Molecular Physics

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Molecular simulation of shale gas adsorption onto

overmature type II model kerogen with control
microporosity

Lukáš Michalec & Martin Lísal

To cite this article: Lukáš Michalec & Martin Lísal (2017) Molecular simulation of shale gas
adsorption onto overmature type II model kerogen with control microporosity, Molecular Physics,
115:9-12, 1086-1103, DOI: 10.1080/00268976.2016.1243739

To link to this article: https://doi.org/10.1080/00268976.2016.1243739

Published online: 24 Oct 2016.

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MOLECULAR PHYSICS, 
VOL. , NOS. –, –
http://dx.doi.org/./..

SPECIAL ISSUE IN HONOUR OF JOHANN FISCHER

Molecular simulation of shale gas adsorption onto overmature type II model

kerogen with control microporosity
Lukáš Michaleca,b and Martin Lísala,b
a
Laboratory of Aerosols Chemistry and Physics, Institute of Chemical Process Fundamentals of the CAS, v. v. i., Prague, Czech Republic;
b
Department of Physics, Faculty of Science, J. E. Purkinje University, Ústí n. Lab., Czech Republic

ABSTRACT ARTICLE HISTORY

We use an all-atom molecular dynamics simulation to generate the dense porous structures of over- Received  July 
mature type II kerogen with control microporosity. The structures mimic the organic part of Barnett Accepted  September 
shale under a typical reservoir condition of 365 K and 275 bar. First, we build an atomistic model of
KEYWORDS
kerogen unit using the consistent valence force field and chemical structure proposed by Ungerer Barnett shale; clay; multiscale
and his colleagues. Second, we generate kerogen structures by gradual cooling and compression kerogen model; organic
of the initial low-density random configurations of kerogen units. During the structure generation, matter; pore space
we use a dummy particle of varying size to introduce microporosity into the kerogen structures. We accessibility
systematically characterise the microporous kerogen structures by calculating the geometric pore
size distribution, pore limiting diameter, maximum pore size, accessible surface area, and pore vol-
ume and by analysing the pore network accessibility. Third, we employ grand canonical Monte Carlo
(GCMC) to study the adsorption of two proxies of shale gas (pure methane and mixture of 82% of
methane, 12% of ethane and 6% of propane) in the kerogen structures. The shale gas adsorptions
are compared with GCMC simulation of CO2 adsorption in the kerogen structures. Hydrocarbons are
modelled using the all-atom optimized potential for liquid simulations (OPLS) force field while car-
bon dioxide is represented by the EPM2 model. We complement the adsorption studies by exploring
accessibility of pore space of the kerogen structures using molecular dynamics simulation. Finally,
we introduce a mesoscale pore void into a microporous kerogen structure and probe the adsorption
behaviour of the hydrocarbon mixture in such a multiscale kerogen model.

1. Introduction natural gas supply worldwide in recent years. The shale

gas is extracted by hydraulic fracturing which is the
Shale gas is an important unconventional energy resource
process where typically water with additives is pumped
that has had a potential game-changing effect on
into shale formations to fracture the rock and increase

