Fuel 129 (2014) 173–181

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Evolution of nanoporosity in organic-rich shales during thermal

maturation
Ji Chen a,b, Xianming Xiao a,⇑
a
State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
b
University of Chinese Academy of Sciences, Beijing 100049, China

h i g h l i g h t s

 Laboratory-matured shale samples were produced by an anhydrous pyrolysis experiment.

 Low-pressure gas adsorption was used to characterize the pore structure of laboratory-matured shales.
 There are substantial differences in evolution of nanoporosity between organic-rich and organic-poor samples.
 Evolution of organic matter-hosted nanopores of gas shales can be roughly divided into three stages.

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

Article history: Artificial shale samples with equivalent vitrinite reflectance values (VRo) ranging from 0.69% to 4.19%
Received 7 January 2014 were obtained from an anhydrous pyrolysis experiment. Microporous and mesoporous characteristics
Received in revised form 18 March 2014 of these samples were investigated by low-pressure nitrogen and carbon dioxide adsorption techniques.
Accepted 25 March 2014
The result shows that the nanoporosity (microporosity plus mesoporosity) increases with thermal
Available online 13 April 2014
maturity after the oil window stage, and this increase is attributed to the formation of porosity within
organic matter and/or mineral–organic matter groundmass, rather than in the pure clay minerals. By
Keywords:
combining the gas generation and porosity evolution of these shales, a general model for formation
Gas shale
Anhydrous pyrolysis
and development of the nanoporosity is proposed.
Thermal maturation Ó 2014 Elsevier Ltd. All rights reserved.
Nanoporosity evolution

1. Introduction pressure (MICP), and scanning electron microscopy (SEM) [5,13–

A gas shale reservoir is characterized by abundant pores having
sizes in a range of several to several hundreds of nanometers [1–8].
Pores are subdivided into micropores (pore width <2 nm),
mesopores (pore width between 2–50 nm) and macropores (pore
width >50 nm) according to the classification of International
Union of Pure and Applied Chemistry (IUPAC) [9]. It has been found
that a considerable part of gas occurs in an adsorbed state within
micro- and mesopores of gas shales [3,4,10–12]. Elucidating the
complex pore networks in gas shales has become a strategic
subject because many studies have shown that shale pore struc-
ture is one of the most important factors controlling gas capacity
[1–4,10–12]. Several measurement techniques have successfully
been developed to characterize the complex pore systems such
as small-angle and ultra small angle neutron scattering (SANS/
USANS), low-pressure gas adsorption, mercury injection capillary
⇑ Corresponding author. Tel.: +86 20 85290176; fax: +86 20 85290706.
E-mail address: xmxiao@gig.ac.cn (X. Xiao).
17]. The geological controls of pore structure in gas shales include
the total organic carbon (TOC) content, thermal maturity and
mineralogy, which have preliminarily been discussed in previous
works [3,4,10,18,19].
Effect of thermal maturation on porosity has recently attracted
more attention because of the growing recognition that porosity in
organic matter, to a large extent, is a function of thermal maturity
[4,6,18,19]. The recent efforts toward understanding porosity
evolution with maturation have been matched with documenting
the pore networks in gas shales. For example, Curtis et al. [20] used
focused ion beam milling combined with scanning electron
microscopy (FIB–SEM) techniques to investigate the organic poros-
ity within Woodford Shale samples with vitrinite reflectance
values (VRo) ranging from 0.51% to 6.36%, finding that secondary
organic porosity is absent in samples with VRo values less than
0.90%, but does occur in samples with VRo values greater than
1.23% except for a 2.0% VRo sample. The exception suggested that
maturity alone is not a reliable predictor of porosity in organic
matter and other factors such as organic matter composition

