Fuel 238 (2019) 402–411

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Fuel
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Full Length Article

Surface thermodynamics of hydrocarbon vapors and carbon dioxide T

adsorption on shales
Xu Tang
⁎

School of Chemistry, Univeristy of Nottingham, Nottingham, NG7 2RD, UK

Key Laboratory of Petroleum Resources Research, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China

ARTICLE INFO ABSTRACT

Keywords: Understanding hydrocarbon vapors and carbon dioxide adsorption mechanism on shales lays the foundation for
Shale in situ hydrocarbon resource estimation and enhanced hydrocarbon recovery via carbon dioxide injection.
Hydrocarbon vapor However, surface thermodynamic potentials of hydrocarbon vapor and carbon dioxide adsorption on shales have
Adsorption rarely been reported. This work develops a rigorous framework for direct description of hydrocarbon vapors and
Enthalpy
carbon dioxide adsorption isotherms on shales and for straightforward calculation of the intrinsic thermo-
Entropy
dynamic potentials by considering non-ideal gas behavior. On the basis of the Langmuir adsorption model, the
maximum adsorption capacity of methane, ethane, propane, n-butane, iso-butane and carbon dioxide adsorption
on shales positively correlates to each gas’ molecular mass. Carbon dioxide adsorption capacity is higher than
methane and ethane but is lower than propane, n-butane and iso-butane. According to the generalized multilayer
adsorption model, the monolayer adsorption capacity of n-hexane is slightly higher than that of n-heptane due to
the small molecular diameter of n-hexane. The temperature-dependent behavior of isosteric enthalpy and en-
tropy for these vapors is attributed to their non-ideal gas behavior and the temperature-dependent adsorption
uptakes. Isosteric enthalpy and entropy in general positively correlate to the molecular mass of vapors. Isosteric
enthalpy and entropy of carbon dioxide and propane are almost identical in behavior given that their molecular
masses are very close. Isosteric enthalpy and entropy of iso-butane are lower than that of n-butane due to their
molecule polarity difference. The shale selectivity of propane, n-butane and iso-butane is higher than carbon
dioxide while the shale selectivity of methane and ethane is lower than carbon dioxide. These surface ther-
modynamic characteristics therefore provide new perspectives on understanding the interaction of hydrocarbon
vapors/carbon dioxide and shales for enhanced hydrocarbon recovery via carbon dioxide injection.

1. Introduction under atmosphere pressure and transform into liquids. NGLs are also
central ingredients in many industrial processes like the petrochemical
The application of hydraulic fracturing and horizontal drilling un- process, ethylene production, ethanol denaturing and fuel uses, which
locks hydrocarbon resources in low permeability shale formations plays an essential role in most sectors of the economy [5–7]. NGLs
around the world and revolutionizes the world energy supply chain production therefore provides incentives to drill in liquids-rich shale
[1–3]. Natural gas production from unconventional shale reservoirs has reservoirs with significant NGLs content and also yields added benefits
been a primary focus of energy companies in North America over the for shale gas development in major shale basins in North America.
past decades. Natural gas produced from subsurface shale formations Organic-rich shale is a complex natural material manifesting na-
can be generally grouped into dry natural gas and wet natural gas [4,5]. noscopic properties such as abundant nanopores and extremely low
Dry natural gas is composed of mostly methane (CH4), and wet natural permeability (nanoDarcy), as well as complex compositions, including
gas contains methane and a descent amount of natural gas liquids minerals and organic matter [8–12]. These nanoscopic characteristics
(NGLs). The NGLs are hydrocarbon mixtures of ethane (C2H6), propane along with the high temperature and high pressure in situ reservoir
(C3H8), n-butane (nC4H10), isobutane (isoC4H10), and natural gaso- conditions limit a realistic understanding of hydrocarbon fluid storage
line (known as pentane (C5H12) and heavier hydrocarbons) [6]. While and transport mechanisms in shale formations. Previous studies argue
NGLs are gaseous at subsurface reservoir conditions, they condense that the phase behavior of hydrocarbons in a confined nanospace is

⁎
Address at: Room B-44a, School of Chemistry, University of Nottingham, Nottingham, NG7 2RD, UK.
E-mail address: [email protected].

