Gas-in-Place Calculations in Shale Gas Reservoirs using

Experimental Adsorption Data with Adsorption Models

Sukru Merey* and Caglar Sinayuc

Middle East Technical University, Department of Petroleum and Natural Gas Engineering, Ankara, Turkey

In this research, experimental adsorption measurements for a Dadas shale sample were conducted at various pressures (up to 13 790 kPa (2000
psia)) and temperatures (25, 50, and 75 8C) using pure methane (CH4). The effects of temperature and pressure on adsorption were observed. As
pressure increases, CH4 adsorption increases. However, as temperature increases, CH4 adsorption decreases. Moreover, by using Langmuir isotherm
and Ono-Kondo models, experimental adsorption results were evaluated and adsorption isotherms were constructed. Although Ono-Kondo and
Langmuir isotherm models have similar fittings to the experimental adsorption data of Dadas shale, Ono-Kondo models have several advantages.
Different from Langmuir isotherms, the volume of adsorbed fluid, absolute adsorption data, and surface area of Dadas shale sample were predicted
by Ono-Kondo models. By comparing the results of the Ono-Kondo monolayer and three-layer models, the adsorption type of the Dadas shale
sample was found as a monolayer (Type I). It was concluded that the Ono-Kondo monolayer model is capable of fitting adsorption isotherms,
especially at high pressures for shale samples. For initial gas-in-place calculations, the equations derived using the Langmuir isotherm were modified
by the Ono-Kondo monolayer model. For the first time, the Ono-Kondo monolayer model was used in the formula of initial gas-in-place calculation.
This formula provides better adsorption data evaluation, initial gas-in-place amounts, and adsorbed gas ratios in shale gas reservoir conditions
compared to the values obtained with the Langmuir isotherm. This method is suggested to be used in flow and gas production simulations of shale
gas reservoirs.

Keywords: shale gas, gas-in-place, CH4 adsorption, adsorption models, Ono-Kondo model

INTRODUCTION local-density (SLD) model was applied for CH4 and CO2. Similarly,
Lu et al.[8] determined the adsorption capacity of CH4 on 24

T
he amount of technically recoverable shale gas in the world
samples of Devonian shale. It was proposed that the CH4
is
200 730 m3 (7795 trillion cubic feet (tcf)) according to
adsorption capacity is > 50 % of the total gas stored. Moreover,
the Energy Information Administration.[1] This amount is
the adsorption capacity of shales depends mainly on total organic
crucial to fulfil the world’s natural gas demand in the future. In
carbon content (TOC) and clay content such as illite.[7,8,9,10] There
shale gas reservoirs, significant amounts of natural gas exist as
are two different experimental procedures to measure adsorption
conventional “free” gas in porous spaces as well as “adsorbed” gas
capacities: the gravimetric and volumetric methods. The volumet-
on the shale matrix.[2] When a gas and a solid interact, there are
ric method is the most common method for adsorption experi-
intermolecular attractive forces between them. If these intermo-
ments.[7,8,9,10,11,12,13] In the volumetric method, adsorption
lecular attractive forces are greater than those existing between
capacity is determined by measuring pressure changes in a
molecules of the gas itself, gas accumulates on the solid surface.
reference cell and a sample cell. In this study, the volumetric
This phenomenon is called adsorption of gas on solid.[3]
method was also used to measure adsorption, because it is cheap
Adsorption capacities of shale gas reservoirs range from
and easy to apply compared to the gravimetric method.[11,12]
20–85 %.[2]
There are many adsorption models, such as the Langmuir
Although shale gas reservoirs have low porosity and extremely
isotherm, BET isotherm, Freundlich Isotherm, Ono-Kondo model,
low permeability values (9.869  1021–9.869  1020 m2 (10–
etc.[13,14] However, the Langmuir isotherm is commonly used for
100 nanodarcies)), hydraulic fracturing and horizontal drilling
evaluating adsorption data, because it is easy to use and practical
operations make gas production feasible from these reservoirs.[4,5]
for engineering purposes.[11,14,15] After determining the adsorp-
Hence, understanding adsorption capacities and behaviours of
tion data of a shale gas reservoir, the constants of adsorption
shale gas reservoirs is vital in exploitation and resource
models are found. These constants and adsorption models are
evaluation. To calculate initial gas-in-place, determining adsorp-
integrated into the simulators. These simulators are mainly used to
tion capacity of a shale gas reservoir is also very crucial. However,
predict flow type and gas production from shale gas reservoirs.
initial gas-in-place calculations of shale gas reservoirs are quite
Adsorption data and models provide information about the
different from other conventional gas reservoirs, because gas is
amount of gas-in-place and the adsorbed gas ratio at different
stored as both a free phase and adsorbed phase.[5,6]
Adsorption experiments are important for understanding the
amount of gas-in-place and adsorbed gas ratio in shale formations.
Chareonsuppanimit et al.[7] measured adsorption capacities of * Author to whom correspondence may be addressed.
methane (CH4), nitrogen (N2), and carbon dioxide (CO2) on New E-mail address: merey@metu.edu.tr
Albany shales at 328.2 K and pressures up to 12.4 MPa. The Can. J. Chem. Eng. 94:1683–1692, 2016
adsorption capacities of CO2 on samples are higher than CH4 © 2016 Canadian Society for Chemical Engineering
DOI 10.1002/cjce.22538
adsorption capacities. The lowest adsorption capacities were Published online 22 June 2016 in Wiley Online Library
obtained for N2. For the evaluation of adsorption data, a simplified (wileyonlinelibrary.com).