http://dx.doi.org/10.1016/j.fuel.2014.03.058
0016-2361/Ó 2014 Elsevier Ltd. All rights reserved.
174 J. Chen, X. Xiao / Fuel 129 (2014) 173–181
complicate this predication. While SEM observations of organic-
rich mudstones from the Upper Jurassic Kimmeridge Clay Forma-
tion indicate that there are no differences of organic pore shape
and size between immature and mature samples, and the minimal
preservation of organic pores during hydrocarbon generation is
attributed to the highly ductile nature of clays and organic materi-
als [21]. Mastalerz et al. [22] examined the evolution of porosity
with maturation in a suit of five New Albany Shale samples span-
ning a maturity range from immature (VRo = 0.35%) to postmature
(VRo = 1.41%), observing that total porosity and total pore volume
exhibit a significant decline from immature sample to late mature
sample with a reduction of more than 80%, and then regain their
higher values in the post mature sample. After addressing the
influence of TOC content and mineralogy on porosity, they further
suggested that maturity appears to exert the dominant control
upon porosity development in shales. However, their data was lim-
ited to shales with VRo value less than 1.41%.
Therefore, response of shale porosity, especially organic
porosity to hydrocarbon generation and cracking caused by ther-
mal maturation remains puzzling in gas shale systems (especially
highly-matured shales), additional systematic studies need to be
carried out. In the present study, three suites of artificial shale
samples across a maturation gradient were produced by laboratory
anhydrous pyrolysis of three low maturity shale samples with dif-
ferent kerogen types or TOC contents at a wide range of tempera-
tures. The evolution of their micro- and mesoporous characteristics
with thermal maturation was evaluated by low pressure nitrogen
and carbon dioxide adsorption measurements. The relationship
between gas generation and nanopore formation is also discussed.
2. Samples and experiments
2.1. Samples
Three suites of shale samples covering a range of maturities
were produced by anhydrous pyrolysis of three low maturity
shales/mudstones (approximately 0.60% VRo). The starting samples
used to be pyrolyzed originated from three different deposits across
China, including two organic-rich shales (samples LCG and DL) and
one organic-lean mudstone (sample EP). Sample LCG was collected
from an Upper Permian outcrop (Yaomoshan, Urumqi) of the south-
ern Junggar Basin, sample DL from an Upper Permian outcrop
(Changjianggou, Guangyuan) in the northern Sichuan Basin, and
Sample EP from an Oligocene deposit of well WC19-1M-1 in the
western Pearl River Mouth Basin. Their locations were present in
the Refs. [23–25]. A coal sample with a similar initial maturity
(VRo = 0.56%) was also pyrolyzed under the same conditions as
the three shales to give a measure of the thermal maturity of the
shale samples at different pyrolysis temperatures.
2.2. Anhydrous pyrolysis
The anhydrous pyrolysis experiment was carried out under
inert conditions in a programmed muffle furnace. The four raw
samples were first crushed to <250 lm, dried for 24 h at 60 °C in
a vacuum oven, and then each was separated into 10 fractions,
transferred to a series of quartz tubes (with an inner diameter of
30 mm) and sealed under vacuum condition. The four raw samples
were simultaneously heated in the furnace from room temperature
to a preset temperature at a heating rate of 200 °C/h, and then kept
for 24 h. The target temperature was set within a range of 300–
750 °C at 50 °C intervals. Every heating run was performed on a
new batch of powdered samples. The pyrolysis products at each
temperature point were recovered and were subject to an ongoing
multidisciplinary analytical program.
2.3. Organic geochemistry and petrology analysis
The total organic carbon (TOC) of the three initial shales was
measured by a Leco CS230 Carbon/Sulfur analyzer after the sam-
ples were treated by hydrochloric acid to remove the carbonates.
The Rock–Eval pyrolysis was conducted using a Rock–Eval 6 Turbo
analyzer to assess their hydrocarbon generation potential. Stan-
dard IFP55000 was applied to calibrate the instrument before
and after sample analyses.
A 3Y-Leica DMR XP microscopy equipped with a microphotom-
eter was used to identify the macerals of the initial shales and mea-
sure the vitrinite reflectance (VRo) values of the coal samples
obtained from the different pyrolysis temperatures. According to
the maturities achieved from different pyrolysis temperatures, a
