SPE-173390-MS

Acid Fracturing Shales: Effect of Dilute Acid on Properties and Pore

Structure of Shale
Weiwei Wu, and Mukul M. Sharma, The University of Texas at Austin

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Hydraulic Fracturing Technology Conference held in The Woodlands, Texas, USA, 35 February 2015.
This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract
Many microfractures created during hydraulic fracturing are too small to be filled with proppants and are
likely closed during production. However, for some shales that are rich in calcite (calcareous mudstones),
such as the Bakken and Eagle Ford shale, dilute acids can be used while fracturing to maintain the
conductivity of these microfractures under closure stress by non-uniformly etching the fracture surfaces.
The mineralogy and pore structure of the shale and their evolution during acid fracturing are critical
factors on the surface surface etching profile and the fluid leakoff. Therefore, understanding how acid
dissolution changes the microstructure, petrophysical properties and pore structures of shale is essential
in the design and application of acid fracturing in shales.
In this paper changes in shale properties and pore structure by acid fracturing were demonstrated and
visually observed for the first time with a scanning electron microscope. Acidized sections of a shale core
sample were carefully isolated, and its microstructure, pore structure and petrophysical properties were
systematically studied and compared with non-acidized sections of the core.
Microstructure changes were found to be strongly dependent on mineral distribution, and several
patterns were identified: channels developed in carbonate-rich regions; cavities or grooves formed in
carbonate-rich islands or carbonate rings; and surface roughness was created in mixed zones of scattered
carbonate and inert minerals. Inert minerals such as clay, organic matter stay relatively undisturbed in the
structure, while some mineral grains can be dislodged from their original locations by dissolution of the
surrounding carbonates. Many macropores with size up to 120 m were created and mesopores mostly
associated with clay gained more accessibility. Significantly increased permeability and porosity was
measured in an acidized shale matrix. Brinell hardness measurements show that, as expected, the hardness
of the shale was reduced by acidizing. This means that for acidizing to work effectively, it is important
to not etch the fracture surfaces uniformly. Doing so will result in a reduction in the fracture conductivity
under stress. The microstructure changes introduced by acid fracturing demonstrated in this study will
result in the formation of surface asperities which is likely to improve the fracture conductivity of induced
unpropped fractures. The acidized shale matrix close to the fracture surface with increased abundance of
macropores and accessibility to mesopores may serve as a preferred pathway for fluid flow as well.

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Figure 1Schematic of acid fracturing shale.

Introduction
Production in shale has been revolutionized and significantly enhanced by hydraulic fracturing which
involves the injection of large volumes of fluid and proppants into fractures in the formation. These
hydraulic fractures are usually filled with proppants (propped-fractures) in order to stay conductive when
subjected to a closure stress. Hydraulic fracturing also creates many microfractures (Fig.1), which can be
pre-existing natural fractures or induced unpropped (IU) fractures branching from the main propped
fractures (Fisher et al. 2005; Gale et al. 2007; Gasparrini et al. 2014; Manchanda et al, 2014). However,
these microfractures at reservoir depth are estimated to have width ranging from of 101 to 106 cm, and
105 to 106 cm for natural factures in shale (Nelson 2001). They are too small to be accessed by most
common proppants used, such as 40 70 or 100 mesh sand.
Microfractures thus are likely to be closed during production, and considerable productivity may be lost
given that these microfractures contribute in a substantial way to the production. Their contribution to
production is evident from the fact that to history match the production response of shale oil and gas wells,
it is always necessary to introduce a stimulated rock volume, a region of high permeability around the
main propped fracture (SRV), to get a good match. Microseismic mapping also shows that shear failure
events usually occur both near and some distance away from the propped fracture. The increase in
permeability in the SRV is a direct result of the creation of IU fractures in the rock. Manchanda and
Sharma (2012) have shown that over time, as the well is produced and fluid leaks off from the IU
fractures, their width and conductivity goes to near zero. This loss in a large portion of the created fracture
area can reduce the well productivity unless a way can be found to keep these unpropped fractures and
microfractures open.
The use of acid is one possible method of accomplishing this objective. As contrasted with proppants,
acid does not have any physical restriction in accessing microfractures. If fractures were etched nonuniformly by selectively dissolving carbonate minerals from channels created on the fracture faces or
through acid penetration along bedding planes or planes of weakness, the well productivity would
continue to benefit from the fluid pathways provided by the acid etched micro-fractures even after fracture
closure. Therefore, acid fracturing can be a potential solution to improve the productivity of microfractures in a carbonate-rich shale.
The fracture surface etching profile and the extent of leakoff are two critical factors that control the
effectiveness of acid fracturing. The surface etched profile determines the geometry and conductivity of
the etched fractures, while the leakoff controls the depth of penetration of the acid into the fracture. In
carbonate formations, due to the relatively permeable matrix (permeability can reach mD) and the