VOLUME 94, SEPTEMBER 2016 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 1683
production pressures. For flow and diffusivity equations, these
data are very important. Leahy-Dios et al.[16] proposed two
different transport models to model the flow through shale gas and
coal-bed methane (CBM). They developed a new multicomponent
adsorption model. The difference in cumulative gas production
between the model and field data is 10 %. Similarly, Feast et al.[17]
developed their simulator using BET and the Langmuir isotherm.
They compared their model data with the actual field data of the
Marcellus shale field and a good history match was obtained.
Generally, it is assumed that natural gas includes 100 % CH4
during the adsorption studies. However, Hartman et al.[18]
extended the Langmuir model to calculate the initial gas-in-place
amount for a natural gas mixture. Moreover, by using their
modelling and Monte Carlo simulation methods, the adsorbed-
phase density of the natural gas mixture was predicted. They
concluded that although the total gas storage capacity predictions
may not be influenced by the gas mixture composition, a
significant adsorbed amount could be predicted incorrectly by
considering the gas-in-place as pure CH4 and/or by not consider-
ing the adsorption layer effect. When pressure increases, the
adsorption capacity increases. Hence, the volume of adsorbed gas
becomes important when the adsorbed gas amount increases, and
this was called the adsorbed layer effect by Hartman et al.[18]
However, the adsorption layer effect is generally ignored.
Different than the study of Hartman et al.,[18] for determining
the volume of adsorbed fluid, Ono-Kondo models were used in this
study. This model was used in a few studies for the evaluation of
adsorption data.[19,20,21] None of these studies try to use the model
data to predict initial gas-in-place amounts and adsorbed gas ratios
in shale gas reservoirs by using Ono-Kondo models. However, this
is the aim of this study.
In this study, the adsorption capacities of a shale sample taken
from the Dadas Formation (TOC:
4 % and medium clay content)
in Turkey at 25, 50, and 75 8C were measured using the volumetric
adsorption experimental setup. Then, experimental adsorption
data were evaluated by Langmuir isotherm and Ono-Kondo
models. In this study, MATLAB codes were written for Ono-Kondo
monolayer and three-layer models, which are used for the
evaluation of experimental adsorption data and layered structure
of adsorption. Moreover, the Ono-Kondo model was used to
calculate the surface area of the shale sample. Finally, using the
Ono-Kondo monolayer model and taking into account the
adsorbed volume on the surface of the adsorbent, a formula was
proposed for initial shale gas-in-place calculations after modifying
Ambrose et al.’s[22] formula.
MATERIALS AND METHODS
Sample Preparation
Adsorption experiments were performed on powdered samples of
BPL activated carbon and shale samples that were ground and
sieved to 0.297–0.177 mm particle size (50/80 mesh size) using a
standard screening method. BPL activated carbon was used in this
study to prove the reliability of adsorption experimental setup and
calculation procedures. BPL is a virgin granular activated carbon
designed for use in gas-phase applications. It is a bituminous coal-
based product activated at a high temperature in a steam
atmosphere. Because of its surface area, density, and strength
characteristics, BPL can be reactivated for reuse and thus eliminate
disposal problems.[23]
Shale and BPL samples were dried in a vacuum oven at
105 8C for 24 h until constant mass was achieved before each
1684 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
isotherm measurement. This procedure was used to ensure
that samples were completely dry and that any adsorbed gas
was completely removed from the samples. Moreover, after
putting samples into the sample cell, the filled sample cell was
connected to the experimental setup and system leak tests
were performed using helium (0.9999 g/g, 99.99 mass % purity)
because helium is a non-adsorbing gas.[12] Pressure and tempera-
ture were monitored with pressure transducers (accuracy 6.894
757 kPa (1 psia)) and thermocouples (accuracy 0.2 8C)
every 10 s during the test. After there were no leakages in the
system for 24 h, void volume and adsorption experiments were
conducted.
Experimental Procedure
In this study, the volumetric method was used to measure
adsorption capacity. The experimental setup is shown in Figure 1.
The sample cell is filled with the adsorbent (sample) to be studied.
After connecting the sample cell and the reference cell, the whole
system is put into a constant temperature water bath. At the
beginning of the experiment, the sample cell, the reference cell,
and connections such as lines, fittings, and valves are evacuated
from air by a vacuum. As seen in Figure 1, the sample and
reference cells are separated by closing the shut-off valve V1. In the
next step, the desired amount of gas is admitted to the reference
cell by opening the gas access valves V2 and V4. Desired pressure
values in the reference cell are supplied by a syringe pump. After
the desired pressure is achieved in the reference cell, valve V2 is
closed, and a certain time is allowed for pressure and temperature
equilibrium in the reference cell. Using Angus’s equation of state
(EOS) for methane (CH4),[24] the amount of moles of gas in the
reference cell can be computed from pressure, temperature, and
the volume of the reference cell. Then, valve V1 between the
reference and sample cells is opened. Adsorbate gas (CH4,
0.9999 g/g, 99.99 mass % purity) is admitted to the sample cell
from the reference cell. Then adsorption starts, causing a decrease
of pressure in the system. Until pressure equilibrium is satisfied,
pressure and temperature values are recorded every 10 s both
in the sample and reference cells. By measuring pressure values
before and after expansion both in the sample and reference
cells, gas molar densities at different stages are calculated using
Angus EOS[24] and the amount of gas adsorbed at the applied
pressure level is determined. The adsorption isotherm, a graph
of adsorption capacity versus pressure at a constant temperature,
is constructed by repeating these procedures until the measure-
ment at the highest desired gas pressure is achieved (1380 kPa
(200 psia) increments are generally preferred for adsorption at
high pressures).
THEORY
Adsorption Calculation Procedure
Excess (Gibbs) adsorption is expressed in the following equa-
tion:[12]
ads ¼ ninj  nunads
nGibbs ð1Þ
Gibbs
The amount of gas injected from the reference cell to the sample
cell can be determined using the following formula:


V ref Pref1 Pref2
ninj ¼  ð2Þ
RT zref1 zref2
VOLUME 94, SEPTEMBER 2016
Figure 1. Schematic diagram of the adsorption experimental apparatus.

The amount of un-adsorbed gas (free gas) in the sample cell at
equilibrium pressure is calculated using the following formula:


V void Pvoid2
unads ¼
nGibbs
RT zvoid2
To calculate absolute adsorption, the adsorbed density of gas
is needed. When adsorption equilibrium pressure increases, the
volume occupied by adsorbed gas increases. Therefore, this
reduces void volume in the sample cell, causing excess
calculation of free gas in the porous spaces of the sample cell
because helium void volume, measured before the adsorption
experiment, is used in adsorption calculations. If helium void
volume is not corrected, adsorption capacity is calculated as
lower than absolute adsorption, which is called excess (Gibbs)
adsorption.[20]
At lower pressures, the volume of adsorbed phase is negligible.
Hence:
Equations of State
Peng and Robinson equations of state (EOS) and other traditional
equations of state are not highly accurate. When pressure
increases, errors due to EOS calculations increase. Hence, more
ð3Þ
accurate equations of state, Angus’s EOS for CH4[24] were used in
this study to analyze experimental adsorption data. These
equations are considered the most reliable equations of state.[24]
Adsorption Models
In this study, to evaluate raw experimental adsorption data,
Langmuir isotherm and Ono-Kondo models (monolayer and three-
layer) were preferred.
Langmuir isotherm
The Langmuir isotherm was proposed by Irving Langmuir in 1918.
It is for gases adsorbed on solids. It is generally considered the
simplest model. Langmuir made some assumptions to propose this
model:[14]

1) The surface of an adsorbent is homogenous. This means that

void  V unads
V He ð4Þ
all the adsorption sites are energetically equivalent.
2) Adsorbed molecules do not interact with neighbouring
ads ¼ nads ¼ ninj  rgas V void
nabs ð5Þ
Gibbs He
adsorbed molecules.
3) Each site can hold one adsorbate molecule.
At higher pressures, the volume of adsorbed phase is significant: 4) At the maximum adsorption, only a monolayer is formed.