standard with a reflectance closest to the measured value was
selected from three available standards: yttrium aluminum garnet
YAG-08-57 (Ro = 0.904%), NR1149 (Ro = 1.24%), and cubic zirconia
(Ro = 3.11%). An oil objective of 50  /0.85 and a measuring fiber
with a diameter of 0.6 mm were employed. VRo% for each sample
was determined by averaging 50 measurements on vitrinite
particles.
2.4. Mineral composition analysis
X-ray diffraction (XRD) analysis of the shale powders (including
the three initial shales and some of their heated samples) was car-
ried out on a Bruker D8 Advance X-ray diffractometers at 40 kV
and 30 mA with a Cu Ka radiation (k = 1.5406 for Cu Ka1). Step-
wise scanning measurements were performed at a rate of 4°/min
in the range of 3–85° 2h. The relative mineral percentages were
estimated semi-quantitatively using the area under the curve for
the major peaks of each mineral with correction for Lorentz Polar-
ization [4].
2.5. Gas adsorption and data analysis
Nitrogen adsorption at 77 K is universally used to examine the
micro-, meso-, and macroporosity of solid materials if a wide range
of relative pressures (P/P0) were applied [26]. Carbon dioxide
adsorption at 273.15 K is often the preferred choice to investigate
the microporosity of carbonaceous materials, since the ambient
temperature promote the gas diffusion in the microporous system
compared to the low temperature (77 K) used in nitrogen adsorp-
tion [26]. However, a limitation of CO2 adsorption at 273.15 K is
that CO2 molecular cannot fill larger micropores and also may have
additional interactions with organic matter [26,27]. With more
attention focused on the shale pore systems, nitrogen and carbon
dioxide adsorption techniques have widely been introduced to
study the pore characteristics of shales [5,13–17]. The experimen-
tal methods and parameter calculations may be briefly described
as follows.
Low-pressure gas adsorption measurements were conducted on
a Micromeritics ASAP 2020M surface area and porosimetry ana-
lyzer. Nitrogen adsorption and carbon dioxide adsorption were
used to obtain information about meso- and micropores respec-
tively. The term ‘‘nanopore’’ or ‘‘nanoporosity’’ used in this article
referred in particular to the micropores and mesopores. Each sam-
ple was degassed at 110 °C for 16 h in a vacuum chamber prior to
the analysis to remove its residual volatile material. Nitrogen iso-
therms were collected within a relative pressure (P/P0) range of
0.01–0.995 at liquid nitrogen (77 K). The equivalent surface area
was calculated within a relative pressure range of 0.05–0.20 by
the multi-point BET (Brunauer–Emmett–Teller) equation [28]:
1 1 C1 P
¼ þ  ð1Þ
VðP0 =P  1Þ V m C V m C P0
 J. Chen, X. Xiao / Fuel 129 (2014) 173–181
where P is the gas pressure (Pa), P0 is the saturation pressure (Pa), V
is the volume of sorbed gas at equilibrium pressure (cm3/g, STP), Vm
is the volume of monolayer (cm3/g, STP), C is the BET constant.
The mesopore volume was calculated by the BJH (Barrett–
Joyner–Halenda) theory using the adsorption branch of nitrogen
isotherms [29]. This classical pore size model is based on the Kelvin
equation assuming a cylindrical pore and corrected for multilayer
adsorption.
Carbon dioxide adsorption isotherms were collected within a
relative pressure range of 105–3.0  102 at ice/water bath
(273.15 K) [30]. Micropore surface area was calculated by the
well-known Dubinin–Radshkevich (D–R) equation [31], which is
based on the theory of volume filling of micropores (TVFM) and fol-
lows the fundamental relation as below:
 2  2
RT P0
ln V ¼ ln V 0  ln
E P
where V is the volume of sorbed gas at equilibrium pressure (cm3/g,
STP), V0 is the micropore capacity (cm3/g, STP), R is the universal gas
constant (8.314 J mol1 K1), T is the analysis temperature (K), E is
the characteristic energy (kJ mol1).
The micropore volume was determined by the Dubinin–Astak-
hov (D–A) equation based on the CO2 isotherms [31]. They intro-
duced the structural factor n (Astakhov index) to expand the D–R
equation on heterogeneous adsorbents. This equation can be
defined as:
 n  n
RT P0
ln V ¼ ln V 0  ln
E P
3. Results and discussion
3.1. Organic geochemistry and mineralogy
The organic geochemistry data of the three initial shales are
shown in Table 1. Although the three shales have a similar matu-
rity with VRo range from 0.56% to 0.62%, their kerogen types are
different and the TOC contents vary widely. Sample LCG has a
TOC content of as high as 29.1% with a HI (hydrogen index) of
839 mg/g TOC (Table 1). The shale is rich in lamalginite and poor