CONTACT Martin Lísal lisal@icpf.cas.cz

©  Informa UK Limited, trading as Taylor & Francis Group
 MOLECULAR PHYSICS 1087

the extraction rate of natural gas or crude oil [1,2]. It

should be noted that any liquid may be used to create
fractures and light hydrocarbons like propane have been
also considered for fracturing the rock. Shale is com-
prised of two distinct parts: organic material and clay
minerals. The organic material is primarily composed
of kerogen, a mixture of organic chemical compounds
insoluble in common polar solvents such as chloro-
form or dichloromethane [3]. Clays are comprised of
a large number of particles arranged in piles of sheets.
The most abundant types of clay minerals are smectites
(swelling) and illites (non-swelling). Besides clay miner-
als, the inorganic part of shales may also contain fine-
grained quartz, carbonates, pyrite and so on. Kerogen
is generally hydrophobic while clay is hydrophilic, and
water can easily be adsorbed onto clay surfaces [3,4].
In shale formations, shale gas (typically a mixture of
methane, ethane and propane with a very small amount
of butane and heavier hydrocarbons as well as carbon
dioxide and nitrogen) is stored as free gas, adsorbed gas
and dissolved gas. The free gas gathers in the fractures
and pores of a shale rock, the adsorbed gas occurs on
the surfaces of both the organic material and clay min-
erals, and the dissolved gas enriches the organic mat-
ter. The adsorbed and dissolved gas is in equilibrium
with a homogeneous free gas phase in an interconnected Figure . The van Krevelen diagram, a plot of hydrogen-to-carbon
shale pore structure. If some shale pores are not inter- (H/C) and oxygen-to-carbon (O/C) atomic ratios, was used to clas-
connected, there may be a departure from the equilib- sify different types of kerogen in terms of depositional origin and
rium between the adsorbed and dissolved gas, and the maturity [,]. R is the vitrinite reflectance, a geochemical indica-
tor that measures thermal maturity of type II kerogens by integrat-
free gas. The amount of free gas is relatively easy to esti- ing the effects of time and temperature during the maturation of
mate based on the temperature and formation pressure, sediments. The star indicates the overmature type II kerogen stud-
its porosity, and the fraction of porosity which is filled by ied in this work.
the gas. The contribution of adsorbed gas to the total gas
in place (GIP), estimated to reach up to 60%, is still poorly of kerogens due to exposure to high temperature and
understood, mainly due to complexity of the gas adsorp- pressure over geological time scales leads to a shift of the
tion on shale. Generally, most of the adsorption area is kerogen H/C and O/C atomic ratios in the van Krevelen
located in the organic material and the contribution of diagram from the top-right to bottom-left corners.
the adsorbed gas to the total GIP is less significant in the In recent years, there has been an increasing effort
inorganic matrix [3]. to use atomistic simulations and provide molecular level
Kerogen, a main part of the organic matter, is a insight into shale gas behaviour in different types of kero-
complex material composed of an amorphous porous gen. The effort starts with the construction of realis-
carbon skeleton and exhibits significant pore-shape and tic kerogen models which is followed by simulations of
pore-connectivity variations. Depending on its shale gas adsorption, diffusion and transport in the kero-
geographic origin, maturity and sedimentary history, gen models. The structure of real kerogens is unknown
kerogen displays a broad range of density and, chemical and experimental techniques such as XPS, 13 C NMR and
composition in terms of atomic contents and chemical S-XANES are utilised to characterise kerogen samples
functions, porosity and tortuosity. The van Krevelen in terms of their elemental composition (H, C, O, S,
diagram (Figure 1) [5,6], a plot of hydrogen-to-carbon N), functional groups containing carbon and hydrogen,
(H/C) and oxygen-to-carbon (O/C) atomic ratios, pro- oxygen, sulphur and nitrogen, percentage of aromatic
vides a tool to distinguish different types of kerogen in carbon with attachments, average number of aromatic
terms of depositional origin: type I (lacustrine), type II carbons per polyaromatic cluster and average aliphatic
(marine), type III (terrestrial) and type IV (originating carbon chain length [7]. The experimental data on the
from residues) and maturity. Increasing the maturity kerogen characterisation can then be employed first to
1088 L. MICHALEC AND M. LÍSAL
reconstruct a two-dimensional model of kerogens and
subsequently based on the two-dimensional model, to
construct a three-dimensional model of kerogens using a
combination of ab initio and molecular mechanics calcu-
lations. Siskin’s model of Green River oil shale kerogen is
a typical example of such an approach [8–10]. However,
the size of such kerogen models is generally large since
it is necessary to match the elemental analysis including
minor elements such as sulphur and nitrogen, and the
qualitative distribution of pyrolysis products.
A somewhat different approach was taken by Coasne’s
group [11] that employed a Molecular Dynamics-
Hybrid Reverse Monte Carlo (MD-HRMC) reconstruc-
tion method [12] and built various realistic kerogen
models that differ in geological origin, elemental com-
position and maturity. By imposing the H/C and O/C
atomic ratios, distribution of chemical groups and carbon
hybridisation, the MD-HRMC method, powered with
reactive force fields [13,14], reconstructs a model of kero-
gens by matching experimental and simulated C–C pair
distribution functions.
A rather general and efficient approach for the con-
struction of realistic kerogen models of different types
and maturity has recently been proposed by Ungerer
and his colleagues [15–17]. The approach first consid-
ers model units with 170–260 carbon atoms (300–650
atoms in total) that match as closely as possible the ele-
mental analysis, the distribution of functional groups and
the structural features of kerogen. The units then serve as
building blocks for the generation of dense porous kero-
gen structures.
Building a kerogen unit begins with the selection of
a total number of carbon atoms and a number of aro-
matic carbons to match the aromaticity that is known
from XPS and NMR, the determination of the number of
H, O, S and N atoms required to approximate the elemen-
tal analysis and distribution in functional groups, and
determination of the number of aromatic units match-
ing the number of aromatic carbons per aromatic unit.
The second step includes building a preliminary struc-
ture of the kerogen unit using an appropriate force field
by matching equilibrium bond lengths, bond angles and
dihedral angles as closely as possible and by selecting the
appropriate level of cross-linking between aromatic units.
The preliminary structure is then subject to energy min-
imisation, i.e. atom coordinates of the structure are itera-
tively adjusted to minimise the potential energy given by
the force field. In the last step, the minimised structure
is refined to improve the agreement with elemental and
functional group analyses. The refinement involves either
a change in the shape of polyaromatic units or a change
in the location of functional groups to better represent
the percentage of aromatic carbons with attachments and
the percentage of aromatic carbons linked with hydro-
gen atoms only. The process of building the kerogen unit
avoids stacking the polyaromatic nuclei. Finally, start-
ing from a low-density random configuration of kerogen
units, a dense kerogen structure is typically obtained by
gradual cooling and compression of the initial configura-
tion using a molecular dynamics (MD) simulation [18].
Besides the effort to build realistic kerogen mod-
els and determine their volumetric, thermodynamic
and mechanical properties [11,17], grand canonical
Monte Carlo (GCMC) and equilibrium as well as non-
equilibrium MD [18,19] have been used to study gas
adsorption, diffusion and transport in model kerogen
structures under typical reservoir conditions. The studies
include GCMC simulations of adsorption of pure alka-
nes and alkane mixtures, N2 and CO2 onto type II kero-
gen models as well as proxies of kerogen, the equilibrium
MD of alkane and CH4 /CO2 diffusion in dense kerogen
structures, and non-equilibrium MD of alkane transport
in microporous structures of kerogen [11,15,20–26], to
name just a few.
GCMC simulations provide the total gas content,
i.e. the entire quantity of gas that resides in the pore
space at a given temperature and pressure. To bet-
ter understand adsorption behaviour in the kerogens,
it is useful to differentiate between the number of
gas molecules that would fill a given volume in the
absence of pore walls and the number of molecules that
would fill that same volume, but with the inclusion of
pore-wall effects at the same temperature and pressure
[27–29]. This can be discussed in terms of the excess
adsorption defined as the additional amount of gas
adsorbed per unit of pore volume compared with the
amount of gas in the same volume of a given pore in the
absence of pore walls [28]. To systematically examine
the effect of pressure, temperature and pore size on
methane adsorption in kerogens (which is carbon-based
three-dimensional pore-networks with a significant
amount of surface area contained in micropores) Mosher
et al. [28] simulated methane adsorption in idealised
carbon slits with widths ranging from 4 to 90 Å at various
temperatures and pressures characteristic of shale rock
conditions. They found that when pressure increased, the
amount of the excess increased up to a certain pressure,
and then decreased to zero at the pressure for which
there was no noticeable change in density as a result of
adsorption. The increase with pressure followed by a sub-
sequent decrease suggests that there exists a maximum
adsorbed quantity. An increase of temperature reduced
adsorption for equivalent pressures, but the maximum
number of adsorbed molecules remains constant. As
pressure increased at higher temperatures, the excess
adsorption isotherm peaks and subsequently descends at
 MOLECULAR PHYSICS 1089