https://doi.org/10.1016/j.fuel.2018.10.034
Received 12 July 2018; Received in revised form 5 September 2018; Accepted 4 October 2018
0016-2361/ Crown Copyright © 2018 Published by Elsevier Ltd. All rights reserved.
X. Tang Fuel 238 (2019) 402–411

different from the conventional equation of state [13–15]. It has also adsorption indicates that decreasing gas pressure accelerates CH4 des-
been shown that a good history match for oil production from wells in orption but enhances nC4H10 adsorption, and CO2 injection has the
the middle Bakken formation is obtained only after considering the capacity to enhance heavier hydrocarbon recovery [37]. GCMC simu-
fluid phase behavior in small pores [14]. Therefore, a true under- lation combined with engineering DFT was also applied to study the
standing of hydrocarbon phase behavior in shales is important for de- effect of pressure, temperature, and nanopore sizes on the bubble/dew
veloping new technologies for enhanced hydrocarbon recovery. point and hysteresis of hydrocarbons in nanopores, and it was found
Adsorption is generally defined as the enrichment of molecules, that the dew point of pure confined fluids approaches bulk saturation
atoms or ions in the vicinity of an interface. In the case of gas/solid point as pore size increases, but bubble point can be very different from
systems, adsorption takes place in the vicinity of the solid surface and bulk even for very large pores [38]. These modeling insights were also
outside the solid structure [16–18]. Adsorption is a consequence of validated by experimental data using differential scanning calorimetry,
surface energy and is generally classified as physical and chemical ad- which indicates that as pore diameter decreases from 37.9 to 4.1 nm,
sorption. The physical adsorption is the characteristic of weak of van the bubble point increases by as much as 15 K above bulk until the
der Waals forces and chemical adsorption is characteristic of covalent observed supercritical state [39,40]. A phase equilibrium model inside
bonding covalent bonding [17]. Gas adsorption approach, as a physical shales by considering capillary pressure and adsorption effects was
adsorption process, has been widely used for evaluating nanoconfine- developed, and the modeling results of hydrocarbon mixtures show that
ment effect on phase behavior, separating pure gas from mixtures as adsorption and capillary pressure can significantly change the bulk
well as probing nanopore structure of porous media [16–23]. This phase composition and its corresponding phase envelope [41]. The
routinely used approach has been adopted by researchers in shale gas heavier components are always preferentially adsorbed, the adsorption
industry to understand hydrocarbon vapores and shales interaction. selectivity of heavier components is moderate at high pressure and low
Butane adsorption and condensation behavior in shale and semectite temperature compared to that at low pressure and high temperature,
clay were studied using NMR, which indicates that when the pore size and the adsorption effects are stronger for the gas bulk phase region,
and pressure satisfy the Kelvin equation and the surface is hydrophobic, leading to bigger changes in the gas phase composition and the shift of
both nanopores in kerogen and nano/micropores between clay crystals the dew point curve [41].
can provide storage for hydrocarbons [24,25]. Adsorption isotherms of Even though previous studies advance our understanding about
n-hexane and n-heptane on two retorted oil shales were measured to heavier hydrocarbons and shale interactions, some fundamental ques-
probe the surface area of the shale samples which indicates the internal tions still remain unclear for the hydrocarbon vapor adsorption process
surface area of both shales are relatively low [26]. Sorption of methane, in shales. First, current available adsorption models such as the classic
ethane, propane, butane, carbon dioxide and nitrogen on asphaltene Langmuir model and the multilayer adsorption model have rarely been
shows that asphaltene is a swellable amorphous sorbent and it also has employed to describe measured hydrocarbon vapors adsorption iso-
a comparable adsorption capacity of microporous carbon with specific therms on shales. Even though high quality adsorption isotherm data
surface area over 1000 m2/g [27]. Sorption of methane, ethane, pro- were measured, quantitative analysis of these adsorption isotherms via
pane, butane, carbon dioxide and nitrogen on kerogen shows that these adsorption models were not conducted [34,35]. The lack of a suitable
vapors not only adsorb on the surface of kerogen but also dissolve in adsorption model makes it challenging to study the impact of shale
kerogen itself, and the heat of enthalpy was studied using Clausius- material properties on hydrocarbon vapor adsorption behavior on
Clapeyron relationship [28]. Pore structure and surface properties of shales quantitatively. Second, investigation of surface thermodynamic
shales were characterized by octane and heptane through Zeta ad- potentials such as enthalpy and entropy for hydrocarbon vapors and
sorption isotherms [29]. Based on the assumption that an organic pore carbon dioxide on shales were rarely reported. The isosteric enthalpy of
is hydrophobic and a mineral pore is hydrophilic, three vapors, water, adsorption is historically estimated by applying the Clausius-Clapeyron
hexane and nitrogen, were used to probe the surface area of different (C-C) relationship to measured adsorption isotherm data, and the C-C
shales [30]. Energetic effects of adsorption of heptane, heptene, octane, approach is based on the ideal gas law and ignores the contribution of
hexene and hexane on hard coal samples of different metamorphism the adsorbed phase [42,43]. This means a non-ideal gas behavior
were studied, which shows that hexane behaves differently than other cannot be considered using the C-C approach [44,45]. The non-ideal
hydrocarbons of longer chains which may represent micropore pene- behavior of hydrocarbon vapors and carbon dioxide is presented via the
tration [31]. Adsorption properties of hydrocarbons (n-decane, me- compressibility factor (Z), which is a function of temperature and
thylcyclohexane and toluene) on clay minerals were investigated, pressure as shown in Fig. 1. Even though an analytical approach has
which shows that the adsorption properties of n-decane, methyl cy- been developed for calculating the thermodynamic potentials of su-
clohexane and toluene are associated with the specific surface areas, the percritical fluids and water vapor adsorption on shales and coal accu-
pore volumes of mesopores and equilibrium pressures [32]. A n-alkane rately [46–49], whether the same principle can be used for hydro-
adsorption evaluation model was developed on the basis of n-decane carbon vapors adsorption on shales has not been validated yet.
adsorption data on shales, and this study reveals that the adsorbed and Thermodynamic potentials are essential indicators of adsorbate-ad-
condensed amounts of n-decane are directly controlled by total pore sorbent interactions, and a suitable adsorption model is the basis of
volume provided maily by organic matters and pyrite and siderite in thermodynamics analysis. Therefore, it is urgent to find suitable ad-
shales [33]. Ad/desorption isotherms of various hydrocarbons and sorption models for describing hydrocarbon vapors and carbon dioxide
carbon dioxide on two shales were measured, which shows the sig- adsorption behavior on shales and to develop a rigorous framework for
nificant adsorption hysteresis of ethane, propane, n-butane and iso- accurate estimation of the corresponding thermodynamic potentials.
butane adsorption on shales and the hysteresis is more pronounced This work first develops a rigorous framework for describing vapor
under high pressure conditions [34,35]. Apart from these experimental adsorption behavior in porous media based on the classic Langmuir
studies, molecular dynamics simulation of adsorption was also used to model and the generalized multilayer adsorption model. The frame-
study phase behave of hydrocarbon vapors on shale pores. The phase work also allows the direct calculation of the thermodynamic potentials
behavior of various hydrocarbons in nanopores was studied via an relevant to adsorption by considering non-ideal gas behavior. The de-
engineering density functional theory (DFT) combined with Peng Ro- veloped frame is then tested and validated by measured hydrocarbon
binson equation of state, which shows that capillary condensation and vapors (methane, ethane, propane, n-butane, iso-butane, n-heptane and
hysteresis are more likely in heavier hydrocarbons, at lower tempera- n-hexane) and carbon dioxide adsorption isotherms on four shales.
tures and in smaller pores, and phase change always occurs below the Finally, the adsorption capacity, isosteric enthalpy and entropy as well
critical temperature and saturation pressure [36]. Grand canonical as some insights for engineering application are discussed in detail.
Monte Carlo (GCMC) simulation for CH4 and nC4H10 mixture These results provide initial answers for modeling hydrocarbon vapor