in vitrinite and inertinite (Fig. 1). The TOC content and HI of sample
DL are 8.63% and 278 mg/g TOC (Table 1), respectively, and it is
characterized by liptodetrinites and telalginites with a few vitrinite
and inertinite (Fig. 1). These data suggest that samples LCG and DL
have kerogens classified as type I and type IIb respectively. Sample
EP is poor in organic matter with a TOC content of 0.18% (Table 1).
Table 2 presents the mineralogical data of the three initial
shales and their sub-samples at some selected pyrolysis tempera-
tures. The initial samples LCG and DL have similar amounts of brit-
tle minerals and clays, but the former is dominated by quartz plus
feldspar (total 66%) and mixed illite–smectite (20.1%), the latter by
Quartz (60.8%) and mixed illite–smectite (18.9%). The initial sam-
ple EP has a clay content of 56.8%, including 37.9% kaolinite and
18.9% mixed illite–smectite.
During the pyrolysis, the clay mineral types of samples LCG and
DL are not changed, while the kaolinite of sample EP was not
Table 1
Geochemical data of the three initial shales.
Sample Age VRo (%) TOC (wt.%)
LCG Upper permian 0.61 29.1
DL Upper permian 0.62 8.63
EP Oligocene 0.56a 0.18
a
Data from organic-rich mudstone at similar depth.
175
examined after 500 °C, which can be interpreted to the formation
of amorphous metakaolinite caused by the dehydroxylation of kao-
linite [32]. The dolomite in sample LCG disappears at 600 °C
because of its thermal decomposition [33]. The contents of quartz,
feldspar and illite–smectite show an irregular change with the
temperature. It is believed that this change is mainly related to
the heterogeneity of their sub-samples as well as the above decom-
position or dehydroxylation which affects their percentage.
3.2. Pyrolysis temperature and vitrinite reflectance
The vitrinite reflectance values of the coal samples at different
pyrolysis temperatures are presented in Table 3. They show an
approximately linear correlation. The sub-samples of samples
LCG and DL range from 150 to 200 mg at each temperature point,
ð2Þ which make difficulty to prepare their polished blocks to measure
the vitrinite reflectance. It is generally accepted that the thermal
maturity of sedimentary organic matter or the rank of coal depends
mainly on its temperature history [34–36]. The famous tempera-
ture and time index model [34,35] and the widely used EASY%Ro
model [37] quantified the relationships between maturity (VRo),
temperature and time. According to these models, different
sedimentary organic matter (shale or coal) will achieve the same
maturity if they experience the same thermal history (temperature
and duration). The shale samples have a similar initial maturity
with the coal sample and the pyrolysis experiment for each sample
and temperature point was carried out in the same batch, thus
ð3Þ the VRo values of the coal sub-samples can be used to characterize
the maturities of the shale sub-samples obtained from the
same temperatures.
3.3. Adsorption isotherms
The nitrogen isotherms for the three suits of samples are shown
in Figs. 2–4, which are corresponding to type IV isotherms as
defined by IUPAC [9]. Such type of isotherm is characterized by
its hysteresis loop, which is associated with capillary condensation
taking place in mesopore structures [9]. The shape of hysteresis
loop is close to type H3 [9]. Although the effect of various factors
on hysteresis loop is not fully understood, the type H3 loop is usu-
ally thought to be associated with aggregates of plate-like particles
giving rise to slit-shaped pores based on the interpretation of
IUPAC [9]. Nevertheless, this interpretation is subject to error in
the case of natural materials such as gas shales [16,17]. Many
SEM observations have repeatedly shown that pores in organic
matter of shales are not slit-like but bubble- or foam-like
[5,6,20,21]. SANS/USANS data from Clarkson et al. also suggested
that the assumption of slit-shaped pores inferred from hysteresis
loop shape was incompatible with SANS scattering results [14].
For the nitrogen amounts adsorbed at P/P0 around 0.995, sample
LCG shows a decrease from 6.50 cm3/g at 0.69% VRo to 1.67 cm3/
g at VRo of 0.89%, and then turns to increase to 22.50 cm3/g at
4.19% VRo (Fig. 2). Sample DL shows an increase from 12.67 cm3/
g at 0.69% VRo to 36.75 cm3/g at 4.19% VRo (Fig. 3), whereas sam-
ple EP shows a relatively stable value of about 22 cm3/g before
1.95% VRo and then a sharp decline with further increasing
S1 (mg/g) S2 (mg/g) Tmax (°C) HI (mg/g TOC)
2.92 230.4 435 839
1.24 25.4 437 278
/ / / /
176 J. Chen, X. Xiao / Fuel 129 (2014) 173–181