higher pressures than for the same-sized pores at lower Table . The MD relaxation procedure for the generation of dense
temperatures. When the slit width was varied, larger porous kerogen structures. NVT denotes the canonical MD while
pores exhibit a lower excess density as compared to NPT denotes the constant pressure–constant temperature MD
with anisotropic box changes. T is the temperature, t is the length
smaller pores. At a pressure above 10 bar, the adsorp- of particular MD runs and P is the pressure. The values of t were
tion capacities of 6 Å pores drops below those of the set to be long enough to ensure the relaxation of the inter-
wider pores and decreases below that of the 12 Å pore at and intramolecular configurational energy, and system density to
180 bar. The density of the adsorbed methane changes their equilibrium values.
non-monotonically with increasing pore width, and Ensemble T (K) t (ns) P (bar)
drops to a minimum in 12 Å pores at 120 bar [28].
NVT  . –
In this work, we employ GCMC and study the adsorp- NPT  . 
tion of shale gas and carbon dioxide onto overma- NPT  →  . 
NPT  . 
ture type II kerogen structures of varying microporos- NPT  →  . 
ity which aim to mimic the organic part of Barnett shale. NPT  . 
Although kerogen is generally the most abundant compo- NPT  →  . 
NPT  . 
nent of the organic matter, a real organic matter also con- NPT  .  → 
tains asphaltenes, resins, hydrocarbons and other fluids NPT  . 
NPT  →  . 
such as carbon dioxide, water and nitrogen. Simulations NPT  . 
of organic matter containing both kerogen and minor
components will be the subject of our future work. Shale
gas and CO2 are modelled using the all-atom optimized kerogen is indicated by a star. The kerogen unit has a
potential for liquid simulations (OPLS) [30] and EPM2 chemical formula C175 H102 O9 S2 N4 , the molecular weight
[31,32] force fields, respectively. The kerogen structures is Mw = 2468.9 g/mol, and its molecular model is shown
are built using MD simulations from a kerogen unit in Figure 2(a). Figure 2 also provides the composition and
whose chemical structure was proposed by Ungerer et al. structural parameters of the kerogen unit.
[17]. The kerogen structures are modelled using the con- To generate a representative kerogen structure, we
sistent valence force field (CVFF) [33]. In addition, we placed 12 kerogen units (to avoid self-interactions of
explore the accessibility of the pore space of the kerogen kerogen units through the periodic boundary conditions)
structures and probe shale gas adsorption behaviour in to a large simulation box of 100 Å × 100 Å × 100 Å (initial
a multiscale kerogen model for the shale gas. The mul- kerogen density about 0.05 g/cm3 ) with periodic bound-
tiscale kerogen model is constructed by introducing a ary conditions in all directions and compressed the ini-
mesoscale pore void into our microporous kerogen struc- tial kerogen configuration from a high temperature to a
ture. The remainder of the paper is organised as fol- typical reservoir condition of 365 K and 275 bar, corre-
lows. The methodology for the generation of dense kero- sponding to the Barnett shale. The kerogen units were
gen structures with control microporosity is outlined in placed into the simulation box randomly without over-
Section 2. Section 3 presents molecular models of the lap and with the same orientation. We chose the same
kerogen structure, methane, ethane, propane and car- initial orientation of the kerogen units since they are flat
bon dioxide. Section 4 provides computational details and we anticipated they tend to stack parallel in a com-
about the MD and GCMC simulations. In Section 5, we pressed state. The compression and cooling of the initial
then present and discuss our results for the adsorption configuration was performed in stepwise fashion using
of methane, mixture of methane, ethane, and propane MD, and Table 1 summarises the details of MD relaxation
and carbon dioxide in the kerogen structures. Finally, we procedure. In contrast to Ungerer’s MD relaxation proce-
present our conclusions in Section 6. dure [15–17], we added a refinement step that involved
heating the final configuration at 365 K and 275 bar to
2000 K, followed by 1 ns gradual cooling back to 365 K
2. Methodology
under a constant pressure of 275 bar and a subsequent
1 ns relaxation run at 365 K and 275 bar. The tempera-
2.1. Microporous kerogen structures
ture of 2000 K guaranteed that the system did not expand
We are interested in shale gas behaviour in kerogens asso- when we switched on the gradual cooling. This leads to
ciated with unconventional gas reserves [34]. Therefore, refinement of the stacking of the kerogen units, and in
we used the chemical structure of kerogen unit proposed turn, to an increase in system density. Figure 2(b) displays
by Ungerer et al. [17] that represents overmature type II an example of the time variation of the system tempera-
kerogens found in shale formations of the Barnett play ture and kerogen density during MD generation of the
[35]. In the van Krevelen diagram (Figure 1), the studied kerogen structures. A final structure typically contained
1090 L. MICHALEC AND M. LÍSAL

Figure . (a) Molecular model of a kerogen unit representing overmature type II kerogen. The red, blue, yellow, grey and white spheres
represent oxygen, nitrogen, sulphur, carbon and hydrogen atoms, respectively. The chemical formula of the kerogen unit is C H O S N ,
its molecular weight Mw = . g/mol, and the atomic ratios H/C = ., O/C = ., S/C = . and N/C = .. Another composition
and structural parameters of the kerogen unit can be found in Ref. []. (b) Example of time variation of the system temperature and
kerogen density during the MD generation of the porous kerogen structure which was accomplished within . ns. (The colour ranges
refer to the online version of the paper).
 MOLECULAR PHYSICS 1091

Figure . Geometric pore size distribution, PSD, as a function of the pore diameter for the porous kerogen structures with different micro-
porosity. The microporosity was introduced via the dummy particle of size σ LJ .

Table . The kerogen density, ρ, accessible surface area, SA , constant pressure–constant temperature (NPT) ensem-
pore volume, Vpore , pore limiting diameter, Dmin , and maxi- ble with anisotropic box changes. We employed the
mum pore size, Dmax , of the kerogen structures with different Nose–Hoover thermostat [37,38] and the Nose–Hoover
microporosities corresponding to the dummy particle of size
σ LJ . The simulation uncertainties are given in the last digits as barostat [39,40].
subscripts. The GCMC established an equilibrium between a
homogeneous free gas in an interconnected shale pore
σ LJ (Å) ρ (g/cm ) SA (m /g) Vpore (cm /g) Dmin (Å) Dmax (Å)
structure and adsorbed gas in the kerogen network, i.e.
 . . . . . equivalence of the chemical potentials of gas species. The
 . . . . .
 . . . . .
chemical potential of the free gas was obtained by config-
 . . . . . urational bias Widom’s insertion method [18,19] during
 . . . . . an NPT MC simulation at 365 K and 275 bar, performed
in a cubic simulation box with periodic boundary condi-
ultramicropores (pore width <1nm) that was a result of tions in all directions.
the void space left between kerogen units in the com- The GCMC employed two types of trial moves: parti-
pressed state. To introduce micropores (pore width of 1–2 cle displacement and particle insertion/deletion to/from
nm) into our kerogen models, we used a dummy particle the kerogen structure. The displacement moves involved
of varying size during the MD relaxation procedure. The transitional, rotational and configurational bias moves to
dummy particle was then removed from the compressed satisfy temperature equilibration. The insertion/deletion
kerogen structure, leaving a void where gas adsorption is moves included insertion of a gas molecule in the
likely to occur. kerogen structure or removal of a gas molecule from
the kerogen structure, both using the configurational
bias technique, to ensure chemical potential equili-
2.2. MD and GCMC bration [19]. The NPT MC and GCMC simulations
were carried out using the Towhee simulation package
The MD simulations were performed with the LAMMPS [41].
code [36] in a canonical (NVT) ensemble and
1092 L. MICHALEC AND M. LÍSAL