void ¼ V unads  V ads

V He ð6Þ The Langmuir equation describes the adsorption capacity of
rock as pressure changes under isothermal conditions:
ads ¼ ninj  rgas V void  rads V ads
nabs ð7Þ
He
VLP
V ads ¼ ð9Þ
PL þ P
By combining the adsorption formulas above, the following
formula is obtained for absolute adsorption:
Ono-Kondo lattice model
nGibbs Adsorption occurs in shale gas and coalbed methane reservoirs at
ads ¼
nabs  ads  ð8Þ high pressures. However, there are not enough studies and models
rgas
1  rads to represent adsorption at high pressures, especially for shales.

VOLUME 94, SEPTEMBER 2016 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 1685
The Langmuir isotherm is widely used but it is not suitable for Excess (Gibbs) adsorption then simplifies to the following:
especially high pressure adsorption. In the Langmuir isotherm, the


volume of the adsorbed phase is ignored and there is no correction r r
G ¼ 2Cðxads  xb Þ ¼ 2C ads  b ð14Þ
for adsorbed phase volume. rmc rmc
Considering the drawbacks of adsorption models such as the
Langmuir isotherm and other traditional methods, the Ono-Kondo
The parameters of the model rmc, eii/k, eis/k, and C are obtained
lattice model is based on lattice theory and was proposed
by fitting the model with experimental adsorption isotherm data.
originally by Ono and Kondo in 1960[11,20] and further developed
The parameters are fit when the average absolute percent
by Donohue[11,20] and recently by Sudibandriyo.[20] In this model,
deviation (AAD) in each isotherm is at a minimum. The AAD is
the adsorption system is composed of layers of lattice cells that
calculated using the following equation:
contain fluid molecules and vacancies. For the case of adsorption,
more fluid molecules reside in the cells of the adsorbed-phase N  
X 
layers than in the cells of the bulk-phase layers.[21] ADD ¼ nexp  nmodel   100 % ð15Þ
 
The Ono-Kondo model has several advantages:[20,21] i
nexp

1) It is used to describe multilayer adsorption.

The fluid-fluid energy parameter, eii/k, is estimated as being
2) It is able to describe adsorption behaviour based on the
proportional to the Lennard-Jones well depth energy
physical properties of the adsorbate and adsorbent.
parameter.[20]
3) It can estimate adsorbed-phase densities, which provide a
The following estimate for the fluid-fluid energy parameter is
calculation of absolute gas adsorption.
used in the Ono-Kondo model:
4) It can be used to incorporate accurate density calculations
from EOS models, which reduce the correlative burden on the
eii ¼ 0:432e ð16Þ
adsorption model.

In the Ono-Kondo model, the fluid system consists of lattice cells

Two-Parameter Ono-Kondo Model
occupied by fluid molecules or just empty cells. When adsorption
occurs, more molecules will occupy cells in the adsorbed-phase For the two-parameter Ono-Kondo model, the fluid-solid energy
layer than the gas-phase (bulk). parameter, eis/k, is regressed for each specific adsorption system,
When equilibrium exists between the gas-phase and multilayer and the parameter C is regressed for each adsorption isotherm
adsorbed phase, the expression for thermodynamic equilibrium using experimental adsorption data. Hence, it is called the two-
for pure-component adsorption under the mean-field approxima- parameter Ono-Kondo model.[20] In this study, the two-parameter
tion can be written as follows:[20] Ono-Kondo model was preferred to evaluate experimental
adsorption data for both Ono-Kondo monolayer and three-layer
 
