VOLUME BULK VOLUME POROSITY KA HCL RATE

cm cm g g cc cc % md wt% ml/min

1 2.5 5.0 30 43 13 25 52 1810 5 10

2 2.5 5.1 31 43 13 25 51 1822 5 2
3 2.5 5.0 30 43 13 25 51 1951 5 5
4 2.5 5.1 31 44 13 25 50 1910 3 10
5 2.5 5.1 31 44 13 25 51 1479 3 5
6 2.5 5.0 31 44 13 25 51 1761 3 7
7 2.4 5.0 29 41 12 23 51 1600 1 5
8 2.5 5.1 31 44 13 25 51 1210 1 10
9 2.5 5.1 31 44 13 25 51 1792 1 20

Fig. 2. Setup of the core flooding experiment.

conducted at a fixed HCl-concentration of 5 wt% HCl and injection rates
were varied at 10, 5, and 2 ml/min using samples#1, 3 and 2, respec­
tively. The second set of experiments were conducted with a fixed
HCl-concentration of 3 wt% HCl, and the injection rates were varied at
10, 7, and 5 ml/min using samples#4, 6 and 5, respectively. Finally, the
last set of experiments were run at a fixed HCl-concentration of 1 wt%
HCl and injected at several flow rates: 20, 10, and 5 ml/min using
samples#9, 8 and 7, respectively. The objective here is to identify at
least one injection rate where a wormhole would form and another in­
jection rate where a wormhole is absent for each HCl-concentration to
validate the numerical model’s borderline of the wormhole formation.
4. Results and discussion
4.1. HCl-concentration fixed at 5%
Three injection rates were used at 5 wt% HCl; 10, 5 and 2 cc/min.
Injection rates of 10 and 5 ml/min using samples#1 and 3, respectively,
resulted in a wormhole formation (Fig. 3(a,c)). A build-up pressure at
the beginning of the acidizing process was observed and then a sharp
decrease in the pressure after injecting five pore volumes (PVs) for both
samples (Fig. 4), which indicates a wormhole breakthrough. The pres­
sure profile is consistent with the results obtained by (Mahmoud et, al
2017). The increase in pressure is attributed to the significant increase in
the production of fines released by the dissolution and calcite particles
that clogs the pore throats (Qajar, 2012). Moreover, since the reference
experiments were conducted at ambient conditions, CO2 is evolved into
a gaseous phase at the outlet, which may potentially increase resistance
to flow and hence increase the pressure prior to breakthrough (Cheng
et al., 2017; Muhemmed et al., 2020). After the wormhole breakthrough,
the pressure decreases sharply, indicating a complete connected path
that links the inlet to the outlet face of the core sample resulting in
almost no resistance to flow.
In the case when the injection rate was decreased to 2 ml/min
(Sample#2), no wormhole was observed. Sample#2 showed a different
pressure trend (Fig. 5) compared to samples#1 and 3, where the pres­
sure increased at the beginning of the acidizing process then stabilized
throughout the experiment. Therefore, after injecting seven PVs, the
experiment was terminated.
4.2. HCl-concentration fixed at 3%
When reducing the HCl-concentration to 3%, a wormhole was
developed only at an injection rate of 10 ml/min using sample#4 (Fig. 3
(d)), where no wormholes were confirmed at 5 and 7 ml/min for sam­
ples# 5 and 6, respectively. The normalized pressure of sample#4 also
indicated a wormhole breakthrough where the pressure increased at the
beginning of the acidizing process (Fig. 4) and then decreased after
injecting 4.5 PVs. As for samples#5 and 6, the pressure trend was
consistent with the samples that did not develop a wormhole where the
pressure increased at the beginning of the acidizing process then stabi­
lized till the end of the tests (Fig. 5). Consequently, the experiments were
terminated after injecting 7 PVs.
4.3. HCl-concentration fixed at 1%
When further reducing the HCl-concentration to 1%, a wormhole
was showing only at a high injection rate of 20 ml/min using sample#9
(Fig. 3(i)). This confirms that HCl-concentration plays a major role in
defining the wormhole initiation conditions. Sample#7 and 8 with in­
jection rates of 5 and 10 ml/min did not result in a wormhole Fig. 3(g
and h). The normalized pressure of sample#9 also shows a similar
pressure trend to sample#1, 3 and 4, where a pressure build-up was
noticed at the beginning of the acidizing process (Fig. 4) and then a

5
H. Al-Arji et al. Journal of Petroleum Science and Engineering 203 (2021) 108593

Fig. 3. Microscopic images of wormhole breakthrough from the outlet face of Mount Gambier limestone samples.