Fig. 1. Photomicrographs (oil immersion) of samples LCG and DL before anhydrous pyrolysis taken under the fluorescent light.

Table 2
Mineralogical compositions (in wt.%) of three initial shales and their sub-samples at selected pyrolysis temperatures.

Sample Quartz (wt.%) Feldspar (wt.%) Calcite (wt.%) Dolomite (wt.%) Illite–smectite (wt.%) Kaolinite (wt.%) Pyrite (wt.%)
LCG-initial 37.8 28.2 0 13.9 20.1 0 0
LCG-300 °C 35.5 23.8 0 11.0 29.7 0 0
LCG-400 °C 39.6 22.9 0 13.7 23.8 0 0
LCG-500 °C 40.8 27.9 0 12.3 19.0 0 0
LCG-600 °C 43.8 29.4 0 0 26.8 0 0
LCG-700 °C 44.4 30.8 0 0 24.8 0 0
DL-initial 60.8 0 13.5 0 18.9 0 6.8
DL-300 °C 61.2 0 16.1 0 22.7 0 0
DL-400 °C 65.1 0 17.3 0 17.6 0 0
DL-500 °C 66.5 0 14.8 0 18.7 0 0
DL-600 °C 63.8 0 16.1 0 20.1 0 0
DL-700 °C 67.7 0 14.0 0 18.3 0 0
EP-initial 28.8 14.4 0 0 18.9 37.9 0
EP-300 °C 25.1 17.0 0 0 30.8 27.1 0
EP-400 °C 27.8 17.6 0 0 41.4 13.2 0
EP-500 °C 30.1 13.0 0 0 45.4 11.5 0
EP-600 °C 31.1 21.7 0 0 47.2 0 0
EP-700 °C 30.0 23.6 0 0 46.4 0 0