xt ð1  xb Þ z0 ðxt  xb Þeii z2 ðxtþ1  2xt þ xt1 Þeii models. A MATLAB program for the Ono-Kondo monolayer and
ln þ þ ¼0 three-layer models was written in this study.
xb ð1  xt Þ kT kT
ð10Þ
RESULTS AND DISCUSSION
For t ¼ 2, 3, ..., m, number of the layer, and for 1st adsorbed
layer: Verification of Adsorption Experiments and Models
  Before carrying out the CH4 adsorption experiments on the shale
x1 ð1  xb Þ ðz1 x1 þ z2 x2  z0 xb Þeii eis sample, it is very important to prove the reliability of the
ln þ þ ¼0 ð11Þ
xb ð1  x1 Þ kT kT adsorption experiments and calculation procedures. In this study,
BPL activated carbon was used for this purpose by following Reich
For a hexagonal configuration of lattice cells, the coordination et al.’s[25] experimental procedure. In Runs #1 and #2, CH4
numbers z0 and z1 are 8 and 6, respectively, and by definition, adsorption experiments on BPL at 28.3 8C were performed.
z2 ¼ (z0 z1)/2. In Lancaster et al.,[2] the adsorption isotherm experiments on
The analytical expression for the excess (Gibbs) adsorption from Antrim Shale were conducted by different laboratories and their
this model is as follows: results were compared. However, different results were obtained
due to different sample treatments, calibration mistakes in
X
m pressure transducers and thermocouples, and mistakes in
G¼C ðxt  xb Þ ð12Þ adsorption calculations. To avoid similar mistakes, BPL activated
t carbon was used in this study. In the literature, several
experimental data sets of BPL-activated carbon are available.
where xt ¼ rt/rmc and xb ¼ rb/rmc Figure 2 shows the experimental results of Run #1, Run #2, and
To simplify the model, it is assumed that the adsorption occurs Reich et al.’s[25] results. As can be seen, all adsorption isotherms
within a slit. For monolayer adsorption inside a slit, the agree closely. Therefore, it can be concluded that the experimental
equilibrium expression is written as follows: setup and calculation procedure used in this study are suitable for
  adsorption experiments.
xads ð1  xb Þ ððz1 þ 1Þxads  z0 xb Þeii eis In this study, to evaluate raw experimental adsorption data,
ln þ þ ¼0 ð13Þ
xb ð1  xads Þ kT kT Langmuir isotherm and Ono-Kondo models (monolayer and
three-layer) were used. An algorithm was written for the
where z1 ¼ 6 and z0 ¼ 8 for the hexagonal lattice cell. Ono-Kondo monolayer and three-layer models using MATLAB

1686 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 94, SEPTEMBER 2016
 Table 1. Comparision of Ono-Kondo monolayer and three-layer model
results

Model Parameters Monolayer Three-layer

Model in this study %AAD 0.8 2.9

efs/k (K) 1381 1721
C (mmol/g) 3.14 4.34
Model in Sudibandriyo %AAD 0.6 2.8
et al.'s[20] study efs/k (K) 1385 1690
C (mmol/g) 3.26 4.53

Table 2. Experimental data for the adsorption experiments with Dadas

shale sample
Figure 2. Comparison of CH4 adsorption isotherms on BPL for Reich Parameters Runs #3, #4, #5, #6
et al.'s[25] adsorption experiments and Runs #1 and #2.
Reference cell volume 44.3 cm3
Sample mass 121.7 g
Sample cell volume (empty) 122.4 cm3
to find the adsorbed phase densities at different layers, surface
Mesh size of the sample (20/35) or 841–500 mm
areas,[19] and Ono-Kondo model parameters. The written algo- Average void volume in the sample cell 58.61 cm3
rithm is checked using Sudibandriyo et al.’s[20] experimental CH4
adsorption results for BPL. As shown in Table 1, the model
parameters in this study and Sudibandriyo et al.’s[20] study were
compared. The values of the model parameters are quite close to models. As seen in Figure 5, experimental CH4 adsorption data
each other. Small differences in the results are due to different from shale samples at 25, 50, and 75 8C were fitted well by the
initial guesses and different regression methods used. Langmuir isotherm and Ono-Kondo models.
The parameters of these models are listed in Tables 3–4. As seen
CH4 Adsorption Isotherms
in Table 4, model parameters of the Ono-Kondo three-layer model
Before carrying out CH4 adsorption experiments on the shale are close to the parameters of the Ono-Kondo monolayer model.
sample, the data in Table 2 were obtained and used for adsorption Small differences in adsorption parameters for the Ono-Kondo
calculations. In Figure 3, CH4 adsorption isotherms of the shale models are mostly related to the regression model used in the
sample at 25 8C (Run #3), 50 8C (Run #5), and 75 8C (Run #6) are program, and differences in initial guesses of fluid-solid energy
shown. As seen in Figure 3, adsorption capacities of CH4 on the parameters. Adsorption occurred as a monolayer in Runs #3, #5,
shale sample decrease with increasing temperature, as expected. It and #6 because the first layer’s adsorbed densities are higher than
is known that adsorption is exothermic, because heat is released as the bulk phase densities of CH4. However, the second and third
new bonds form.[14] Hence, the bonds between adsorbate (CH4) layer’s adsorbed densities are close to CH4 gas densities. This
and adsorbent (shale sample) are weakened and desorption occurs means that adsorption occurred as a monolayer in Runs #3, #5,
when temperature increases. The adsorption capacities increase and #6. It is also known that the Type I adsorption isotherm
linearly with pressure in Figure 2. However, after certain happens as a monolayer because of microporous structure.[14]
pressures, this increase stops and there is even a small decrease This supports the results of the Ono-Kondo models in this study.
in the adsorption capacities. Shales have nano-porous structures
in the shale matrix, so they have molecular diameters of pore
dimensions. Therefore, there are potential forces from the
neighbouring walls of the pores. These forces increase the
interaction energy between the shale sample surface and CH4
molecules, which causes an increase in adsorption and may cause
complete filling of pores at low pressures. This is a typical
behaviour of a Type I adsorption isotherm which depicts
monolayer adsorption on the adsorbent surface.[14] Hence, after
filling nearly all pores, at high pressures, adsorption becomes
almost stable. This indicates that pore sizes and surface area are
important for adsorption capacities and behaviours. Run #3 was
conducted again to check the repeatability of the experiments in
this study. As shown in Figure 4, CH4 adsorption experiments
conducted at the same conditions for Runs #3 and #4 at 25 8C show
that adsorption experiments in this study were repeatable.