Fig. 4. Normalized pressure drop for samples with wormholes.

sharp decrease in the pressure after injecting 3.5 PV. On the other hand,
the pressure of sample#7 and 8 increased at the beginning of the acid­
izing process and then stabilized throughout the experiment process
(Fig. 5) similar to sample#2, 5 and 6 pressures trend. As a result, the
experiments were terminated after injecting seven PVs.
Table-4 shows a summary of all experimental runs. At each HCl-
concentration, the injection rate was varied until a wormhole was
observed. All samples that resulted in wormholes showed a pressure
decline in less than 5 PVs. On the other hand, all samples that did not
result in a wormhole have not shown any signs of pressure decline even
after injecting 7 PVs, which is taken as indirect evidence of wormhole
breakthrough if there was any, and accordingly, the experiments were
terminated. This indirect evidence was confirmed by the microscopic
imaging showing that no wormholes exist.
It can be seen from Fig. 6 that there is a direct relationship between
HCl-concentration and injection rates. The results of this set of experi­
ments indicate that higher HCl-concentration requires less injection rate
to initiate the wormhole. For example, at an injection rate of 5 cc/min,
we could not achieve the wormhole at either 1 or 3 wt% HCl. However,
when we increased the HCl-concentration up to 5%, we managed to

6
H. Al-Arji et al. Journal of Petroleum Science and Engineering 203 (2021) 108593

Fig. 5. Normalized pressure drop for samples with no wormholes.

by an implicit lattice Boltzmann method, and a random walk algorithm

Table 4
was used to model the transport of dissolved species, which effectively
Experiments’ runs summary.
integrates the chemical kinetics at the solid surfaces. Our experiments
HCL SAMPLE RATE WORMHOLE confirm the reliability of using the phase dissolution plot as a prediction
WT % # ml/min Y/N tool for wormhole formation in single-phase hydro-chemically coupled
5 1 10 Y
acid stimulations. Fig. 7 shows a phase diagram of three different areas
2 2 N that describe the behaviour of rock dissolution structures: surface
3 5 Y inundation (face dissolution), wormholes, and uniform dissolution
3 4 10 Y pattern. Four samples fell into the wormhole region, whereas five
5 5 N
samples fell into the face dissolution region. The results show that
6 7 N
1 7 5 N wormholes are observed for Péclet and Damköhler numbers at Pe > 0.1
8 10 N and 1/10> Da > 1/40 as have been seen in samples#1, 3, 4 and 9.
9 20 Y In this paper, we have tested the wormhole formation boundaries
using a phase diagram by plotting two dimensionless numbers namely,
Damköhler and Péclet numbers. We have studied the effect of HCl-
concentrations at different injection rates through highly porous car­
bonate samples. Microscopic images of core samples were taken to
assess the wormhole evolution throughout the experiments. This
allowed us to test the hypothesis that the flow of single-phase acidized
fluid in a porous medium can be defined by just two significant
dimensionless numbers that govern the stimulation fluids flow
throughout the rock matrix. These are the Damköhler and Péclet
dimensionless numbers. In this study, the effect of injecting hydrochloric
acid (HCl) solution is tested for a wide range of acid concentrations and
different injection rates through carbonate rocks. Damköhler and Péclet
dimensionless numbers are calculated and plotted to identify different
dissolution patterns. It is worth mentioning that, as can be seen from
Fig. 7, two dissolution patterns (namely face dissolution and wormhole)
Fig. 6. The relationship between injection rate versus HCl concentration.
can be obtained and validated through the laboratory approach as they
require either low or moderate injection rates, however, a uniform
observe the wormhole. Also, at an injection rate of 10 cc/min, we could
dissolution pattern can only be achieved at a very high injection rate
not observe the wormhole at 1 wt% HCl, however, when increased the
which is difficult to achieve in the laboratory. The simple phase disso­
HCl-concentration up to 3 wt% HCl, we managed to observe the
lution diagram based on these two numbers was found to capture the
wormhole. These results confirm the relationship between the injection
wormhole formation region for highly porous carbonate rocks. How­
rate and HCl-concentration and that for every injection rate, there exists
ever, a tight carbonate rock needs to be tested to assess whether addi­
a critical HCl-concentration that at or above this value, the wormhole
tional factors need to be considered. In such samples, the potential
starts to develop.
inclusion of hydro-fractures as a new physics phenomenon needs to also
To better understand acid transportation in the rock matrix and
be considered.
predict the creation of wormholes, Damköhler, and Péclet dimensionless
numbers were calculated for each experiment. The effective diffusion
coefficient used in this study was obtained from (Taylor et al., 2003) 5. Conclusion
study. For example, at 1 wt% HCl, the effective diffusion was found to be
Our study clearly documented that the theory of Szymczak and Ladd
3.1 × 10− 5 cm2 /sec. The result was plotted against (Szymczak and Ladd,
(2009) is valid for the investigated end-member high porosity Mount
2009) numerically constructed phase dissolution plot. In their model,
Gambier rock. The study found that wormhole formation of Mount
the fracture space is defined by two-dimensional height profiles repre­
Gambier rock is observed for Péclet and Damköhler numbers at Pe > 0.1
senting the upper and lower fracture surfaces. The velocity is calculated
and 1/10> Da > 1/40 as expected from the theory. In addition to the