Table 3 3.4. Response of pore structure parameters to thermal maturity

Vitrinite reflectance values of coal samples obtained from different pyrolysis
temperatures.
Specific surface area and pore volume for the three suites of
Temperature (°C) Vitrinite reflectance VRo (%) samples are shown in Fig. 6. For sample LCG (Fig. 6A1 and A2),
300 0.69 the specific surface area and volume of its micro- and mesopores
350 0.89 pass through a minimum value around the oil window
400 1.25 (VRo = 0.89%). After the oil window, its micropore surface area
450 1.51
and volume as well as its mesopore surface area increase to a max-
500 1.95
550 2.60 imum at 3.48% VRo, and then decrease with further increase of
600 3.02 maturity. But its mesopore volume increases up to the maximum
650 3.48 maturity achieved in this study. Compared with sample LCG, sam-
700 3.89 ple DL has similar variations of the four parameters with increasing
750 4.19
maturity except for the lack of minimum value around the oil win-
dow, in which range there is a slight increase (Fig. 6B1 and B2).
Valenza et al. [18] reported the geochemical controls on micro-
structure of North American shales having maturities from approx-
maturity from 19.41 cm3/g at 2.60% VRo to 5.69 cm3/g at 4.19% VRo imately 0.5% to 2.7% VRo/VRb (vitrinite or bitumen reflectance),
(Fig. 4). also observing a marked increase in surface area and pore volume
Fig. 5 gives an overview on the carbon dioxide isotherms, which with increasing maturity. In the case of sample LCG, its evolution of
are close to type I isotherm given by microporous solids [9]. The porosity indicates that porosity can undergo a reduction to some
limiting uptake of these isotherms with increasing relative pres- extent in the oil window stage, which is different from a monoton-
sure is governed by the accessible micropore volume rather than ically growing trend as indicated by previous studies [4,18,19]. A
the internal surface area [9]. The carbon dioxide adsorption capac- similar reduction of pore volume or porosity around the matura-
ity of samples LCG and DL at P/P0 around 0.03 shows an increase tion stage is also observed in naturally buried samples such as
with increasing maturity after 0.89% VRo, with a maximum of gas shales and coals, interpreted to be the result of bitumen swell-
6.84 cm3/g and 2.60 cm3/g respectively at VRo of 3.48%, and then ing and compaction [22,38,39]. Effect of pore clogging by bitumen
a decrease with further increasing maturity. However, the carbon has been assessed by Valenza et al. via comparing surface areas and
dioxide adsorption capacity of sample EP gradually decreases from micropore volumes before and after solvent extraction [18]. They
0.71 cm3/g (VRo = 0.69%) to 0.22 cm3/g (VRo = 4.19%), which is observed a largely consistent rise in surface area and micropore
consistent with its nitrogen adsorption characteristics. volume after the solvent extraction, especially in the oil window.
 J. Chen, X. Xiao / Fuel 129 (2014) 173–181 177

Fig. 2. Nitrogen isotherms for sample LCG with different maturities.

Fig. 3. Nitrogen isotherms for sample DL with different maturities.