Evaluation of Experimental CH4 Adsorption Experimental Data

using Langmuir Isotherm and Ono-Kondo Models
After obtaining adsorption isotherms with the help of the Figure 3. Comparison of CH4 adsorption isotherms of Dadas shale sample
experiments, it is very important to fit the data to adsorption for Runs #3, #5, and #6.

VOLUME 94, SEPTEMBER 2016 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 1687
 Table 3. Langmuir isotherm parameters for Runs #3, #5, and #6

Model parameters Run #3 (25 8C) Run #5 (50 8C) Run #6 (75 8C)

VL (mmol/g) 0.0545 0.0463 0.0293

PL (psia (MPa)) 387.9 (2.67) 965 (6.65) 992 (6.84)
R2 0.995 0.996 0.994

densities. In contrast, using adsorbed phase densities obtained

with the Ono-Kondo monolayer model, excess adsorption values
can be corrected for absolute adsorption. In Figure 6, absolute
adsorption values are shown for each pressure value after
correction. As seen in Figure 6, there are significant differences
between absolute adsorption and excess adsorption for all
temperatures, indicating the high capability of Ono-Kondo models
compared to the Langmuir isotherm.
Figure 4. Comparison of CH4 adsorption isotherms of Dadas shale sample
for Runs #3 and #4. Initial Gas-in-Place Calculations in Shale Gas Reservoirs
Shale gas reservoirs are classified as unconventional reserves.
Hence, initial gas-in-place calculation equations for conventional
Adsorption is expected to occur as a monolayer because of the
reserves cannot be used for shale gas reservoirs. Ambrose et al.[22]
small molecule sizes of shale samples in pore networks. Therefore,
proposed a new technique to calculate shale gas-in-place.
for evaluating the adsorption data of shale samples, the
However, in Ambrose et al.’s[22] equations, only Langmuir
Ono-Kondo monolayer model is sufficient and there is no need
isotherm parameters are used, and volume occupied by adsorbed
to use the Ono-Kondo three-layer model. Another advantage of
gas molecules is ignored. In this study, in addition to the Langmuir
Ono-Kondo models is the prediction of the surface area of shale
isotherm, Ono-Kondo models were used to evaluate experimental
samples. As shown in Table 4, the surface area values of shale
adsorption data. Hence, modifications were made to Ambrose
samples at 25, 50, and 75 8C are between 13.376–16.070 m2/g by
et al.’s[22] shale gas-in-place calculations to take into account the
applying the method of Sudibandriyo.[19] Therefore, Ono-Kondo
volume of adsorbed gas on the surface of the adsorbent in this
models are capable of approximately predicting the surface area of
study.
shale samples with their experimental adsorption data.
Ambrose et al.’s[22] initial shale gas-in-place formula is given as
The adsorption capacity is calculated by ignoring the volume of
follows:
the adsorbed gas on the surface of the adsorbent; this is called
" #
^

excess or Gibbs adsorption. After getting the results of excess
(Gibbs) adsorption capacities from the experiments, especially at 32:0368 fð1  Sw Þ 1:318  106 M P
Gst ¼  GsL
high pressures, it is very important to make void volume Bg rrock rs P þ PL


corrections in order to calculate absolute adsorption. In adsorp- P
þ GsL ð17Þ
tion, adsorbed molecules form a layer on the adsorbent. At low P þ PL
pressures, the volume of the adsorbed layer is negligible.
However, with increasing pressure, the volume of the adsorbed
Instead of the adsorbed gas amount calculated by the Langmuir
layer becomes important. The Langmuir model is not capable of
isotherm as used in Equation (17), the Ono-Kondo monolayer
calculating the volume of the adsorbed layer using adsorbed phase
model parameters (Equation (18)) were preferred to calculate
adsorption capacity, as it was indicated that adsorption occurs as a
monolayer in shale gas reservoirs.