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dominance of reactive minerals (over 99 wt% calcite), the surface etching profile and leakoff are mainly
controlled by acid diffusion to the mineral surface, acid reaction kinetics and convection of acid in fracture
and matrix (Hoefner and Fogler 1988; Mou et al.2007; Oeth et al. 2014). Etching patterns, channels, or
roughness are developed and etched fracture half widths range from 1 to 5 mm (Ruffet et al.1998; Dong
et al.1999; Nieto et al. 2008; Pournik et al. 2009). Leakoff acid can create wormholes of various widths
from 1 to 16 mm into the surrounding matrix depending on the leakoff rate (Hoefner and Fogler 1988).
Unlike carbonates, many calcareous shales contain only a modest percentage of carbonate minerals, a
much lower permeability (nD to D level) and have a very different pore structure (Nelson 2009;
Sondergeld et aj. 2010; Loucks et al. 2012). The surface etching profile and leakoff in shales is, therefore,
expected to be highly dependent on the distribution of reactive minerals and the accessibility of of these
minerals to the acid. This is controlled by the microstructures and pore structure of the shale and its
evolution during acid fracturing. The conductivity of etched fractures in shale was found to be three or
four orders of magnitude lower than that in carbonates at the same closure stress (Tripathi and Pournik
2014). The etched fracture half-width in a shale is expected to be in the range of 10-100 m. Therefore,
before designing and applying acid fracturing in shale, it is important to understand how acid fracturing
affects the pore structure of shale, an issue that has not been addressed by previous studies. What kinds
of structure or surface pattern can develop when carbonate minerals are dissolved? How would acid
fracturing affect minerals like clay, quartz and organic matter that are present in high abudance in a shale
but do not react with acid? How would the pores structure change in acid fracturing? These and other
related questions are addressed in this paper.
In this work, we chose Bakken shale (which has high carbonate content) to study the effects of acid
fracturing on its microstructure and pore structure. We first performed an in-situ study in which the
microstructures and pore structures in representative areas were observed with field-emission scanning
electron microscope (FE-SEM) using pre- and post-acidized shale samples. These images can directly be
compared. We then identified and isolated the acidized zone of a shale core sample through which acid
had been flowed under a pressure gradient, and characterized its microstructure and pore structure as well
as petrophysical properties.

Experimental Stduies
Mineralogy and Acid Solubility Tests.
Preserved core from the Bakken shale was used in this study, and its mineralogy was measured with X-ray
diffraction (XRD). Acid solubility tests were also conducted to evaluate the acidizing potential of the
shale. Samples were first ground to powder and filtered through a sieve (102 m), then dried at 105 C
for 24 hr. Pulverization ensures that most parts of samples are accessible to acid. A known amount of dried
powder shale (around 0.5 g) was then mixed with 50ml of 3 wt% HCl in 3wt% KCl and stirred in a sealed
container under ambient temperature (25 C) for 24 hr. At several time points, 2 ml mixture of solid
powder and solution was sampled and filtered to collect the liquid phase to measure dissolved minerals
by inductively coupled plasma mass spectrometry (ICP-MS); at the same time, another 2 ml mixture was
filtered through a pre-weighed 0.45 m filter paper then dried for 24 hr at 105 C to measure the solid
concentration for monitoring weight loss. To quantify the weight loss caused by acidizing, solubility in
3 wt% KCl was also measured under the same conditions as a control.
In-Situ Microstructure and Pore Structure Study.
Shale microstructures and pore structure at the same location pre- and post-acidizing were visually
compared with FE-SEM. Small sections of preserved Bakken shale were first cut from core samples and
rinsed with hexane to remove residual oil on their surface; the sections were then polished and milled by
broad ion-beam milling (Leica EM TIC020 mill) to prepare the surface for SEM imaging. Milling was
performed with argon-ions at an accelerating voltage of 8 kV and a sample current of 2.8 mA for 10 hr,