403
X. Tang Fuel 238 (2019) 402–411

(Guggenheim-Anderson-de Boer) or Dent’s model [53–55]. The general-

ized multilayer adsorption model and the corresponding surface coverage
( M ) have the following form,
n m K1 P 1
na =
(1 K2 P + K1 P ) (1 K2 P ) (3)

M na K1 P 1
= =
nm (1 K2 P + K1 P ) (1 K2 P ) (4)
where na is the adsorption uptake, nm is the monolayer adsorption ca-
pacity, K1 and K2 are related adsorption energies of different adsorption
( )
sites as a function of temperature, K1 = A1 exp RT1 and K2 = A2 exp RT2 ,
E E
( )
where 1 and 2 are corresponding prefactors, 1and 2 are corre-
A A E E
sponding binding energy of the adsorption sites, respectively. If one as-
sumes there is only one type of adsorption sites and set K2 = 1, Eq. (3) is
Fig. 1. Compressibility factor (Z) of hydrocarbon vapors and carbon dioxide as reduced to the classic BET model. It is worth emphasizing the different
a function of pressure and temperature; blue color represents 283.15 K and red derivation routes of the BET model and its generalized forms here. Both
color represent 342.15 K. The data is obtained using NIST Reference Fluid BET model and GAB model are on the basis that that the adsorbed phase
Thermodynamic and Transport Properties Database (REFPROP) version 8.0. in higher layers is in a condensed states and the heat of adsorption in
(For interpretation of the references to color in this figure legend, the reader is higher layers is either equal to or less than the heat of liquefaction
referred to the web version of this article.) [16,53,55] while Dent’s model is developed from kinetics theory and does
not necessarily assume the condensed state of higher adsorbed layers
and CO2 adsorption isotherms on shales as well as analyzing corre- [54]. Although these adsorption models are not physically and mathe-
sponding thermodynamic potentials. matically equivalent, they do yield essentially equivalent results and in-
terpret the same adsorption process.
2. Theory
2.2. Isosteric enthalpy
2.1. Adsorption model
Based on the Clausius–Clapeyron relationship [42,43], it is known
Adsorption isotherms present the relation, at constant temperature, that,
between adsorption uptake and equilibrium pressure of gas. The ex-
dP
perimentally measured adsorption uptake is Gibbs excess adsorption Had = ·T · v
dT (5)
uptake and is always lower than the absolute (true) adsorption uptake na