Bernard et al. [40] documented the chemical evolution of Missis-
sippian Barnett Shale samples from Fort Worth Basin ranging from
immature to postmature, suggesting that kerogen exhibits a trend
of aromatization, demethylation and deoxygenation during matu-
ration. In contrast, bitumen generated in the oil window stage
appears aromatic-poor, aliphatic-rich and oxygen-rich, which is
likely to fill in intra- and intergranular spaces, thereby reducing
the porosity [40]. Thus, the difference of the nanopore evolution
between sample LCG and sample DL in the oil window stage can
be referred to their oil generation potentials. Sample LCG contains
oil-prone kerogen which could generate a large amount of
asphaltene-rich bitumen, leading to a pore occlusion in the oil win-
dow stage. Sample DL contains gas-prone kerogen, which could
generate a relatively small amount of bitumen, thus the influence
on the nanopores would be small.
A further examination of the pore volume of samples LCG and
DL reveals that micropore volume exhibits a noticeable decrease
with VRo > 3.48%, while the mesopore volume and total volume
(micropore volume plus mesopore volume) still increase with the
maturity (Fig. 6A2 and B2). This phenomenon implicates the trans-
formation of micropore to mesopore and expansion of the meso-
porous pore size with further increasing maturity. In general,
there is an inverse relationship between pore size and specific sur-
face area for a given pore volume [4,5], thus this transformation
and expansion also result in a reduction of micro- and mesopore
surface areas (Fig. 6A1 and B1).
178 J. Chen, X. Xiao / Fuel 129 (2014) 173–181
Fig. 4. Nitrogen isotherms for sample EP with different maturities.
Fig. 5. Carbon dioxide isotherms for three suits of shale samples with different
maturities.
In order to evaluate the effect of thermal maturation on nano-
pore structure of clay minerals, sample EP containing rare organic
matter (TOC = 0.18%) was pyrolyzed under the same conditions as
the two organic-rich shales. The surface areas and volumes of its
micro- and mesopores present a monotonically decreasing trend
with increasing maturity (Fig. 6C1 and C2). As compared to the ini-
tial sample, the micro- and mesopore volumes reduce by 86.7% and
83.8% respectively, and its micro- and mesopore surface areas
reduce by 50.1% and 71.3% respectively, when it is matured to
the VRo value of 4.19 %. The result is in agreement with the heating
treatment of clay minerals [41,42]. Noyan et al. [42] observed an
overall trend of decline in both specific surface areas and micro-
mesopore volumes with increasing heating temperature from100
to 900 °C for Hancili bentonite from Turkey. In consideration of
the high content of clay minerals (56.8%), but a very small amount
of organic matter (TOC = 0.18%) in sample EP, it is believed that the
evolution of its nanopore structure is primarily controlled by
changes in the clay minerals. Diagenesis of clay minerals mainly
includes the dehydration and microstructural change (such as
reduction of interplanar spacing) [43,44], resulting in an obvious
decrease of the porosity [41,42], as well as the transformation of
mineral type (typically smectite to illite through a mixed-layer
illite–smectite) [45–48]. This transformation of clay mineral types
exists in normal geological environments [45,46] and also happens
under strictly controlled laboratory conditions [47,48]. However, it
does not occur under the experimental conditions of this study
(Table 2). The trends exhibited by sample EP can be ascribed to
the dehydration and framework collapse of clay minerals during
the process of thermal maturation [41–44].
Types and contents of quartz can also affect the pore volumes in
shales [10,17,49,50]. Especially for quartz of biogenic origin, it is
produced by precipitation during diagenesis with silica derived
from dissolution of opal if the geofluids are active, which may also
change the pore volume and structure in shales [10,51–53].
Although types of quartz were not examined for the studied shales,
any quartz should be stable under the anhydrous pyrolysis condi-
tion of the present study. From Table 2, the quartz contents vary
irregularly within a narrow range with increasing pyrolysis tem-
perature, indicating that quartz has not a significant effect on the
nanoporosity evolution of the studied shale samples.
These observations demonstrate two evolutionary routes of
nanopore structure in these shales under the present study condi-
tions: increase of nanoporosity in the organic matter (regardless of
the possible reduction taking place in the oil window stage) and
 J. Chen, X. Xiao / Fuel 129 (2014) 173–181
Fig. 6. Surface areas and pore volumes of micro- and mesopores, as functions of thermal maturity as indicated by vitrinite reflectance (VRo). A1, A2: sample LCG; B1, B2:
sample DL; C1, C2: sample EP.
reduction of nanoporosity in the clay minerals. This opposite evo-
lutionary tendency will largely affect how the nanopore structure
of the shales as a whole develops with thermal maturity. Thus, it
can be concluded that an increase in shale porosity with thermal
maturation is mostly associated with changes in the porosity of
organic matter, which is consistent with previous studies for
natural shale samples [1–4,18,22,54], and evolution of the OM-
hosted nanopores will become an important factor to influence
gas storage capacity of shales with very high maturity.