SPE-173390-MS

producing a milled area of approximate 1000 m x

1500 m, which was big enough to sample a representative area for imaging (Fig. 2). A 6 8 nm
layer of iridium coating for conductive purpose was
then applied to the milled surface before imaging on
the FEI Nova Nano SEM 430. All samples were
observed using both secondary electron and back
scattered electron (BSE) mode. Elements mapping
was performed through Bruker XFlash silicon drift
energy dispersive spectroscopy (EDS) detectors.
When observing pre-acidizing samples, relative coordinates and markers for image field of representative area were recorded for relocation purpose in
Figure 2Broad ion-beam milling process prepares surface for SEM
the following imaging process.
imaging. Sample above the mask is milled from one side by ion beams.
After observations on pre-acidizing samples was Milled area is usually around 1000 m x 1500 m. Original photo was
complete, the conductive coating was removed by obtained at http://www.leica-microsystems.com/.
ion-beam milling for 1 hr stepwise until the removal
of coating was visually confirmed. Then 2 drops of
1 wt% HCl (around 0.5 ml) was applied on the
milled surface for 1 min and then rinsed off with
distilled water at ambient temperature. The microstructure and pore structure of the acidized sample
was first observed under low-vapor detection
(LVD) mode without coating to avoid potential
effects of coating on microstructures. Image fields
that were previously observed in the pre-acidizing
sample were relocated by the relative coordinate
and markers recorded in the previous step. The
sample was then coated with iridium for regular
SEM imaging and elements mapping. The flowchart
for the microstructural study is shown in (Fig. 3).
Acid Penetration Test.
A shale sample of 1.5 inch core or 1.25 inch square
was cast with epoxy in a plastic column of 2.5 inch
Figure 3Workflow for in-situ microstructure study.
inner diameter at 60 psi, and the epoxy was left to
cure for three weeks before being sliced into disks
of 0.25-inch thickness. The preparation process has been described in more detail in the past and details
can be found in a previous study (Al-Bazali et al. 2006). Once the disk sample is ready, it was loaded into
an in-house acidizing cell (Fig. 4). 3 wt% HCl in 3 wt% KCl was continuously pumped into the upstream
chamber at 20ml/min. Most acid flowed past the shale surface through the back pressure regulator, while
the rest penetrated into the shale sample and entered the downstream chamber as permeate. A differential
pressure of 100 to120 psi was used between the upstream and downstream chambers to force the acid
through the sample. The breakthrough time for the acid was at around 40 hr. Epoxy used for casting the
sample was subjected to acid penetration under the aforementioned conditions for 24 hr, and negligible
penetration through epoxy was observed.
The acidized disk sample was scanned by two rounds of micro CT scan at resolution of 47.24 m/voxel
and 5 m/voxel, and the acidized portion of the sample was then carefully sectioned and isolated from

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Table 1Mineralogy of Bakken shale measured by XRD.

Minerals

Wt %

Calcite
Dolomite
Kaolinite
Illite
Quartz
Others

10.19
13.57
6.75
15.66
27.38
26.44

Figure 4 Schematic of acidizing cell for acid penetration test. Shale

disk embedded in epoxy is clamped between upstream and downstream
chambers. Acid flows into upstream chamber and exits partly through a
bypass line controlled by a back pressure regulator, and partly as
permeate which penetrates through shale and enters the downstream
chamber.

the rest of the sample. The microstructure and pore

structure in the acidized portion of the sample was
imaged using FE-SEM. The isolated acidized sample and pre-acidizing sample were also used for
5Weight loss of minerals of different minerals from Bakken
mercury intrusion porosimetry (MIP, Micromeritics Figure
shale in an acid solubility test at ambient temperature over a period of
AutoPore III analyzer) and nitrogen adsorption (Mi- 24 hours. Weight loss was calculated based on dissolved elements decromeritics 3Flex surface characterization analyzer) tected by ICP-MS. Dolomite (diamond), calcite(square) use vertical axis
in the left, Clay (asterisk) and quartz (triangle) use vertical axis in the
to characterize their pore structure. Samples were right.
first pulverized and sieved through 102 m, then
dried at 105 C for 12 hours. The procedure for MIP
was similar to a previous study (Comisky et al.
2006). For nitrogen adsorption, the dried sample
was then heated to 200 C at 10 oC/min and degassed for 2 hours before nitrogen adsorption.
Measurement of Mechanical Properties.
A shale disk sample embedded in epoxy was exposed to 3 wt% HCl in 3 wt% KCl with only one
face contacted by the acid solution. The hardness of
the pre-acidizing sample and the sample acidized
for 1 hr and 24 hr was measured by an indentation
test, in which a spherical tungsten carbide indenter
of 5mm diameter was used to indent a shale disk Figure 6 Solubility of Bakken powder sample in 3 wt% KCl and in 3
sample at a constant strain rate of 0.0003 in/min wt% HCl in 3 wt% KCl at ambient temperature. Weight loss was
until the load reached around 50 lb. Indentation and measured by solid concentration in solution.
load were monitored for the entire process. Indentation was performed at least five random locations for each sample. Hardness was calculated by the
maximum load applied divided by the contact area of the indenter to the sample at maximum indentation
(Oliver and Pharr 2004).

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Figure 7Microstructures of pre-acidizing Bakken shale. (A): A representative image field contains typical microstructures and pore structures.
Carbonate (CB) appears as carbonate-rich region, carbonate islands, carbonate rings and mixed zone of carbonate/clay/organic matter (OM). (B):
A subfield of (A) showing inter-particle pores (interpore) in carbonate; (C): Another subfield of (A) showing iner-particle pores in clay; (D): A
subfield of (C) showing microstructure of organic matter with OM pores. WD working distance; mag magnification; HV high voltage; HFW
horizontal frame width; spot spot size; BSED backscattered electron detector; mix mixed images of secondary electron detector and BSED.