P r rgas
Ga ¼ GsL ! Ga ¼ 1518C ads  ð18Þ
P þ PL rmc rmc

The initial shale gas-in-place calculation formula (Equa-

tion (19)) is obtained using the Ono-Kondo monolayer model
by inserting Equation (18) into Equation (17):
" #
^

rads rgas 
32:0368 fð1  Sw Þ 2:001  103 M
Gst ¼  C 
Bg r r rmc rmc


rock  ads
r rgas
þ 1518C ads  ð19Þ
rmc rmc

In both Ambrose’s equation (Equation (17))[22] and the

modified equation (Equation (19)), the volume occupied by
Figure 5. Comparision of CH4 excess adsorption data and adsorption
the adsorbed phase is ignored. Especially at high pressures, the
model predictions for Runs #3, #5, and #6.

1688 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 94, SEPTEMBER 2016
 Table 4. Ono-Kondo (OK) model parameters for Runs #3, #5, and #6

Run #3 (25 8C) Run #5 (50 8C) Run #6 (75 8C)

Model OK monolayer OK three-layer OK monolayer OK three-layer OK monolayer OK three-layer

parameters model model model model model model

%AAD 2.406 2.741 2.177 2.025 4.268 4.093

efs/k (K) 785 765 540 540 490 490
C (mmol/g) 0.0489 0.0496 0.0523 0.0506 0.0408 0.0403
Surface area 14.398 14.627 16.070 15.835 13.550 13.376
(m2/g)

volume occupied by the adsorbed phase becomes important. (Equation (17))[22] and modified Equation (19) gave similar
Hence, in the following equations (Equations (20–21)), a results, as seen in Figure 7.
correction was done using adsorbed phase density to consider However, to correct the volume of gas adsorbed in the
the volume occupied by the adsorbed gas. experiments, Equation (21) was used for initial gas-in-place
Excess (Gibbs) adsorption in Equation (18) was converted to calculations (Figure 8). As seen in Figure 9 at 75 8C, between
absolute adsorption for the Ono-Kondo monolayer model by 3447–34 470 kPa (500–5000 psia), the adsorbed gas percentage
Equation (20). calculated by Equation (21) changes from 41.6 % to 26.9 % for
the shale reservoir. The results show that the adsorbed gas

 !
r rgas rads percentages using Equation (21) are 1.3–2.4 times higher than the
Ga absolute ¼ 1518C ads  ! Ga absolute values calculated by Equation (17). Similar differences were
rmc rmc rads  rgas

 obtained for 25 and 50 8C. These differences are quite large.
rads
¼ 1518C ð20Þ Therefore, the correction in Equation (21) for absolute adsorption
rmc can be suggested for the most accurate shale gas-in-place
calculations.
Then, Equation (20) was inserted into Equation (17) to obtain For the exact initial gas-in-place calculations, accurate experi-
the corrected form of the shale gas-in-place equation (Equa- mental adsorption data are needed at different pressures. Although
tion (21)) which accounts for absolute adsorption. the Langmuir isotherm is commonly used in the experimental
adsorption data evaluation, such as in the study of Heller &
" #
^
32:0368 fð1  Sw Þ 2:001  103 MC Zoback,[10] adsorption is calculated lower than its actual value due
Gst ¼  to ignoring the volume of adsorbed gas. In this and similar
Bg r rmc


rock  studies,[19,20,21] it was shown that the Ono-Kondo monolayer
rads rgas
þ 1518C  ð21Þ model is useful for predicting the volume of adsorbed gas, and by
rmc rmc using this value, absolute adsorption is calculated. For example,
using the experimental adsorption data of Heller & Zoback,[10] the
For the shale gas reservoir, the data in Table 5 were used for absolute adsorption is calculated by applying Ono-Kondo
initial gas-in-place calculations for 25, 50, and 75 8C. Initial gas-in- models. When Langmuir isotherm parameters are used for initial
place calculations done without considering the volume of gas-in-place calculations as in Equation (17), the adsorbed amount
adsorbed gas (excess adsorption) using Ambrose’s equation of gas is calculated lower than its actual value and the free gas
amount is calculated higher than its actual value at reservoir
conditions. Therefore, it is important to find the density of
adsorbed gas on the layer of shale. In Hartmann et al.,[18] the pore
structure and density of adsorbed gas were measured using a
scanning electron microscope, and then the volume of
adsorbed gas was considered in the initial gas-in-place calcu-
lations. In contrast, in this study, the density of adsorbed gas is