7
H. Al-Arji et al.
Fig. 7. Phase dissolution diagram of Mount Gambier samples using the two dimesnssionless numbers Da and Pe against (Szymczak and Ladd, 2009) phase dissolution
diagram borders.
confirmation of the basic theory, the following observations were made:
• In general, the pressure tends to increase in case of wormhole for­
mation and then decreases to almost zero psi, indicating a dominant
wormhole that connects both ends of the core sample.
• The increase in pressure is attributed to the fines migration released
by the dissolution and calcite particles that clogs the pore throats,
and the evolved gaseous CO2 phase (due to conducting experiments
at ambient conditions) which may potentially increase resistance to
flow and hence increase the pressure drop.
• All samples that resulted in a wormhole breakthrough required
4–6.5 PVs for the wormhole to breakthrough and reach a near-zero
pressure value.
• In contrast, all samples that did not result in a wormhole have not
shown any signs of pressure decline even after injecting 7 PVs, which
is taken as indirect evidence of wormhole breakthrough if there was
any, and consequently, the experiments were terminated. This in­
direct evidence was confirmed by the microscopic imaging showing
that no wormholes exist.
Our results were compared with the phase diagram proposed by
Szymczak and Ladd (2009) and showed excellent agreement. The result
confirmed that the critical point for dissolution pattern formation
including the wormholes phenomenon can be fully captured by a
domain diagram of inverse Damköhler versus Péclet number as pre­
dicted by the theoretical numerical model. Our experimental results on
highly porous limestones validated the numerically constructed phase
diagram.
This research outcome is recommended to be applied to reliably
predict the wormholes initiation under different operation conditions,
namely injection rate and HCl concentration. Experiments with back­
pressure >1000 psi are necessary to keep the CO2 in solution to identify
the effect of the evolved CO2 on the experiments’ outcome and to be
compared with the obtained results. Finally, a different rock type with
lower porosity and permeability needs to be performed to identify the
effect of varying microstructure on the wormhole development region.
Credit author statement
Hamad Alarji: Methodology, Lab work, Result and Discussion,
Validation, Writing – original draft, Abdulaziz Al-Azman: Lab work
(Experiment set-up), rock samples, Furqan Le-Hussain: Helped in
designing the experiment set-up, results and analysis, manuscript
Reviewing and Editing, Klaus Regenauer-Lieb: Conceptualization,
8
Journal of Petroleum Science and Engineering 203 (2021) 108593
Supervision, Writing-Reviewing and Editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors would like to thank the management of the School of
Minerals and Energy Resources Engineering at UNSW and the office of
the Vice-Chancellor Research for supporting the laboratory studies. This
work was funded through the strategic SPF01 fund of UNSW.
References
Akbar, M., Chakravorty, S., Middle, S., Russell, S.D., Deeb, M.A.A.I., Adco, R.S.E.-,
Thower, R., Adma-opco, H.K.-, Mohamed, S.S., Mohamed, N., Zadco, B.-., 2000.
Unconventional Approach to Resolving Primary and Secondary Porosity in Gulf
Carbonates from Conventional Logs and Borehole Images, 1996.
Buijse, M.A., Glasbergen, G., 2005. SPE 96892 A Semiempirical Model to Calculate