Results and Discussion

Mineralogy and Acid Solubility.
The mineralogy of a Bakken shale sample used in this study is shown in Table. 1. Carbonate minerals
make up around 24 wt% of the rock matrix with about equal amounts of calcite and dolomite. Acid
dissolved 34.91.6 wt% of the Bakken powder sample, the dissolved calcite and dolomite matched well
with XRD results (Fig. 5). Only 76.6 wt% of the dissolved solid was carbonate, elements from inert
minerals such as quartz and clay were also detected in the dissolved solids. The dislodgement of inert
minerals was also observed in in-situ microstructure study. By comparing with solubility in 3 wt% KCl,
the dissolution and weight lost were confirmed to be mostly caused by acidizing (Fig. 6). The results
suggest that shales with high carbonate content will be rapidly dissolved by acid once appropriate access
is provided.
Microstructure In Pre-Acidizing Shale.
Shale contains pores of various sizes, shapes and structures. Generally, pores can be categorized into three
types in terms of structure: inter-particle, intra-particle and organic matter (OM) pores (Loucks et al.
2012); and into another three types in terms of size: macropores (greater than 50 nm), mesopores (between

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Figure 8 In-situ comparison of microstructures of pre-acdizing Bakken shale and their corresponding post-acidizing microstructures in the same
image field. (A): An typical example of microstrcture in pre-acidizing Bakken; (B): Post-acidizing microstructures of the same image field as (A).
Carbonate dissolution create channels in CB-rich reigion; cavities in carbonate islands; grooves in carbonate rings, and roughness in mixed zone of
carbonate with other minerals. Inert minerals was dislodged and formed cavities by dissolution of surrounding carbonate; (C): Another image filed
of pre-acidizing Bakken; (D): Post-acidizing microstructure of the same image field as (C). Changes in microstructure were similar to (B). WD
working distance; mag magnification; HV high voltage; HFW horizontal frame width; spot spot size; BSED backscattered electron
detector; mix mixed images of SE2 and BSED; LVD low vapor detection.

2 and 50 nm) and micropores (under 2 nm) (Rouquerol et al. 1994). All these typical pore types were
observed in the pre-acid Bakken sample (Fig.7, 8A, 8C). Inter-particle pores were found mostly associated
with carbonate or clay (Fig. 7B, 7C). These pores are the remaining space between grain or clay platelets
after compaction and cementation. Inter-particle pores in carbonate were mostly angular macropores with
long dimension from around 100 nm to 2 m (Fig. 7B). Two different types of inter-particle pores
presented in clay: those between the clay platelets, with long dimension from 50-100 nm; the other
appeared between the rigid edge of carbonate or quartz grains and the compacted clay, ranging from 100
nm to 2 m (Fig. 7C). Pores between clay platelets tend to be smaller, it is because clay platelets are more
deformable and the inter-particle space can be more compressed than for carbonate or quartz grains.
Specific clay types can be identified based on morphology and EDS X-ray spectra (by comparing with
standard spectra, results not shown).
Intra-particle pores were found in pyrite framboids (Fig. 9E), but were a much smaller proportion than
inter-particle pores, and are not the focus of this study. OM pores only appeared in a very small portion
of the organic matter (Fig. 7D). The OM pores we observed were 5 to100 nm, poorly aligned and irregular

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Figure 9 Microstructures and pore structure of post acidizing Bakken. (A): Wavy surface and pit-like structure in channels developed in
carbonate-rich region; (B): Grooves and cavities caused by carbonate dissolution increased accessibility to pores in clay; (C): Roughness formed in
mixed zone and cavities created by dissolution of carbonate islands; (D): Grooves, and roughness in silica and clay filled portions with increased pores
accessibility; (E): Structure of organic matter and pyrite stayed relatively stable during acidizing compared to surrounding roughness formed by
dissolution of carbonate; (F): Inert minerals quartz maintained stable structure in acidizing. WD working distance; mag magnification; HV
high voltage; HFW horizontal frame width; spot spot size; LVD low vapor detection.

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Figure 10 In-situ comparison of mineral distribution in pre-acidizing (A, B, C) and post-acidizing (D,E,F) Bakken shale samples at the same micro
location.