3.5. Evolutionary characteristics of nanoporosity in shales
Gas generation of organic matter in shales mainly includes the
three pathways [55]: (1) kerogen cracking to asphaltene and gas;
(2) asphaltene cracking to oil and gas; (3) oil cracking to gas and
pyrobitumen. Gas generation is always accompanied by the forma-
tion and transformation of porosity. Based on the results of the
present study, the evolution of OM-hosted nanoporosity of gas
shales can be roughly divided into three stages.
(1) Formation stage of OM-hosted nanopores (0.6% < VRo < 2.0%)
In this stage, oil is generated from kerogen and the generated oil
is cracked to gas, with the formation of organic porosity in shales.
Primary and secondary migration of the generated oils will occur in
the oil window stage, with residual oil rich in asphaltene and resin,
filling in intra- and intergranular spaces, resulting in a decrease of
shale porosity. At higher maturation, pyrobitumen is produced by
oil cracking to gaseous hydrocarbons [56,57]. This pyrobitumen
179
and residual kerogen are nanoporous due to the expulsion process
of hydrocarbon gas during oil cracking, which make a contribution
to the total porosity of shales [6,19,40,50]. Therefore, naoporosity
of oil-prone shales, in this stage, will typically shows a decrease,
and then an increase.
(2) Developing stage of OM-hosted nanopores (2.0% < VRo < 3.5%)
In this stage, methane is generated further from kerogen and
pyrobitumen, and the secondary cracking of heavy hydrocarbon
gases (C2–5) [56,57], with more matured residual kerogen and
pyrobitumen. These solid organic matters will gradually evolve
towards the development of a graphitic-like structure with a large
number of nanopores, leading to a rapid increase of the pore
volume and specific surface area of micro- and mesopores.
(3) Conversion and destruction stage of OM-hosted nanopores
(VRo > 3.5%)
A large amount of nitrogen will be generated through further
decomposition of solid organic matter in shales at very high matu-
rity with further increasing temperature and pressure, and trans-
formation and destruction of nanopores will occur. Under the
experimental conditions of the present study, the nanopores are
enlarged after VRo > 3.5%, with a decrease of microporosity and
an increase of mesoporosity, which can be attributed to the trans-
formation of micropores to mesopores and/or mesopores to
macropores. However, organic porosity may also be affected by
post-compaction under geological conditions. Using field-emission
180 J. Chen, X. Xiao / Fuel 129 (2014) 173–181
scanning electron microscopy (FE–SEM) techniques on a suit of
Marcellus Shale samples from northern Pennsylvania ranging from
VRo 1.0 to 2.1%, Milliken et al. [54] found that the preservation of
organic porosity is related to the content of organic matter, and a
reduction of organic nanoporosity occurs by compaction when
the organic matter content exceeds a certain value, for instance
TOC > 5.5% for Marcellus Shale.
It should be noted that the proposed pattern is a general model,
and it should be celebrated by substantial natural shale samples.
Many factors such as types, quantities and occurrence of organic
matter in shales, variations in mineral components and composi-
tions, as well as features of geothermal fluids may, on further
investigation, result in significant differences in nanoporosity
evolution with increasing maturity.
4. Conclusions
Three suites of artificially matured shale samples spanning a
range of 0.69–4.19% VRo were obtained from anhydrous pyrolysis
experiments, and their microporosity and mesoporosity were
investigated by low pressure nitrogen and carbon dioxide adsorp-
tion. The following conclusions were obtained.
(1) The two organic-rich shales have a substantially similar
evolutionary tendency in their micropore and mesopore
characteristics. Their micropore volumes, micro- and meso-
pore specific surface areas show an increase within the
maturity range from the oil window to about 3.50% VRo,
and then turns to a slight decrease with further increasing
maturity, but their mesopore volume shows an increase
after 3.50% VRo up to the maturity (VRo = 4.19%) achieved
by the pyrolysis experiment.
(2) The micro- and mesopore specific surface areas and pore
volumes of the organic-poor shale show a simple decrease
with maturity. From 0.69% to 4.19% of VRo, the reduction
is 86.7% and 83.8% respectively for the micro- and mesopore
volumes, and 50.1% and 71.3% respectively for its micro- and
mesopore surface areas.
(3) The increase of the nanoporosity in organic-rich shales dur-
ing thermal maturation is mainly attributed to the formation
of a large number of nanopores within organic matter. The
formation and evolution of the OM-hosted nanopores in
shales can be roughly subdivided into three stages: forma-
tion stage (0.60% < VRo < 2.0%), development stage
(2.0% < VRo < 3.5%), and conversion or destruction stage
(VRo > 3.5%).
Acknowledgements
The authors are indebted to three anonymous reviewers for
their insightful comments and suggestions that have significantly
improved the manuscript, and to Dr. Wilkins, R.W.T. for improving
the English. This study was jointly supported by National Key Basic
Research Program of China (973 Program, No. 2012CB214705),
Chinese Academy of Sciences (XDB10040300) and a Special Found-
ing from the State Major Research Programme of China (No.
2011ZX05008-002-40).
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