[50]. The difference between Gibbs excess adsorption uptake and ab- where Had is the isosteric enthalpy of adsorption, v (=(vg va)) is the
solute adsorption uptake cannot be ignored for gas adsorption mea- volume change of the phase change, vg is the molar volume of the bulk
surement under higher pressures, however, when the equilibrium gas phase, va is the molar volume of the adsorbed phase. If the volume
pressure is relatively low, the Gibbs excess adsorption uptake is iden- of the adsorbed layer can be ignored (Va → 0) and the gas is approxi-
tical to the absolute (true) adsorption uptake [17,18,51]. Previous mated as an ideal gas (Pvg _IG = RT , the subscript IG denotes ideal gas)
studies reveal that hydrocarbon vapors adsorption isotherms on shales under low vapor pressure conditions. Eq. (5) can be written as the
and kerogen follow type I and type II style isotherms according to classic C-C equation as seen in Eq. (6).
IUPAC recommendations [26,28,34,35]. Type I and II style isotherms
dP RT 2 (ln P )
could be described by the monolayer Langmuir model and unrestricted Hads _IG = = R[ ]n
monolayer-multilayer models, respectively. dT na P (1/ T ) a (6)
The classic Langmuir model is the most widely used one because of Eq. (6) is historically used to calculate isosteric enthalpy of ad-
its simplicity, effectiveness, and the reasonable explanation of its sorption for gas (vapor) adsorption from adsorption isotherms. First, a
parameters. Langmuir’s model and the corresponding surface coverage linear relationship ln(P) and 1/T at a specific adsorption uptake is ob-
( L ) can be shown in the following form, tained from multiple adsorption isotherms at different temperatures
n0 K 0 P [47,56,57]. Then, the isosteric enthalpy of adsorption is approximated
na =
1 + K0 P (1) using the slope of the linear relationship. This routinely adopted pro-
cedure is tedious and the obtained isosteric enthalpy are not accurate
L na K0 P because it is not easy to obtain the linear relationship ln(P) and 1/T at a
= =
n0 1 + K0 P (2) specific adsorption uptake, and the temperature-dependency feature of
the isosteric enthalpy of adsorption cannot be revealed either [47].
where na is the adsorption uptake, n 0 is the maximum adsorption ca-
pacity determined by material properties, P is the adsorption pressure, Observing Eq. (5), it is clear that if the derivative term, dT , is ob-
dP
( ) na
K 0 is the Langmuir constant which is a function of temperature, tained from measured adsorption isotherms, the isosteric enthalpy is
K 0 = A0 e( ) , where A0 is prefactors, E0 is the binding energy of the
E0
RT
readily available [58].
If one assumes the adsorption process follows the Langmuir equa-
adsorption site, R is universal gas content, T is temperature.
tion (Eq. (1)) and applies the Chain Rule for implicit differentiation
For monolayer-multilayer adsorption, BET (Brunauer–Emmett–Teller)
[58], one form of the derivative term can be obtained as shown in Eq.
model is the first and basic equation for describing multilayer adsorption
(7),
behavior in porous media [16]. The BET equation is adopted to evaluate
the surface area of porous materials according to nitrogen adsorption data dP
L 1
K P
[16–18]. In practice, the BET model could only describe adsorption be- = = E0 ·
dT na P na K na T na RT2 (7)
havior under a relative low pressure [17,52]. In order to extend the ap-
plication of the multilayer adsorption concept, the BET model was up- If one assumes the adsorption process is monolayer-multilayer ad-
dated as a generalized multilayer adsorption model which is called GAB sorption following Eq. (3), another form of the derivative term can be

404
X. Tang Fuel 238 (2019) 402–411

Fig. 2. Adsorption isotherms of hydrocarbon vapors and CO2 on shales [26,34]; the solid points are measured data and solid lines are fitting curves using Eq. (1) for
Kimmeridge sample and Neuquen shales and Eq. (3) for Colorado and Utah retorted shales.