(likely controlled by the maturation process of kerogen). It is believed that type II kerogen is more likely
to develop OM pores than type III and woody type OM (Loucks et al. 2012).
In-Situ Microstructure and Pore Structure Study.
With relative coordinates and markers recorded during imaging pre-acidizing samples, we successfully
relocated the same image fields in the post-acidizing samples. A direct visual comparison was made
between these images for the same field of view (Fig.8). When imaging the microstructure of the
post-acidizing sample, the coating was not applied to avoid any effects of coating on microstructure. In
this case we had to use low vapor dection mode for imaging, which was different from secondary electron
and BSE mode used for pre-acidizing sample. Because of the difference between these imaging modes,
the same locations in pre-acidizing and post-acidizing samples may appear different in sharpness and
contrast. To facilitate the direct visual comparison, two representative fields with clear markers (large
carbonate region) were chosen on purpose (Fig.8).
Since carbonate is the main mineral that reacts with acid, pre-acidizing distribution and structure of
carbonate directly affects the microstructure and pore structure after dissolution of the carbonate. In the
Bakken shale used in this study, carbonate minerals dominated the appearance of the sample before
acidizing (Fig. 8A, 8C). Four distribution patterns of carbonate were identified : 1) Carbonate-rich
regions, with area over than 100 m x 100 m containing mostly fine grained limestone muds, or
associated with calcite precipitation in natural fractures; 2) Carbonate grains (we called it carbonate
islands in this paper), with dimensions of around 10 to 30 m; 3) Carbonate rings, at the rim of quartz
or clay grains or clusters of grains with dimensions of 10 to 30 m; 4) Finely mixed siliceous and
carbonate grains. Mixed zone was the predominant distribution type of carbonate spanning most area of

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Figure 11Mineral distribution of post-acidizing Bakken at a micro location. (A): Microstructures in pre-acidizing sample; (B): Calcite and dolomite
distribution in post-acidizing sample; (C): Organic matter and clay in post-acidizing sample; (D)Distribution of pyrite and Si (associated with quartz
or clay) in post-acidizing sample.

the sample. The carbonate rings and mixed zone are likely the results of cementation, during which
cementing materials such as carbonates or feldspars precipitated from solution and filled the space
between clay or quartz grains.
The post-acidizing microstructure showed close association with the original carbonate distribution
patterns. Channels were formed in carbonate-rich region after acidizing (Fig. 8B, 8D, 9A). The depth of
the valleys created by the removal of the carbonate-rich region was estimated to be 30-50 m. Since
limited acid (0.5 ml 1 wt% HCl) was used in the test, the channels are expected to be deeper given enough
acid. Channels developed wavy surface features which consisted of pits ranging from 1 to 8 m in
diameter and with various depths. The surface showed clear evidence of the formation of pits where the
carbonate minerals had been dissolved. The pit sizes were slightly larger than the inter-particle pores in
the pre-acidizing carbonate (Fig. 7B).
In carbonate islands, most carbonate was removed after acidizing and created cavities with size (10 to
30 m) similar to the origin island but bigger than the pits (1 to 8 m) developed in carbonate-rich region
(Fig. 8B, 8D, 9B, 9C). Estimated depth of cavities could be over 10 m. Carbonate dissolution from
carbonate rings in some cases developed grooves which replaced the original carbonate (Fig. 8B, 8D, 9B,

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Figure 12Microstructures of acidized Bakken shale in the acid penetration test. (A): An overview of the acidized zone which contains many pores
and cavities that range from 10?m to around 120 m. Porosity was 20.24% based on 20 random image fields; (B): A subfield of (A); (C): A subfield
of (B) shows typical big pores formed by dissolution of carbonate surrounding inert minerals like quartz (Qtz) and clay; (D): A subfield of (B) showing
pores developed at the edge of clay. WD working distance; mag magnification; HV high voltage; HFW horizontal frame width; spot spot
size; BSED backscattered electron detector; ETD Everhart-Thornley Detector.

9D); in some other cases, the carbonate dissolution dislodged the minerals previously enveloped by the
carbonate (Fig. 8B, 8D, 9B).
A rough surface was developed after acidizing because of the selective dissolution of carbonate in the
shale (Fig. 8B, 8D, 9C, 9D). The acidized zone appeared very porous and full of large irregular pores and
channels which may develop a well connected flow network.
Clay, quartz and organic matter are insoluble in acid, and their pores did not change in geometry or
in size by acidizing (Fig. 9D, 9E, 9F). However, it is important to note that dissolution of carbonate
adjacent to these minerals increased access to their pores at the rim which were originally covered by
carbonate as cement. Examples for this increased access can be found in grooves, cavities and other
features on the rough surface (Fig. 9B, 9C, 9D). Although inert minerals did not react with acid, in some
cases they still could detach from the matrix as a result of acidizing
A direct comparison between the mineral distribution in pre-acidizing samples (Fig. 10A, 10C, 10E)
and post-acidizing samples (Fig. 10B, 10D, 10F, 11B, 11C, 11D) showed significant differences. The
sample was originally dominated by calcite (in blue) and dolomite (purple), accompanied with several
clumps of clay (in green), and scatter of quartz (in red), pyrite (in yellow) as well as few dots of organic

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Figure 13Mineral distribution in the acidized zone for post-acidizing Bakken through acid penetration test. (A): Microstructures of the acidized
zone; (B): Calcite and dolomite distribution; (C): Clay distribution; (D)Distribution of pyrite and Si (associated with quartz or clay).

matter (in orange). Most of the calcite other than the calcite in carbonate-rich region was removed by
acidizing, and replaced by dolomite, clay, quartz and organic matter which have a lower reaction rate with
or are inert to acid. Most pre-acidizing inert minerals, remained in place after acidizing.