3. Molecular models 4. Computational details

We modelled kerogen structures using the CVFF [33] We used the particle–particle particle–mesh algorithm
which is a standard and reliable force field for simulations [44] in the MD and Ewald summation technique [18] in
of organic molecules. The functional form of the CVFF NPT MC and GCMC, both with a precision of 1 × 10−4
is [45], to treat long-range electrostatic interactions. We fur-
ther utilised the cut-off radius between 10 and 17 Å, and
U = Ubonded + Unonbonded time step of 1 fs in MD. In NPT MC, we typically used
  500 gas molecules, 5 × 106 equilibration moves, 10 × 106
= kb (b − b0 )2 + kθ (θ − θ0 )2
production moves, and frequency for conformation, rota-
bonds angles
    tion, translation and volume attempts equal to 0.33, 0.33,
+ kφ 1 + cos nφ φ (1) 0.33 and 0.01, respectively. Ten virtual insertions every
dihedrals
 500 production moves were performed to measure the
  
+ kψ 1 + cos nψ ψ chemical potential of the free gas by configurational bias
impropers Widom’s method. Similarly, in GCMC, we utilised 5 × 106
 
12
6   equilibration moves, 10 × 106 production moves, and fre-
 σi j σi j
+ 4εi j − +
ri j ri j
i j>i
where b, θ, φ and ψ denote the bond length, bond angle,
dihedral angle and improper angle, respectively; b0 and θ 0
are the equilibrium bond length and bond angle, respec-
tively; kb , kθ , kφ and kψ are the force constants; nφ and nψ
are the dihedral and improper angle parameters, respec-
tively; εij and σ ij correspond to the Lennard–Jones (LJ)
energy and size parameters, respectively; qk is the partial
charge on atom k; ϵ0 is the permittivity in vacuum and rij
is the distance between atom i and atom j. The dummy
particle, employed to control the structure microporos-
ity, was represented by a repulsive LJ particle with
Mw = 220 g/mol, εLJ /k = 100 K and σLJ =
{0, 9, 11, 13, 15}Å; k is the Boltzmann constant.
We employed the all-atom OPLS models for methane,
ethane and propane [30], and the flexible EPM2 model
for carbon dioxide [31,32]. Both OPLS and EPM2 force
fields have been shown to reproduce rather well the ther-
modynamic and vapour–liquid equilibrium properties
[42,43], and in addition, the force fields are compati-
ble with CVFF [33]. The intramolecular interactions in
methane, ethane and CO2 included the vibrational and
bending contributions, while those in propane involved
the vibrational, bending and torsion contributions. The
functional forms of the intramolecular contributions
are given by Equation (1). The intermolecular interac-
tions were modelled by the LJ and Coulombic potentials
(see Equation (1)). The cross-LJ parameters were given by
the Lorentz–Berthelot combining rules [18]:
√ σii + σ j j
εi j = εii ε j j , σi j =
2
For the values of LJ parameters and partial charges, we
refer the reader to the original papers [30–33].
qi q j
quency for conformation, rotation, translation and inser-
4π0 ri j
tion/deletion attempts equal to 0.25, 0.25, 0.25 and 0.25,
respectively.
We systematically characterised the kerogen structures
by calculating the geometric pore size distribution (PSD),
pore limiting diameter, Dmin , maximum pore size, Dmax ,
accessible surface area, SA , and pore volume, Vpore , and
by analysing the pore network accessibility [46]. The PSD
was determined by MC procedure that probed the kero-
gen pore space to find the largest spheres that contained
test points and did not overlap with the atoms of the kero-
gen structure. The test points were randomly placed in the
simulation box with no overlaps with the kerogen atoms.
Each sphere then defined the volume of a void space that
can be covered by a sphere of radius r or smaller, Vp (r).
The derivative −dVp /dr is the PSD and was obtained by
numerical differentiation of Vp (r) [47]. The value of Dmax
is a by-product of the PSD calculation.
The accessible surface area corresponds to the posi-
tions of the centre of a probe particle rolling over the
kerogen atoms. It is thus defined as a locus of the points
that represents the location of the probe particle at a dis-
tance of the collision diameter σ from a kerogen atom
and at least a distance σ from all other atoms of the kero-
gen structure. Calculation of SA did not involve the actual
rolling of the probe particle but employed an MC proto-
col, described in detail elsewhere [46]. As a probe parti-
cle, we used nitrogen atom with σN = 3.314 Å to directly
relate the calculated SA to that measured in the BET
adsorption experiments. An analogous MC approach was
used for calculation of the pore volume where a He-
size probe of σHe = 2.58 Å was used to provide values of
Vpore consistent with that determined experimentally by
(2) helium pycnometry.
The analysis of the pore space accessibility aimed to
detect if the pore network in the kerogen structures was
fully accessible to a spherical probe of the size chosen to
 MOLECULAR PHYSICS 1093

be equal to σ N . The kerogen pore network was accessible
to the spherical probe if, for this probe, it was possible
to construct a continuous trajectory from one face of the
simulation box to the opposite face of the simulation box
without overlapping with the kerogen atoms. The value
of Dmin is a by-product of the percolation analysis. The
pore limiting diameter, Dmin , corresponds to a maximum
probe size for which a pore network still percolates. The
accessibility of the kerogen pore space was explored in all
three directions and details about its determination are
given elsewhere [46].
is in subcritical state. The model critical temperature, Tc ,
and pressure, Pc , have the following values: (Tc , Pc ) ࣃ
(191K, 46bar) for methane, (Tc , Pc ) ࣃ (285K, 47bar) for
ethane, (Tc , Pc ) ࣃ (372K, 46bar) for propane, and (Tc , Pc )
ࣃ (306K, 77bar) for CO2 [42,43]. They compare rather
well with experimental Tc and Pc : (Tc , Pc ) ࣃ (191K, 46bar)
for methane, (Tc , Pc ) ࣃ (305K, 49bar) for ethane, (Tc ,
Pc ) ࣃ (370K, 43bar) for propane, and (Tc , Pc ) ࣃ (304K,
74bar) for CO2 [48]. In addition, the model vapour
pressure of propane is Psat ࣃ 42 bar [42] while the exper-
imental Psat ࣃ 39 bar [48].