obtained as shown in Eq. (8) [46], dependent and the binding energy (E0) remains constant. Eq. (10)
M -1
shows temperature-dependent behavior as the compressibility factor
dP K (Z), K1 and K2 are temperature-dependent.
=
dT na P na K na T na When gas pressure is extremely low and the gas can be treated ideal
[E1 (1 K2 P )(1 K2 P ) + E2 K2 P (2 2K2 P + K1 P )] P gas (Z = 1), Eq. (9) actually represents the heat of adsorption in Henry’s
= ·
(1 + K1 K2 P 2 K22 P 2) RT 2 law region, also called mean isosteric heat of adsorption,
(8) H
Had _IG = E0 (11)
For dilute gas adsorption, the contribution of the adsorbed phase
(Va → 0) is ignorable. If the real gas law is then applied (Pvg\_RG = ZRT , Eq. (11) is consistent with previous studies that the heat of enthalpy
Z is the compressibility factor of gas and the subscript RG denotes real in Henry’s law region is independent of temperature and essentially
gas), two different forms of isosteric enthalpy can be obtained by sub- reflects the overall heterogeneous properties of the adsorbent [47,56].
stituting Eqs. (7)–(8) into Eq. (5), The heat of enthalpy in Henry’s law region can also be used an index to
evaluate the gas adsorption affinity of adsorbents such as coal and shale
L
Had _RG = Z · E0 (9) in the limit of very dilute adsorption [47,56]. When thermodynamics
analysis is outside the Henry’s law region, Eqs. ((9) or (10)) have to be
M [E1 (1 K2 P )(1 K2 P ) + E2 K2 P (2 2K2 P + K1 P )] employed to consider the non-ideal gas effect.
Had _RG = Z·
(1 + K1 K2 P 2 K22 P 2 )
(10)
2.3. Isosteric entropy
The negative sign means the adsorption process is an exothermic
process as shown in Eqs ((9) and (10)). Eq. (9) indicates that the isos- The isosteric entropy of adsorption ( Sads ) and its change with
teric enthalpy derived from Langmuir model shows temperature-de- surface coverage reveals the mobility of adsorbed phase. The isosteric
pendent behavior as the compressibility factor (Z) is temperature- entropy of adsorption refers to the change in entropy due to adsorption

405
X. Tang Fuel 238 (2019) 402–411

at a constant absolute adsorption uptake, which is readily defined by

0.0005

0.0001

0.0007

0.0011
RMSE
the Clausius–Clapeyron relationship [42,43],
dP
Sads = · v

0.9985

0.9994

0.9969

0.9864
dT na (12)

R2
Comparing to Eq. (5), it is clear that Sads is readily available when
Hads is known as shown in Eq. (13),

E2 (J/mol)

34598.99

32713.09

32199.98

32209.10
Hads
Sads =
T (13)
Eq. (13) indicates the isostereic entropy is negative and the negative
entropy means that the adsorption process is an enthalpy driven pro-

3.43E−11

2.41E−10

1.01E−10

3.21E−10
A2 (Pa−1)
cess.

3. Data acquisition

E1(J/mol)

47062.14

33412.31

41851.66

35000.00
The hydrocarbon vapors and CO2 adsorption in shales are directly
retrieved from two publications [26,34]. In Pedram’s work [26],
hexane (nC6H14) and heptane (nC7H16) vapor adsorption isotherms
on Colorado and Utah retorted shales at temperatures of 284.3, 293.7

6.10E−12

1.71E−09

2.99E−11

9.00E−10
A1(Pa−1)
Multilayer model- Eq. (3)
and 303.2 K. In Zhao’s work [34], CH4, C2H6, C3H8, nC4H10,
isoC4H10 and CO2 sorption on Kimmeridge and Neuquen shales are
conducted at temperatures of 308.15, 323.15 and 338.15 K. The ad-
sorption isotherms are measured using gravimetric approach in both

nm (mmol/g)
works, and detailed information about these tests and shale properties

0.0103

0.0090

0.0085

0.0080
can be found in the original publications [26,34]. The pertinent data
from these papers are shown in Fig. 2, which includes 48 adsorption
isotherms with 498 measured data. Since the maximum equilibrium
pressure is < 4000 kPa for all test data, the measured adsorption up-

nC6H14

nC7H16

nC6H14

nC7H16
Vapors

takes are treated as the absolute adsorption uptakes in the following

discussions according to Gibbs adsorption concept.
The observed CH4, C2H6, C3H8, nC4H10, isoC4H10 and CO2 ad-
Colorado shale

sorption isotherms on Neuquen and Kimmeridge shales under different

Utah shale
temperatures are fitted simultaneously using Eq. (1) within the limits of
Sample

the fitting parameters (0 < n0 < 10 mmol/g, 0 kJ/mol <

E0 < 100 kJ/mol, 0 < A0). The observed nC6H14 and nC7H16 ad-
sorption isotherms on Colorado and Utah retorted shales under dif-
0.0015
0.0030
0.0026
0.0028
0.0020
0.0027
0.0044
0.0226
0.0194
0.0120
0.0174
0.0213
ferent temperatures are fitted simultaneously using Eq. (3) within the
RMSE

limits of the fitting parameters (0 < nm < 10 mmol/g, 0 kJ/mol <

E1, E2 < 100 kJ/mol, 0 < A1, A2). The test data is processed using a
0.9829
0.9948
0.9937
0.9846
0.9931
0.9949
0.9965
0.9905
0.9882
0.9890
0.9812
0.9907

Universal Global Optimization method of the Auto2Fit software (7D-

soft High Technology Inc., China), and the UGO has the capacity to find
2
R

the global maximal/minimal value of any functions without using the

initial start values [46–49]. The obtained fitting parameters are shown
24353.751
25874.329
26425.353
27778.863
27000.083
26210.224
E0 (J/mol)

19843.67
20541.44
22644.35
22999.97
21282.21
21144.50

in Table 1 and RMSE represents the root of mean square error.