Changes in Microstructure and Pore Structure of Shale in Acid Penetration

Tests
Many pores with dimensions of 10 to 120 m were observed in the acidized zone in the acid penetration
tests (Fig. 12), and these pores were much bigger than the pores developed in the study conducted by
simply placing the acid on the shale surface (under 30 m). The acid penetration test forced acid into the
shale matrix until it broke through to the outlet end of the sample. Acid was continuously pumped into
the sample for around 40.4 hrs, compared to a 1-min reaction time in the earlier study. Acidizing was,
therefore, muchmore complete in the acidized zone in the penetration tests and led to pores of bigger size
(by more thorough dissolution of carbonate and other minerals). The more complete acid reaction was also
confirmed by mapping elements in the acidized zone, where almost all calcite was removed and we are
left with predominant clay, quartz and a small proportion of dolomite (Fig. 13).

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Figure 14 Pore-size distribution measured by mercury intrusion prosimitry (MIP) (a) and nitrogen adsorption (b) for pre-acidizing Bakken and
acidized zone of post-acidizing Bakken in acid penetration test. MIP intrusion below 115 Psi, corresponding to pore size above 1787.6 nm, is taken
as confirmation and not considered in pore-size distribution. Pore size from nitrogen adsorption was calculated based on desorption isotherm using
BJH (Barret, Joyner and Halenda) method assuming a cylindrical gemetry, and pores under 4 nm were ignored due to tensile strength effects(Groen
et al.2003).

Pore-Size Distribution.
The pore size in the pre-acidizing Bakken sample and in the acidized zone from the acid penetration test
was characterized using complimentary information from MIP (mercury injection porosimetry) and
low-pressure nitrogen adsorption. MIP measures pore volume by monitoring the volume of mercury
intruding into a porous medium as pressure increases from atmospheric pressure to 60,000 psi, with the
corresponding pore diameter varing from 10,000 nm to 3.6 nm. However, the actual measuring range is
usually narrower because of several reasons: at low pressure, the recorded volume of intruding mercury
includes mercury taken up by structure conformation which in fact does not intrude into pores; at high
pressure, measurement can be biased by potential deformation of rock grain and reopening of closed
pores. Despite these limitations, MIP overall is useful in evaluating the distribution of macropores.
Nitrogen adsorption, in the other hand, is good at characterizing pores between 1.7 and 200 nm. Nitrogen
adsorption measures the amount of adsorbed nitrogen gas at a series of relative pressures P/Po from 0.001
to 1, where Po is the condensation pressure of nitrogen.
MIP results showed that the Bakken sample had a bimodal pore-size distribution with a major peak
between 24-45 nm and a minor peak around 8-10 nm (Fig. 14 a). Pores greater than 100 nm had very little
pore volume. This distribution changed to tri-modal in the post-acidizing sample (8-10 nm, 24-45 nm, and
2000 nm): the major peak changed to around 2000 nm, and the pore volume for pores greater than 100
nm significantly increased, taking up 45% of the total pore volume; while the other two peaks remained
at the same pore size as the pre-acidizing sample but with increased pore volume as well. This change in
pore-size distribution was also found by nitrogen adsorption (Fig. 14b), in which the post-acidizing shale
had a similar bimodal distribution as the pre-acidizing shale at 20-50 nm (major peak) and 7-10 nm but
with a higher pore volume (increased by 97% and 51% after acidizing, respectively). The peak at around
3.4 nm was ignored because of the calculation limitation on the desorption curve (Groen et al.2003). Peaks
in adsorption occurred at slightly higher pore size than the corresponding peaks in MIP. The difference
is caused by the fact that adsorption captures the distribution of pore bodies while the MIP technique
measures the distribution of pore throat radii (Kuila and Prasad 2013).
Shapes of the adsorption isotherm also reveal important information related to pore structure. Both
pre-acidizing and post-acidizing Bakken showed a Type IV nitrogen adsorption isotherm and H3 type
hysteresis with no plateau at high P/Po region (Fig.15). Type IV isotherms are attributed to capillary
condensation that occurs in mesopores (Sing 1984). No plateau at the high P/Po region indicates the
presence of many slit-like macropores, which are often associated with non-rigid aggregates in clay

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Figure 15Nitrogen adsorption and desorption isotherm for pre-acidizing Bakken and acidized zone of post-acidizing Bakken in acid penetration
test.