5. Results and discussion

All of the simulations were performed at a temperature
T = 365 K and pressure P = 275 bar, corresponding to a
reservoir condition of the Barnett shale formation. The
mixture of 82% of methane, 12% of ethane and 6% of
propane used in this work as a proxy of the shale gas rep-
resents a typical composition of the shale gas extracted
in the Barnett play [35]. At this T, methane, ethane and
carbon dioxide are in supercritical state, while propane
5.1. Kerogen structure characterisation
Starting from different initial configurations of kerogen
units, we typically generated 20 compressed configura-
tions for each size of the LJ dummy particle. The density
equilibration was slightly influenced by the initial con-
figurations. For adsorption simulations, we then chose
a high-density structure out of the 20 generated con-
figurations that had the lowest configurational energy.

Figure . Examples of the kerogen structures with low and high microporosities. The left column corresponds to the structure generated
without the dummy particle while the right column is for the structure generated with the dummy particle of size σLJ = 13 Å. We displayed
the periodic images for the sake of clarity. In portions (a) and (b) of the figure, the red, blue, yellow, grey and white spheres represent
oxygen, nitrogen, sulphur, carbon and hydrogen atoms, respectively. The portions (c) and (d) of the figure show the front and top views
of the kerogen structures with the cutting plane in the middle of simulation box to demonstrate percolation of the pore network probed
by nitrogen sphere. (The colour ranges refer to the online version of the paper).
1094 L. MICHALEC AND M. LÍSAL

In addition, we ran a 1 ns NPT MD and collected 10 struc-

tures separated by 0.1 ns for this structure. The dummy
particle was then removed from the collected structures.
The structures were statistically equivalent and repre-
sented the overmature type II kerogen. The size of corre-
sponding simulation boxes was (40–50) Å × (30–35) Å ×
(25–30) Å.
Table 2 summarises the various properties used to
characterise the kerogen structures. Figure 3 displays the
PSD of the kerogen structures with different microp-
orosities corresponding to the dummy particle with σLJ =
{0, 9, 11, 13, 15}Å. Results in Table 2 and Figure 3 were
averaged over the collected structures. Figure 4 provides
examples of the kerogen structures with low and high
microporosities. First, we see that density of the kerogen
structures was typically between 1.2 and 1.3 g/cm3 which
compared quite well with a range of the experimental
density 1.2–1.4g/cm3 found for mature and overmature
kerogens [49]. The kerogen density also agrees with a
range of simulation density 1.21–1.28 g/cm3 reported by
Ungerer et al. [17] on the same kerogen model but sim-
ulated with a different force field. Second, the PSD cor-
responding to no dummy particle suggested the pres-
ence of ultramicropores of size from 3–5 Å (see also
Figure 4(a)). The dummy particle created a host microp-
ore (where gas adsorption is likely to occur) proportional
to σ LJ as indicated by the pronounced peak in PSDs (see
also Figure 4(b)). Besides the host micropore, the kero-
gen structures corresponding to σLJ = {9, 11, 13, 15}Å
also contained smaller micropores and ultramicropores.
Experimental PSDs for isolated kerogens cannot be reli-
ably measured. However, experimental PSDs for shale
(i.e. including organic and inorganic matter) suggest the
existence of micropores larger than 1 nm [50,51], cf. PSDs
corresponding to σLJ = {13, 15}Å. Finally, the values of
SA , Vpore , and Dmax gradually increased with increasing
σ LJ while values of Dmin did not vary significantly with
σ LJ . In addition, the values of Dmin were small in com-
parison with the typical size of gas molecules, indicat-
ing a poor connectivity of pores in the kerogen structures
(see Figure 4(c,d)).

5.2. Adsorption
In GCMC simulations, the kerogen structures were
considered rigid for the sake of computational effi- Figure . The adsorbed amount of (a) methane, (b) shale gas and
ciency, neglecting swelling of adsorbent by the adsorbed (c) carbon dioxide, n, as a function of microporosity introduced
molecules. Tables 3–5 list the simulated adsorbed amount via the dummy particle of size σ LJ at a temperature of  K and
of methane, mixture of methane, ethane and propane pressure of  bar. The open symbols represent the GCMC results
as a proxy of the shale gas, and carbon dioxide, respec- while the filled symbols denote the MD results. For the MD sim-
ulations, we plot the maximal values of n only. The dotted lines
tively. Figure 5 then plots the simulated adsorbed amount,
through the GCMC results serve as a guide for the eye.
n, as a function of microporosity, i.e. in terms of
σ LJ .
 MOLECULAR PHYSICS 1095

Table . The adsorbed amount of methane, nCH4 , in the
microporous structures of overmature type II kerogen at a
temperature of  K and pressure of  bar. The microp-
orosity was introduced via the dummy particle of size σ LJ .
The results written in black correspond to GCMC simula-
tions while those written in red and blue represent MD sim-
ulations for rigid and flexible kerogen structures, respec-
tively, in the x-, y- and z-directions. The GCMC simulation
uncertainties are given in the last digits as subscripts. The
MD simulations were typically run for  ns. The correspond-
ing value of the chemical potential μCH4 /k = 76668 K was
determined by the configurational bias Widom’s method
during NPT MC simulations; k is the Boltzmann constant.
See Ref. [] for definition of the reference state for μCH4 .
(The colour ranges refer to the online version of the paper).
σ LJ (Å) nCH (mmol/g)
4
Table . The adsorbed amount of the shale gas (i.e. mixture of
% of methane, % of ethane and % of propane), nCH4 , nC2 H6 ,
and nC3 H8 , in the microporous structures of overmature type II
kerogen at a temperature of  K and pressure of  bar. The
microporosity was introduced via the dummy particle of size
σ LJ . The results written in black correspond to GCMC simulations
while those written in red and blue represent MD simulations
for rigid and flexible kerogen structures, respectively, in the x-,
y- and z-directions. The GCMC simulation uncertainties are given
in the last digits as subscripts. The MD simulations were typically
run for  ns. The corresponding values of the chemical poten-
tial μCH4 /k = 75767 K, μC2 H6 /k = 1709812 K, and μC3 H8 /k =
2669215 K were determined by the configurational bias Widom’s
method during NPT MC simulations; k is the Boltzmann constant.
See Ref. [] for definition of the reference state for μCH4 , μC2 H6
and μC3 H8 . (The colour ranges refer to the online version of the
paper).