Once all the fitting parameters are obtained from simulating the
observed adsorption isotherms using Eqs. ((1) or (3)), the isosteric en-
thalpy and entropy of adsorption is readily available using Eqs.
1.30E−10
1.61E−10
2.86E−10
6.58E−10
1.52E−10
3.68E−11
3.07E−11
7.23E−11
1.05E−10
6.61E−11
2.95E−11
)
−1

((9)–(11), (13)).
Langmuir model- Eq. (1)

2E−10
A0 (Pa

4. Results and discussion

n0 (mmol/g)

4.1. Adsorption isotherm modeling

0.0548
0.1908
0.2089
0.2083
0.1751
0.1456
0.3694
0.8576
0.8093
0.8244
0.8000
0.7533

The Langmuir model (Eq. (1)) simulates CH4, C2H6, C3H8,

Fitting parameters for shale samples.

nC4H10, isoC4H10 and CO2 adsorption isotherms on Neuquen and

Kimmeridge shales very well as shown in Fig. 2, and this was also in-
isoC4H10

isoC4H10
nC4H10

nC4H10
Vapors

dicated by the fitting parameter R2 and RMSE in Table 1. The maximum

C2H6
C3H8

C2H6
C3H8
CH4

CH4
CO2

CO2

adsorption uptake (n0) of different hydrocarbons has a positive re-

lationship with the molecular mass of hydrocarbon vapors and CO2 on
Kimmeridge sample

Neuquen and Kimmeridge shales; the higher the molecular mass the
higher the maximum adsorption uptake as shown in Fig. 3. The max-
Neuquen Shale

imum adsorption uptake of Kimmeridge sample is much higher than

that of Neuquen shale, which can be attributed to the higher total or-
Sample
Table 1

ganic content (TOC), nitrogen effective surface area and BJH pore vo-
lume. The TOC, nitrogen effective surface area and BJH pore volume of

406
X. Tang Fuel 238 (2019) 402–411

indicates the adsorption process is physical adsorption [47,56]. The

isosteric enthalpy also shows adsorption uptake, temperature and gas
type dependent behavior (Fig. 5). When the adsorption uptake in-
creases, the isosteric enthalpy decreases following a concave-curve
trend. The isosteric enthalpy also decreases with increasing tempera-
ture. These characteristics can be attributed to the non-ideal behavior
of vapors as shown in Eq. (9), where the isosteric enthalpy is a function
of the binding energy (E0) and gas compressibility factor (Z). The
binding energy is constant, and gas compressibility factor (Z) changes
with temperature and pressure. For different vapors, the higher the
molecular mass, the higher the isosteric enthalpy. As molecular mass of
CO2 and C3H8 are very close, the isosteric enthalpy are almost the
same. The isosteric enthalpy of isoC4H10 is lower than nC4H10, which
Fig. 3. Maximum adsorption capacity of hydrocarbons and carbon dioxide on
is attributed to the polarity difference. The similar behavior has been
Neuquen and Kimmeridge shales: triangle represents carbon dioxide, and circle
observed from adsorption uptake where the adsorption uptake of
represents hydrocarbons.
nC4H10 is higher than isoC4H10 under same conditions.
Isosteric enthalpy of nC6H14 and nC7H16 on Colorado shale ranges
from 30 kJ/mol to 48 kJ/mol indicating a physical adsorption process,
and these values are also higher than that of light hydrocarbons and
CO2 on Kimmeridge shales. Fig. 5 also indicates that the isosteric en-
thalpy of nC6H14 and nC7H16 sharply decreases following a convex-
curve trend and then levels off. This characteristic follows a monolayer,
multilayer and capillary condensation behavior of vapors during the
adsorption process. When capillary condensation dominates, the isos-
teric enthalpy almost levels off. High temperature also results in a small
shift of the isosteric enthalpy of adsorption, and the temperature-de-
pendent characteristic is readily available. It is also interesting to find
that isosteric adsorption of nC6H14 is much higher than that of
nC7H16, which does not follow the trend that the higher molecular
mass the higher the isosteric enthalpy. More experiments are needed to
reproduce and clarify this unusual behavior in the future.