platelets such as kaolinite. Very low adsorption in the low relative pressure region (P/Po 0.01) suggests
negligible presence of micropores.
Results from the MIP and nitrogen adsorption agreed with the microstructure observed by FE-SEM.
The increased hysteresis in adsorption isotherm, total nitrogen absorption and pore volume in mesopores
and macropores correlate well with the large pores observed visually and the improved accessibility to
pores resulting from acidizing. The low and relatively stable adsorption in the micropore region during
acidizing was consistent with the lack of micropores in most organic matter. However, it is important to
note that the biggest pores that can be captured by MIP and nitrogen adsorption are under 10 m, and
pores greater than this size were commonly observed in post-acidizing Bakken samples under the SEM.
The SEM images shown in this paper that can characterize pores greater than 10 m should be combined
with our MIP and adsorption data data to give complete picture of the entire range of pore sizes.

Implications for Acid Fracturing in Shale

Fractures in acid fracturing maintain their conductivities if they are supported by fracture surface
asperities formed as a result of non-uniform acid etching. The topology of the asperities determines the
geometry and conductivity of the fracture. In acid fracturing carbonate formations, over 99% of the rock
can be dissolved by acid, and non-uniform etching pattern including channeling, roughness can be
developed (Ruffet et al.1998; Dong et al.1999; Nieto et al. 2008; Pournik et al. 2009). Common etched
fracture width in carbonate formations range from 1mm to 5 mm. Because of the highly reactive
composition and high matrix permeability in carbonates, non-uniform etching in carbonates is more
affected by local differences in acid convection and diffusion, acid concentration and leakoff. These
effects had been observed in experiments (Hoefner and Fogler 1988; Dong et al.1999; Nieto et al. 2008)
and well modeled by simulation (Mou et al.2007; Oeth et al. 2014).
In shales, matrix permeability is much lower (nD level) and only part of the minerals can be dissolved
by acid. Leakoff to the surrounding matrix is much smaller than in carbonates. In this study, it took 40.4
hours for acid to breakthrough a 0.25 inch thick shale sample when 100 Psi was applied across it (data
not shown). It typically takes 512 minutes and 1 6 pore volume for acid to breakthrough a carbonate
inch core of 4 12 inch in length (Hoefner and Fogler 1988; Sayed and Nasr-El-Din 2013). Although it
is difficult to compare the breakthrough time directly with preivous studies, the acid leakoff in shale is still

SPE-173390-MS

15

Figure 16 Comparison of surface profile of pre-acidizing (a) and post-acidizing Bakeen (b), in a quarter round with diameter of 1.5 inch.
Post-acidizing sample was obtained by pre-acidizing sample exposed to 3 wt% acid for 27 hours at ambient temperature. Surface profile was
generated by Konica Minolta Vivid 910 3D non-contact digitizing system.

Figure 17Hardness (a) and Youngs modulus (b) of a pre-acidizing Bakken sample and the same sample acidized for 1 hour and 24 hours.

expected to be significantly lower than in carbonates considering the breakthrough time and pore volume
in shale are 2-3 magnitudes larger than that in carbonates. In fact, in our attempt to pump acid through
a one inch by one inch shale in a Hassler type core holder (without bypass), we could only inject less than
4 ml acid after 60 hours with an injection differential pressure of 1500 Psi.
Non-uniform etching of fracture surfaces in shale greatly depends on the distribution of carbonate
minerals and the access the acid has to these minerals. Heterogeneity, therefore, plays an important role
in this non-uniform etching. At a pore scale, non-uniform etching occurs as channels in carbonate-rich
regions, grooves or cavities caused by dissolution of carbonate rings or islands, roughness in the mixed
zone of carbonate and inert minerals. Based on the microstructures observed, these non-uniform etching
features can create fracture geometry with a half-width from 10 to around 100 m. The depth of these
channels has not been measured accurately in this study, however it is estimated to range from 10 to 100
m. Channels have proved to be very effective in improving the productivity of fractured wells (Dong et
al. 1999; Nieto et al. 2008; Mou et al. 2010).
At a core scale, the depth of the surface roughness in a quarter core exposed to acid for 24 hrs was
smaller than 1 mm (Fig. 16) Channels were observed in Tripathi and Pourniks (2014) study, however the
depth of the channel was not given. At a field scale, the effect of heterogeneity is believed to be even more
significant. The presence of geological features such as calcite veins and calcite filled bedding planes is
more likely, and these features can easily create non-uniform etching and large scale surface topology
such as channels that can promote the flow of hydrocarbons.

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SPE-173390-MS

Figure 18 Typical load-displacement curves with a loading and unloading cycle for a pre-acidzing Bakken, and the same sample acidized for 1 hour
and 24 hours. Acidizing was performed on a disk shale sample embedded in epoxy with acid contacted on one side. Load-displacement curve was
measured on the acidized side of the sample.