Wormhole Growth in Carbonate Acidizing. In: SPE Annual Technical Conference and
Exhibition. https://doi.org/10.2118/96892-ms.
Cheng, H., Zhu, D., Hill, A.D., 2017. The effect of evolved CO2 on wormhole propagation
in carbonate Acidizing. SPE Prod. Oper. 32 (3), 325–332. https://doi.org/10.2118/
178962-pa.
Cikes, M., VranJeaevlc, B., Tomlc, M., Jamnlcky, O., 1990. A Successful Treatment of
Formation Damage Caused by High-Density Brine, 2009, 2017.
Daccord, G., Lenormand, R., 1993. Chemical dissolution of A porous medium by A
reactive fluid-ii. Convection vs reaction, behavior diagram. Chem. Eng. Sci. 48. Issue
I).
Dasgupta, T., Mukherjee, S., 2020. Porosity in carbonates. Adv. Oil Gas Explor. Product.
January 9–18. https://doi.org/10.1007/978-3-030-13442-6_2.
Embry, A.F., Klovan, E.J., 1971. The upper devonian stratigraphy of northeastern banlts
island has. Bull. Can. Petrol. Geol. 19 (4), 730–781.
Frasch, H., 1896. Increasing the flow of oil wells. Patent No. US, 556, 669. Patent No.
Fredd, C., Fogler, H., 1999. Optimum conditions for wormhole formation in carbonate
porous media: influence of transport and reaction. SPE J. 4 (3), 196–205. https://
doi.org/10.2118/56995-PA.
Fredd, C.N., 2000. Dynamic model of wormhole formation demonstrates conditions for
effective skin reduction during carbonate matrix acidizing. In: SPE Permian Basin Oil
and Gas Recovery Conference. https://doi.org/10.2118/59537-MS.
Fredd, C.N., Fogler, H.S., 1996. Alternative stimulation fluids and their impact on
carbonate acidizing. In: SPE Formation Damage Control Symposium, March, 34–41.
https://doi.org/10.2118/31074-MS.
Fredd, C.N., Fogler, H.S., 1998. Alternative stimulation fluids and their impact on
carbonate acidizing. SPE J. 3 (1), 34–41. https://doi.org/10.2118/31074-PA.
Fredd, Christopher N., Hoefner, M.L., Fogler, H.S., 2017. Microemulsion applications in
carbonate reservoir stimulation. Properties and Uses of Microemulsions. https://doi.
org/10.5772/65973.
H. Al-Arji et al.
Fredd, Christopher N., Scott Fogler, H., 1998. Influence of transport and reaction on
wormhole formation in porous media. AIChE J. 44 (9), 1933–1949. https://doi.org/
10.1002/aic.690440902.
Frenier, W.W., Frederick, T., Growcock, B., Arrow, B., 1988. Mixtures of Ag-unsaturated
aldehydes and surface active agents used as corrosion inhibitors in aqueous fluids.
Patent No. 4,734,259.
Frick, T., Mostofizadeh, B., Economides, M., 1994. Analysis of radial core experiments for
hydrochloric acid interaction with limestones. SPE Formation Damage Control
Symposium 577–592. https://doi.org/10.2118/27402-MS.
Furui, K., Burton, R.C., Burkhead, D.W., Abdelmalek, N.A., Hill, A.D., Zhu, D.,
Nozaki, M., 2012. A comprehensive model of high-rate matrix-acid stimulation for
long horizontal wells in carbonate reservoirs: Part I–Scaling up core-level acid
wormholing to field treatments. SPE J. 17 (1), 271–279. https://doi.org/10.2118/
134265-PA.
Gomaa, A.M., Nasr-El-Din, H.A., 2010. Rheological and core flood studies of gelled and
in-situ gelled acids. In: North Africa Technical Conference and Exhibition, 201024,
pp. 14–17. https://doi.org/10.2118/128056-MS.
Hoefner, M.L., Fogler, H.S., 1988. Pore evolution and channel formation during flow and
reaction in porous media. AIChE J. 34 (1), 45–54. https://doi.org/10.1002/
aic.690340107.
Hoefner, M.L., Fogler, H.S., 1989. Fluid-velocity and reaction-rate effects during
carbonate acidizing: application of network model. SPE Prod. Eng. 4 (1), 56–62.