Fig. 4. Monolayer adsorption capacity of nC6H14 and nC7H16 on Colorado 4.3. Isosteric entropy
and Utah retorted shales.
For CH4, C2H6, C3H8, nC4H10, isoC4H10 and CO2 adsorption on
Kimmeridge shale, the isosteric entropy is lower than 0.09 kJ/(mol K).
Kimmeridge and Neuquen shale is 51.19%, 7 m2/g, 0.038 cm3/g and Since the process is an enthalpy driven process, the isosteric entropy
3.65%, 5.6 m2/g, 0.023 cm3/g, respectively [34]. shows similar behavior of isosteric enthalpy, which depends on ad-
The multilayer adsorption model (Eq. (3)) has the capacity to de- sorption uptake, temperature and gas type. Fig. 6 also shows that as the
scribe nC6H14 and nC7H16 adsorption behavior on Colorado and Utah adsorption uptake increases, the isosteric entropy decreases. The reason
retorted shales as well as calculate the monolayer adsorption capacity is that the freedom of gas molecular decreases when free gas molecular
of each vapor shown in Fig. 2. The monolayer adsorption capacity of becomes adsorbed molecular. When temperature increases, the isosteric
Colorado shale is higher than that of Utah shale, which is consistent entropy also decreases as the adsorbed phase is “less restricted” pro-
with the nitrogen effective surface area (Fig. 4). The measured nitrogen moted by higher temperature. It is also clear that the temperature-de-
effective surface area of Colorado and Utah shale is 3.4 m2/g and pendent characteristics is more pronounced for isosteric entropy com-
2.1 m2/g, respectively [26]. The monolayer adsorption capacity of pared to isosteric enthalpy. For different vapors, the higher the
nC6H14 is slightly higher than that of nC7H16. This could be attributed molecular mass, the higher the isosteric entropy. As molecular mass of
to the smaller diameter of nC6H14 compared to nC7H16, and some CO2 and C3H8 are identical, the isosteric entropy are almost the same.
local surface area may be inaccessible to larger molecular. The kinetic The isosteric entropy of isoC4H10 is also lower than nC4H10. It is
diameter of nC6H14 and nC7H16 is 0.45 and 0.47 nm, respectively worth emphasizing that the decreasing trend of the isoseric entropy
[59]. does not violate the second law of thermodynamics which states that
In the following sections, only Kimmeridge shale and Colorado the entropy of the universe always increases. This is because the ad-
shales are taken as an example to discuss isosteric enthalpy and entropy sorption process is not an isolated system. The entropy of the adsorption
behavior of hydrocarbon vapors and carbon dioxide during the ad- process does decrease but is more than compensated by the increased
sorption process. The isosteric enthalpy and entropy in all figures are entropy of the surroundings due to the heat release.
presented as absolute/positive values for convenience. The isosteric Isosteric entropy of nC6H14 and nC7H16 on Colorado shale ranges
enthalpy and entropy of hydrocarbon vapors and carbon dioxide on from 0.11 kJ/mol to 0.17 kJ/mol, which is higher than that of light
Neuquen and Utah shales are shown in the Supplementary Materials, hydrocarbons and CO2 on Kimmeridge shale. The isosteric entropy
which are similar to that on Kimmeridge shale and Colorado shales. sharply decreases and then levels off as the adsorption uptake increases.
Considering the monolayer, multilayer and capillary condensation
4.2. Isosteric enthalpy process, the isosteric entropy indicates the freedom of the molecular
decreases by the following order: adsorbed molecular of a monolayer,
For CH4, C2H6, C3H8, nC4H10, isoC4H10 and CO2 adsorption on adsorbed molecular of a multilayer, and liquids of pore surface. Higher
Kimmeridge shale, the isosteric enthalpy is < 30 kJ/mole, which temperature leads to a lower isosteric entropy as less energy is needed

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Fig. 5. Isosteric enthalpy of CH4, C2H6, C3H8, nC4H10, isoC4H10 and CO2 adsorption on Kimmeridge shales and nC6H14 and nC7H16 adsorption behavior on
Colorado shale.