 . σ LJ (Å) nCH (mmol/g) nC (mmol/g) nC (mmol/g)

H H
0.21/0.03/0.19 4 2 6 3 8

0.45/0.26/0.44
 . . .
 .
0.13/0.02/0.11 0.03/0.01/0.03 0.06/0.01/0.05
0.24/0.23/0.21
0.23/0.07/0.19 0.08/0.02/0.07 0.06/0.01/0.05
0.64/0.66/0.37
 . . .
 .
0.14/0.13/0.15 0.03/0.03/0.02 0.08/0.06/0.04
0.06/0.43/0.15
0.18/0.18/0.13 0.04/0.09/0.03 0.16/0.20/0.13
0.23/0.56/0.34
 . . .
 .
0.04/0.25/0.10 0.01/0.07/0.03 0.02/0.10/0.04
0.29/0.27/0.47
0.14/0.38/0.15 0.02/0.07/0.03 0.07/0.10/0.12
1.13/0.49/1.33
 . . .
 .
0.23/0.17/0.37 0.07/0.04/0.06 0.02/0.06/0.10
0.17/0.37/0.39
0.56/0.28/0.66 0.11/0.06/0.14 0.26/0.14/0.35
0.39/1.33/1.57
 . . .
0.11/0.24/0.24 0.02/0.05/0.07 0.05/0.07/0.09
0.14/0.34/0.70 0.01/0.12/0.18 0.14/0.28/0.29

We first see that n’s increased with rising σ LJ although

that increase was small for the kerogen structure corre-
sponding to σLJ = 9 Å. The values of nCH4 in the kero-
gen structures corresponding to σLJ = {13, 15}Å com-
pared rather well with the simulation results of Ho et al.
[26] in similar kerogen structures when Ho at al.’s sim-
ulation results were extrapolated to our temperature and
pressure. Second, gas adsorption onto the kerogen struc-
tures was stronger for CO2 than for CH4 and the ratio
nCO2 /nCH4 was about 1.3. The same finding about CO2
and CH4 adsorption onto similar type II kerogen struc-
tures was reported by Sui and Yao [25]. A stronger CO2
adsorption in comparison with CH4 adsorption on Bar-
nett’s shale samples was also experimentally measured
by Heller and Zoback [52]. This can be attributed to
stronger van der Waals and electrostatic gas–gas and gas–
adsorbent interactions in the case of CO2 adsorption.
To better understand the stronger CO2 adsorption, we
performed an additional GCMC simulation for the kero-
gen structure corresponding to σLJ = 15 Å and switched
off the partial charges in the CO2 model. We found
that the adsorbed amount decreased by about 10% with
respect to the original CO2 model, demonstrating an
enhancement of CO2 adsorption due to electrostatic
interactions. However, the adsorbed amount of CO2 of
the modified model was still higher than that for CH4 ,
demonstrating stronger van der Waals interactions for
CO2 –kerogen systems compared to CH4 –kerogen sys-
tems. Third, our results for the proxy of Barnett’s shale
gas, i.e. a mixture of 82% of methane, 12% of ethane
and 6% of propane indicated preferential adsorption of
propane and to a lesser extent ethane. An example is
that for the kerogen structure without the host microp-
ore (σLJ = 0 Å), the adsorbed mixture contained about
74% of CH4 , 20% of C2 H6 and 6% of C3 H8 . With increas-
ing microporosity (i.e. with increasing σ LJ ), the molar
percentage of methane decreased, that of ethane was
roughly constant (i.e. around 20%) and that of propane
gradually increased. For instance, for the kerogen struc-
ture corresponding to σLJ = 15 Å, the adsorbed mixture
consisted of about 59% of CH4 , 18% of C2 H6 and 23%
of C3 H8 . The strong preferential adsorption of propane
molecules can be associated with the condensation of the
propane molecules in larger micropores since, in contrast
to methane and ethane (which are in supercritical state),
propane is in subcritical state above the vapour pressure.
A similar observation was reported by Falk et al. [22] for
subcritical dodecane in model kerogens.
1096 L. MICHALEC AND M. LÍSAL
Table . The adsorbed amount of car-
bon dioxide, nCO2 , in the microporous
structures of overmature type II kerogen
at a temperature of  K and pressure
of  bar. The microporosity was intro-
duced via the dummy particle of size σ LJ .
The results written in black correspond
to GCMC simulations while those writ-
ten in red and blue represent MD sim-
ulations for rigid and flexible kerogen
structures, respectively, in the x-, y- and
z-directions. The GCMC simulation uncer-
tainties are given in the last digits as sub-
scripts. The MD simulations were typically
run for  ns. The corresponding value of
the chemical potential μCO2 /k = 18095
K was determined by the configurational
bias Widom’s method during NPT MC sim-
ulations; k is the Boltzmann constant. See
Ref. [] for definition of the reference
state for μCO2 . (The colour ranges refer to
the online version of the paper).
σ LJ (Å) nCO (mmol/g)
2
 .
0.19/0.22/0.17
0.90/0.45/0.62
 .
0.22/0.20/0.19
0.80/0.98/0.72
 .
0.06/0.37/0.14
0.48/1.84/1.08
 .
0.25/0.25/0.48
1.64/1.08/2.08
 .
0.16/0.37/0.40
0.48/1.97/2.31
Our simulation data on the methane adsorption in the
kerogen structures with the host micropore of size above
10 Å, i.e. in those corresponding to σLJ = {13, 15}Å can
be compared with the experimental data for the Bar-
nett shale reported by Gasparik et al. [53] and Zhang
et al. [54]. Comparison of the methane adsorption from
the simulations and experiments was made through the
excess adsorbed amount, nexcess . Excess adsorption is
the difference between the (total) adsorbed amount and
the amount of gas in the free volume in kerogen pores and
was estimated as
nexcess = n − Vpore ρPT (3)
where ρ PT is the density of bulk methane at T = 365 K
and P = 275 bar. The value of ρ PT = 891750 mol/m3 was
obtained by NPT MC simulation during measurement of
the chemical potential. The simulated value agreed rather
well with the experimental value of ρ PT = 9263 mol/m3
[48]. From Equation (3), we obtained nexcess CH4  0.77 and
0.95 mmol/g for the kerogen structures corresponding to
σ LJ = 13 and 15 Å, respectively. Extrapolation of experi-
mental data to our T and P yielded a nexcessCH4  1.7 mmol/g
for data from Gasparik et al.’s group [53] and nexcess CH4 
0.7 mmol/g for data from Zhang et al.’s group [54].
The excess adsorption data for the Barnett shale were
measured for the whole shale (i.e. including organic and
inorganic matter) and normalised by the total organic
carbon. The fact that two different samples from Barnett
shales exhibited different excess adsorption data demon-
strated the diversity and heterogeneity of shales. Hence,
the simulation nexcessCH4 for the model Barnett kerogen was
within a range of experimental nexcess
CH4 for the Barnett
shale [53,54]. In addition, the total and excess adsorp-
tion amount together with the pore volume enables us to
evaluate the average total and excess density of methane,
excess
ρ av and ρav , respectively, in the kerogen pore networks
and compare them with the density of bulk methane,
ρ PT = 891750 mol/m3 . For the kerogen structures
corresponding to σLJ = {0, 9, 11, 13, 15}Å, we obtained
ρ av = {15068, 16097, 16474, 17235, 16876} mol/m3 and
excess
ρav = {9041, 8828, 8840, 8259, 8009} mol/m3 . Values
excess
of ρ av are about twice of ρ PT while values of ρav are
comparable or slightly below ρ PT .
5.3. Pore space accessibility
The particle insertion/deletion moves in GCMC can take
place anywhere in the kerogen structure and GCMC thus
allowed adsorption in pores that were not connected to
the external surface of the structure. In contrast, these
inaccessible pores would stay empty in a real adsorption
experiment. To understand the effect of the pore network
accessibility on the gas adsorption in the kerogen struc-
tures we set up MD simulations that mimicked the real
adsorption experiment. In the following, we assume the
kerogen is protected from the total stress supported by
the mineral part of the shale.
An empty rigid kerogen matrix made up two copies
of the kerogen structure without the periodic boundary
conditions in the α-direction (α ࣕ x, y, z) was put in con-
tact with a gas reservoir. The two copies of the kerogen
structure guaranteed that the original kerogen structure
was recovered in the middle of the kerogen matrix. For
practical reasons, we used two reservoirs on the opposite
sides of the kerogen matrix which enabled us to employ
the periodic boundary conditions in all directions and
speed up the adsorption process (see Figure 6(a)). We first
equilibrated the system by NVT MD and then used NPT
MD with box changes in the α-direction only (NPαα T
MD) to allow the gas molecules to imbibe the kero-
gen matrix (see Figure 6(b–d)). We used Pαα = 275 bar,
 MOLECULAR PHYSICS 1097