https://doi.org/10.2118/15573-pa.
Hoefner, Mark L., Of, U., Fogler, M.H.S., 1987. Role of Acid Diffusion in Matrix Acidizing
of Carbonates.
Lund, K., Fogler, H., Mc Cune, C.C., 1973. Acidization. 1 the dissolution of dolomite in
acid hydrolic acid. Chem. Eng. Sci. 28, 691–700.
Lund, Kasper, Fogler, H.S., McCune, C.C., Ault, J.W., 1975. Acidization-II. The
dissolution of calcite in hydrochloric acid. Chem. Eng. Sci. 30 (8), 825–835. https://
doi.org/10.1016/0009-2509(75)80047-9.
Mahmoud, M., Barri, A., Elkatatny, S., 2017. Mixing chelating agents with seawater for
acid stimulation treatments in carbonate reservoirs. J. Petrol. Sci. Eng. 152
(February), 9–20. https://doi.org/10.1016/j.petrol.2017.02.005.
Masalmeh, S.K., Wei, L., Blom, C., Jing, X.D., 2014. EOR options for heterogeneous
carbonate reservoirs currently under waterflooding, 1. Society of Petroleum
Engineers, pp. 1–25.
Journal of Petroleum Science and Engineering 203 (2021) 108593
Mostofizadeh, B., Economides, M.J., 1994. Optimum injection rate from radial acidizing
experiments. In: SPE 69th Annual Technical Conference and Exhibition, New
Orleans, LA, U.S.A., pp. 327–333. https://doi.org/10.2118/28547-MS.
Muhemmed, S., Kumar, H., Nasr-El-Din, H., 2020. A three-phase study on pre-flush stage
in sandstone acidizing: experimental and modeling analysis of evolved CO2 in an oil
and aqueous environment. In: Proceedings - SPE Annual Technical Conference and
Exhibition, 2019-Septe(February), pp. 1–26. https://doi.org/10.2118/195897-ms.
Nasr-El-Din, H.A., Al-Mohammad, A.M., Al-Shurei, A.A., Merwat, N.K., Erbil, M.M.,
Samuel, M., 2006. Restoring the injectivity of water disposal wells using a
viscoelastic surfactant-based acid. J. Petrol. Sci. Eng. 54 (1–2), 10–24. https://doi.
org/10.1016/j.petrol.2006.07.001.
Pal, S., Mushtaq, M., Banat, F., Al Sumaiti, A.M., 2017. Review of surfactant-assisted
chemical enhanced oil recovery for carbonate reservoirs: challenges and future
perspectives. Petrol. Sci. 15 (1), 77–102. https://doi.org/10.1007/s12182-017-
0198-6.
Qajar, J., 2012. Reactive Flow in Carbonate Cores via Digital Core Analysis. September.
http://unsworks.unsw.edu.au/fapi/datastream/unsworks:11176/SOURCE01?
view=true.
Szymczak, Piotr, Ladd, A., 2004. Microscopic simulations of fracture dissolution.
Geophys. Res. Lett. https://doi.org/10.1029/2004GL021297.
Szymczak, P., Ladd, A.J.C., 2009. Wormhole formation in dissolving fractures.
J. Geophys. Res.: Solid Earth 114 (6), 1–22. https://doi.org/10.1029/
2008JB006122.
Tan, X., Weng, X., Cohen, C., 2016. An Improved Wormhole Propagation Model with a
Field Example, pp. 24–26.
Taylor, K.C., Al-Ghamdi, A.H., Nasr-El-Din, H.A., 2003. Measurement of acid reaction
rates of a deep dolomitic gas reservoir. In: Canadian International Petroleum
Conference 2003, CIPC 2003, 4.
Yoo, H., Kim, Y., Lee, W., Lee, J., 2018. An experimental study on acid-rock reaction
kinetics using dolomite in carbonate acidizing. J. Petrol. Sci. Eng. 168 (February),
478–494. https://doi.org/10.1016/j.petrol.2018.05.041.
Zakaria, A.S., Nasr-El-Din, H.A., 2015. Application of novel polymer assisted emulsified
acid system improves the efficiency of carbonate acidizing. SPE-173711-MS, 1–23.
In: SPE International Symposium on Oil Field Chemistry. https://doi.org/10.2118/
173711-MS.
, 69th Edition. https://www.bp.com/content/dam/bp/business-sites/en/global/cor
porate/pdfs/energy-economics/statistical-review/bp-stats-review-2020-full-report.
pdf–. (Accessed 11 January 2021).