to increase the freedom of molecular. The isosteric entropy of nC6H14 the maximum adsorption capacity of CO2 is higher than CH4 and C2H6
is much higher than that of nC7H16. This does not follow the trend that but is lower than C3H8, nC4H10 and isoC4H10, as shown in Table 1.
the higher molecular mass the higher the isosteric entropy, and the This means both shales favorably adsorb C3H8, nC4H10 and isoC4H10
abnormal behavior needs in-depth study in the future. compared to CO2. Even though CO2 is less competitive compared to
heavier hydrocarbon (C3H8 and heavier), injected CO2 still has the
4.4. Insights for enhanced hydrocarbons recovery through CO2 injection capacity to change bulk phase composition of mixture via competitive
adsorption especially under high pressure conditions and thus affect the
It has been evidenced that CO2 has the capacity to displace CH4 in phase envelope of hydrocarbon mixture [38–41]. Molecular simulation
coal seams through competitive adsorption as the adsorption affinity of also indicates that low pressure CO2 can prevent the capillary con-
CO2 on coal is much higher than CH4, and this lays the foundation for densation of nC4H10 [37]. Furthermore, CO2 injection has been his-
enhanced coalbed methane recovery through CO2 injection [60]. A torically adopted to enhanced oil recovery as CO2 can dissolve into
CO2 huff-and-puff test in shale formations demonstrates injected CO2 hydrocarbon liquids and enhance the mobility of these liquids [64–66].
can also enhance heavier hydrocarbons recovery including C2H6, The enhanced fluid mobility and phase change of heavier hydrocarbon
C3H8, and C4H10 [61,62]. It is worth noting that the heavier hydro- could finally lead to the enhanced C2H6, C3H8, and C4H10 in the
carbons like C5H12, C6H14 and C7H16 have not been reported in this production flows as observed in shale formations [61,62].
work because the gas chromatography–mass spectrometry cannot
quantify these heavier hydrocarbons [61–63]. 5. Conclusions
Since the isosteric enthalpy in Henry’s law region is independent of
temperature and reflects the material properties of adsorbent, it may be The Langmuir model and the generalized multilayer adsorption
useful to show the selectivity of hydrocarbons over CO2. The selectivity model can be applied over an arbitrary range of pressure at elevated
of hydrocarbon is defined as the isosteric enthalpy ratio of hydro- temperatures for the chosen hydrocarbon vapors and carbon dioxide
carbons to CO2 in Henry’s law region, i.e. S = Hhydrocarbon
H H
/ HCO 2 . As adsorption on shales. An analytical approach for the direct analysis of
expected, the selectivity describes the shale affinity of hydrocarbons the thermodynamic quantities of interest from both models has then
over CO2 very well. The higher the molecular mass the higher the se- been validated in this work. Some preliminary conclusions can be ob-
lectivity of both shales, and the selectivity of nC4H10 is higher than tained,
isoC4H10, as shown in Fig. 7. It is also found that the selectivity is
higher than one for C3H8, nC4H10 and isoC4H10 but is lower than one 1. The Langmuir model can describe methane, ethane, propane, n-
for CH4 and C2H6. This finding coincidently agrees with the fact that butane, iso-butane and carbon dioxide adsorption isotherms at

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Fig. 6. Isosteric entropy of CH4, C2H6, C3H8, nC4H10, isoC4H10 and CO2 adsorption on Kimmeridge shales and nC6H14 and nC7H16 adsorption behavior on
Colorado shale.

4. Carbon dioxide and propane adsorption on shales shows almost

identical behavior in isosteric enthalpy and entropy as their mole-
cular masses are very close. Isosteric enthalpy and entropy of iso-
butane is lower than that of n-butane because of the molecule po-
larity difference.
5. The shale selectivity of propane, n-butane, iso-butane is higher than
carbon dioxide while the shale selectivity of methane and ethane is
lower than carbon dioxide.

Overall, the proposed framework lays the foundation for in-

vestigating hydrocarbon vapors and carbon dioxide adsorption beha-
vior on shales and the associated thermodynamics potentials. This
Fig. 7. Selectivity of hydrocarbons over carbon dioxide in Henry’s law region.
method also allows investigators to analyze how material properties of
shales such as compositions, pore structure and surface chemistry affect
multiple temperatures via a global fitting approach, respectively. the surface thermodynamic potentials in the future.
The maximum adsorption capacity of methane, ethane, propane, n-
butane, iso-butane and carbon dioxide adsorption on shales posi-
tively correlates to the molecular mass of each gas. Acknowledgements
2. The generalized multilayer model has the capacity to simulate n-
hexane and n-heptane adsorption behavior accurately under ele- The author would like to thank Professor Abbas Firoozabadi at Yale
vated pressures and pressures via a global fitting method for the test University for sharing the raw data of hydrocarbon vapors and carbon
results in this work. The monolayer adsorption capacity of n-hexane dioxide sorption on Kimmeridge and Neuquen shales. The project re-
is slightly higher than that of n-heptane, and this could be attributed ceived fundings from the European Union’s Horizon 2020 research and
to the smaller diameter of n-hexane compared to n-heptane, and innovation programme under the Marie Sklodowska-Curie grant
some local surface area may be inaccessible to larger molecular. agreement No 793128 (Marie Skłodowska-Curie Individual Fellowship)
3. The isosteric enthalpy and entropy exhibit temperature-dependent and the Key Laboratory of Petroleum Resources Research, Institute of
as well as adsorption uptake-dependent behavior, which is attrib- Geology and Geophysics, Chinese Academy of Sciences. The author
uted to the non-ideal gas behavior and temperature-dependent ad- would also like to thank the anonymous reviewers for their comments
sorption uptake. Isosteric enthalpy and entropy in general positively that helped improve the manuscript.
correlate to the molecular mass of vapors.

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Appendix A. Supplementary data of shale using the zeta adsorption isotherm approach. Energy Fuels
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