Figure . Molecular dynamics simulations mimicking a real adsorption experiment. (a) An empty rigid kerogen matrix in contact with
shale gas (i.e. a mixture of % of methane, % of ethane and % of propane). (b) Shale gas molecules imbibed the rigid kerogen matrix
from one side only. (c) Shale gas molecules imbibed a small percolating pore in the rigid kerogen matrix. (d) Methane molecules imbibed
the rigid kerogen matrix with poor space accessibility from the external surface. The red, blue and green spheres represent methane,
ethane and propane molecules, respectively. The light blue spheres denote the host micropores. (The colour ranges refer to the online
version of the paper).

which corresponds to a reservoir condition of the Bar-
nett shale formation, and Pαα represents the fluid pres-
sure. We evaluated the adsorbed amount from density
profiles of gas molecules and kerogen atoms as depicted in
Figure 7. Figure 7 shows an example of methane, ethane
and propane number density profiles and kerogen mass
density profile in the direction of applied pressure. We
first determined boundaries between bulk kerogen and
gas reservoirs as the location where the kerogen structure
reached its bulk density reported in Table 2. We then com-
puted the values of n by integrating the gas number den-
sity profiles and kerogen mass density profile, and taking
their ratio.
The MD simulation results are summarised in
Tables 3–5, and are also shown in Figure 5. In Figure 5,
we plotted the maximal values of n only. Figure 6(b–d)
1098 L. MICHALEC AND M. LÍSAL
Figure . The number density profiles of methane, ethane and propane and the mass density profile of kerogen atoms in the direction
of applied pressure. The dash–dotted lines denote the boundaries between the kerogen and shale gas (i.e. a mixture of % of methane,
% of ethane and % of propane).
further demonstrates various scenarios of the gas
imbibition of the kerogen structures. We can see that for
methane and carbon dioxide, the MD results were below
the GCMC results by about 60 to 80%.
The above MD results for the rigid kerogen matrix
elucidated the pore space accessibility of the kerogen
structures with respect to GCMC. We further explored
the effect of the flexibility of the kerogen matrix on
gas imbibition. In contrast to MD simulations on the
rigid kerogen matrix, we allowed the kerogen atoms to
move. The kerogen matrix flexibility led to enhanced
gas imbibition of the kerogen structures since the
imbibed molecules might more easily diffuse through the
kerogen structures or might cause an opening and inter-
connection of the originally inaccessible pores. The MD
simulation results for the flexible kerogen matrix are
listed in Tables 3–5, and are displayed in Figure 5 where
only maximal values of n were plotted. We can see that the
MD results for the flexible kerogen matrix were still below
the GCMC results by about 10%–50%. An exception was
the mixture adsorption onto the kerogen structures cor-
responding to σ LJ = 9 and 13 Å where nC3 H8 from MD
simulations was above that from GCMC simulations as
a result of the propane preferential adsorption. Finally,
Figure 8 demonstrates the effect of the kerogen-matrix
flexibility by showing examples of methane imbibition for
the rigid and flexible kerogen matrix. The results for the
flexible kerogen matrix should be taken with care since
the moderate molecular weight of the model kerogen unit
along with absence of the cross-linking between the kero-
gen units allows too much flexibility when compared with
real kerogens.
5.4. Kerogen model combining different porosity
scales
Kerogens usually have pore networks that combine more
than one length scale. Hence, we considered a multiscale
model of kerogen with micropores (pore width <2 nm)
and mesopores (pore width of 2–50 nm). Similarly, as
was done in the previous Section 5.3, we used a rigid
kerogen matrix formed by two copies of the kerogen
structure with micropores corresponding to the dummy
particle with σLJ = 11 Å (cf. PSD in Figure 3) and with-
out the periodic boundary conditions in the y-direction.
The mesopores were introduced through a 14-Å-wide
slit cavity placed in contact with the kerogen matrix (see
Figure 9(a)). The size of the corresponding simulation
box was 49.62 Å × 85.32 Å× 28.03 Å. The PSD of
the multiscale kerogen model is shown in Figure 9(b).
Micropores with the width <1 nm came from the kero-
gen matrix while mesopores with the width around
2.5–2.7 nm resulted from the addition of the cavity. Pores
 MOLECULAR PHYSICS 1099