Fractures will close under closure stress after they are non-uniformly etched at the surface. Mechanical
properties of the surface asperities and of the rock matrix close to the fracture surface determine how
asperities deform and the degree the fracture geometry is sustained under closure stress. Fracture
conductivity in acid-fractured carbonates decreases from 1000- 10,000 md.ft at a closure stress of
500-1000 psi to 100-1000 md.ft at 4000-5000 psi by 90-99% (Nierode and Kruk 1973; Ruffet et al. 1998;
Nieto et al. 2008; Pournik et al. 2009). Acid fracturing could weaken the rock matrix while etching the
fracture surface. Empirical, semi-empirical and theoretical correlations describing the decrease of fracture
conductivity with closure pressure have also been developed (Nierode and Kruk 1973; Gong et al. 1999;
Pournik et al. 2009; Deng et al. 2012). For shale, we found exposure to acid for 1 hour and 24 hour can
reduce hardness to 71% and 37%, of its original value respectively (Fig.17). However, no obvious changes
were found in Youngs modulus by acid exposure. Fig.18 shows typical load-displacement curves for
pre-acidizing and post-acidizing samples. Displacement to reach the same load was greater in the sample
with longer acid exposure, while the initial slope of the unloading curve, which relates to Youngs
modulus, stayed about the same. Acidized fracture conductivity was found decrease from around 5-20
md.ft to 0.1-0.5 md.ft (by around 98%) when the closure stress was increased from 500 psi to 3500 psi
(Tripathi and Pournik 2014). Such measurements probably do not reflect the non-uniform etching that is
expected to happen in the field. Since the experiments are being conducted in 1 inch diameter core, it is
likely that the acid will uniformly etch the fracture surface in the lab. This is not likely to happen in the
field where a much larger fracture surface is exposed to the acid and this will lead to much more
non-uniform etching of the fracture surface. Such a scenario is hard to replicate in the lab.
It is also not clear how the acidized shale matrix close to the fracture surface will contribute to the flow.
The contribution can be significant if the fracture conductivity in the acid-fractured shale is of the order
of 0.1 md.ft. The acidized shale has a pore structure that is very similar to a sandstone with many pores
from 10 120 m, and with a porosity of 20.24% and a permeability in 10s of mD calculated by the Lattice
Boltzmann method (results not shown). A similar increase in porosity was also reported in Morsy et al.s
study (2013). The acidized matrix, may provide additional fracture surface area for flow into the fracture.
It should be noted that a fracture with mD permeability is still infinitely conductive compared to the shale
matrix.

SPE-173390-MS

17

Conclusions
Changes to the pore structure and mechanical properties of a shale caused by acid fracturing were
demonstrated for the first time in this study through FE-SEM imaging. Depending on the distribution of
carbonate minerals in the shale, acid fracturing can result in different fracture surface patterns: channels
in carbonate-rich regions, cavities or grooves in carbonate islands or carbonate rings, and roughness in
areas of scattered carbonate and inert minerals. Inert minerals such as clay, quartz and orgranic matter
mostly remain structurally stable, however some of them can be dislodged when surrounding carbonates
are dissolved. Acid fracturing creates many macropores with diameter up to 120 m and this increases
accessibility to mesopores associated with clays. These channels, pores and cavities can form surface
asperities and improve fracture conductivity, especially if this dissolution occurs non-uniformly on the
surface of unpropped fractures. The hardness of the shale fracture surface was reduced by 30 to 70% by
acidizing. This can lead to proppant embedment, closure of some asperities and a reduction in fracture
conductivity. However, if the acid etching is non-uniform, as is expected in the field, the impact of this
shale softening will be mitigated. The non-uniformity of the etch pattern is a function of the heterogeneity
in the shale at many different length scales and is very difficult to replicate in a lab experiment. The
acidized shale matrix immediately adjacent to the fracture face, with significantly increased permeability
and porosity, may also serve as preferred channels to enhance hydrocarbon flow.

Acknowledgements
The authors are grateful for the generous sharing of nitrogen adsorption equipment by Dr. Hugh Daigle
and support from companies in the Hydraulic Fracturing and Sand Control Joint Industry Project at the
University of Texas at Austin. The companies include: Air Liquide, Air Products and chemicals,
Anadarko, Apache, Aramco Services, Baker Hughes, BHP Billiton, BP America, Cairn India, Chevron,
ConocoPhillips, Devon, ENI, Fairmount Minerals/Santrol, Ferus, Halliburton, Hess Corporation, Lanxness, Linde, Marathon, MeadWestvaco, Nexen, Oxy, PEMEX, Pioneer, Range Resources, Schlumberger,
Shell, Southwestern Energy, Statoil, Talisman Energy, TOTAL, Unimin, Weatherford and Wintershall.

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