Figure . Methane molecules imbibed the rigid and flexible kerogen matrix during molecular dynamics simulations that mimic a real
adsorption experiment. In each portion of the figure, the upper snapshot shows a simulation corresponding to the rigid kerogen matrix
while the bottom snapshot displays a simulation corresponding to the flexible kerogen matrix. (a) The pronounced effect of kerogen-
matrix flexibility on the methane imbibition of the kerogen matrix. (b) The small effect of kerogen-matrix flexibility on the methane
imbibition of the kerogen matrix.

with the width ranging from 1–2.5 nm were due to the
interface between the kerogen matrix and cavity.
simulation,we obtained the adsorbed amounts:
We then used GCMC and studied the adsorp-
tion of the shale gas, represented by the mixture of
82% of methane, 12% of ethane and 6% of propane
[35]. Figure 10(a) displays the simulation density
profiles of methane, ethane and propane, and kero-
gen atoms along the y-direction and Figure 10(b)
shows a snapshot demonstrating the adsorption of the
shale gas in the multiscale kerogen model. From the
GCMC
nCH4 , nC2 H6 , nC3 H8 = {4.3913 , 1.168 , 1.278 } mmol/g.
Similarly, as was done in the previous Section 5.3,
we can compute the contribution to ni (i ࣕ CH4 , C2 H6 ,
C3 H8 ) from the kerogen matrix using the density profiles
from Figure 10(a). Integration of the density profiles
in a y-range corresponding to the (bulk) kerogen den-
sity of ∼1.25 g/cm3 (see Table 2), i.e. from 19 to 64 Å,
1100 L. MICHALEC AND M. LÍSAL

Figure . (a) The multiscale kerogen model that consisted of the rigid kerogen matrix with micropores corresponding to the dummy
particle with σLJ = 11 Å and a .-nm-wide slit cavity; density ρ = . g/cm , accessible surface area SA =  m /g, pore volume Vpore =
. cm /g, pore limiting diameter Dmin = 22.5 Å, and maximum pore size Dmax = 27.3 Å. The red, blue, yellow, grey and white spheres
represent oxygen, nitrogen, sulphur, carbon and hydrogen atoms, respectively. (b) The geometric pore size distribution, PSD, as a function
of the pore diameter for the multiscale kerogen model. (The colour ranges refer to the online version of the paper).

  
CH4 , nC2 H6 , nC3 H8
resulted in nmatrix matrix matrix
= {0.81, 0.29, 0.27} cavity cavity cavity
ρCH4 , ρC2 H6 , ρC3 H8 = {3.98, 1.00, 1.12}1/nm3 and
mmol/g. The value of nmatrix CH4 agrees within statisti- cavity
cal uncertainties with the previous GCMC result (see compared ρi with the bulk densities obtained 
Table 4) while the values of nmatrix matrix from NPT MC: ρPT,CH4 , ρPT,C2 H6 , ρPT,C3 H8 =
C2 H6 and nC3 H8 are only
slightly higher {4.593 , 0.671 , 0.341 }1/nm3 . From this comparison, we
than the GCMC results  in Table 4. By sub- cavity cavity
can see that ρCH4 < ρPT,CH4 while ρC2 H6 > ρPT,C2 H6 and
tracting nmatrix
CH4 , nmatrix
C2 H6 , nmatrix
C3 H8 = {0.81, 0.29, 0.27} cavity
mmol/g from ni , we evaluated the average densi- ρC3 H8 > ρPT,C3 H8 , indicating, similarly as was the case
ties of methane, ethane and propane in the cavity: in the microporous kerogen structures, the preferential
 MOLECULAR PHYSICS 1101

Figure . (a) The number density profiles of methane, ethane and propane and mass density profile of kerogen atoms for the multiscale
kerogen model. The dash–dotted lines denote boundaries between the kerogen and cavity. (b) A snapshot demonstrating the adsorption
of the shale gas (i.e. a mixture of % of methane, % of ethane and % of propane) in the multiscale kerogen model. The red, blue and
green spheres represent methane, ethane and propane molecules, respectively. (The colour ranges refer to the online version of the
paper).

adsorption of propane and to a lesser extent ethane in
the mesopores (cavity).
6. Conclusions
In this work, we combined the existing atomistic model
of a kerogen unit [17] and experimental data, and gen-
erated generic structures of overmature type II kerogen
corresponding to the organic part of Barnett shale. The
kerogen structures contained micropores with a pore
width ranging from 4 to 13 Å, in agreement with the
experimental PSDs for shale [50,51] that indicate the exis-
tence of micropores larger than 10 Å. The densities of our
model kerogens were between 1.2 and 1.3 g/cm3 , in agree-
ment with the experimental data [49] on such kerogen at
the same maturity level.
We then used GCMC simulations and studied the
adsorption of pure methane, mixture of methane, ethane
and propane as a proxy of shale gas, and pure carbon
dioxide in the model rigid kerogen structures. The
1102 L. MICHALEC AND M. LÍSAL
adsorbed amount of CO2 was about 30% higher than
that of CH4 (in agreement with the experimental data
[52]) due to stronger van der Waals and electrostatic gas–
gas and gas–adsorbent interactions in the case of the
CO2 adsorption. The structures further showed preferen-
tial adsorption for propane and to a lesser extent ethane
which, in the case of propane, can be associated with con-
densation of propane molecules in larger kerogen micro-
pores. In the case of CH4 adsorption, we were able to
compare the simulated excess adsorbed amount with the
experimental data for the Barnett shale [53,54] and found
that our simulation values were within the range of the
experimental values.
We further employed MD simulations with a set-
up that mimicked the real adsorption experiment and
explored connectivity of pore network in the model
rigid kerogen structures to the external surface. The MD
simulations revealed limiting pore space accessibility of
certain kerogen pores which is related to extremely low
permeability of real shales [1,2]. The kerogen pore net-
work accessibility was enhanced when we considered the
flexibility of the kerogen structures in MD simulations.
Finally, we considered a multiscale kerogen model by
combining our rigid kerogen matrix with a 14-Å-wide
cavity. The structure contained micropores as well as
mesopores with the pore width ranging from 4 to 27 Å.
We studied adsorption of the shale gas in the multiscale
kerogen model by GCMC simulations and found prefer-
ential adsorption of propane and to a lesser extent ethane
in both the micropores and mesopores of the structure.
Acknowledgment
The computer time was provided by the METACentrum com-
puting facility.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work has received funding from the European Union’s
Horizon 2020 research and innovation programme [grant num-
ber 640979], and was also supported by the Czech Science
Foundation (Project No. 16-12291S) and the Internal Grant
Agency of J. E. Purkinje University (Project No. 5322 16
0003 01).
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