Table 5. Properties of Dadas shale sample at different temperatures

Run #3 Run #5 Run #6

(25 8C) (50 8C) (75 8C)

w, fraction 0.06 0.06 0.06

Sw, fraction 0.35 0.35 0.35
rb (g/cm3) 2.06 2.06 2.06
C (mmol/g) 0.0489 0.0523 0.0408
PL (psia (MPa)) 387.9 (2.67) 965 (6.65) 992 (6.84)
Figure 6. Comparison of CH4 excess adsorption data and absolute GsL (VL) 41.37 scf/ton 35.14 scf/ton 22.24 scf/ton
adsorption data for Runs #3, #5, and #6. (0.0545 mmol/g) (0.0463 mmol/g) (0.0293 mmol/g)

VOLUME 94, SEPTEMBER 2016 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 1689
 predicted using Ono-Kondo models and experimental adsorption
data as well as Ono-Kondo model parameters C and efs/k. These
parameters are used in Equation (21) (found and proposed in this
study) for initial gas-in-place calculation at reservoir conditions.
Then, with only adsorption experimental data and reservoir
temperature, the amounts of adsorbed and free gas are calculated
at different pressures. Different from other studies,[9,10,18,22] the
surface areas of shale samples are approximated using Ono-Kondo
models.

Figure 7. Shale gas-in place calculations by Equations (17) and (19) for
Runs #3, #5, and #6.
Figure 8. Shale gas-in place calculations by Equation (21) for Runs #3, #5,
and #6.
Figure 9. Adsorbed gas (CH4) percentages for shale gas reservoir for
Runs #3, #5, and #6.
CONCLUSIONS
In this study, experiments were performed to investigate
adsorption capacities and behaviours of shale samples for initial
shale gas-in-place calculations. Adsorption experiments of CH4
were conducted at 25, 50, and 75 8C up to 13 790 kPa (2000 psia). It
was observed that increasing temperature decreases adsorption
capacity. Hence, the effect of temperature is important for
adsorption.
As seen in adsorption isotherms, as pressure increases,
adsorption capacity increases until the complete filling of pores
on the adsorbate. For desorption, it was observed that when
pressure decreases, most of the desorption happens immediately
because of the high interconnectivity of samples in the sample cell.
Therefore, it can be concluded that pressure and temperature are
determining factors for adsorption capacities and behaviours.
Ono-Kondo and Langmuir equations are capable of modelling
adsorption isotherms both at high and low pressures. However,
Ono-Kondo models differ from the Langmuir model, as can be
evaluated for different layers of adsorption. In this study, the
Ono-Kondo monolayer and Ono-Kondo three-layer models were
used and compared. By using experimental data with the prepared
algorithm which uses the Ono-Kondo model, it was found that
adsorption for the shale sample occurs as a monolayer, as
expected, because of nano-porous structures of shale gas
reservoirs. It was also seen that the shale sample’s adsorption
curve fits with the Type I isotherm curve, which generally
occurs in monolayer adsorption. Hence, for shale gas reservoirs,
the Ono-Kondo monolayer model fits adsorption data sufficiently
closely, and there is no need to use the Ono-Kondo three-layer
model.
Both the Ono-Kondo monolayer model and Langmuir model
can be used to calculate excess (Gibbs) adsorption without
accounting for the volume of the adsorbed phase. However, as
pressure increases, the volume of the adsorbed phase becomes
important for adsorbed gas and free gas calculations. The
adsorbed phase densities cannot be calculated using the
Langmuir model. Hence, Ono-Kondo models are capable of
calculating absolute adsorption by correcting excess (Gibbs)
adsorption values, since they can be used to calculate adsorbed
density values.
Shale gas-in-place equations proposed by Ambrose et al.[22]
were modified for the Ono-Kondo monolayer model with and
without considering the volume of adsorbed gas. The original
equation with the Langmuir model and modified equation with
the Ono-Kondo monolayer model resulted in similar excess
adsorption data. In contrast, when the volume of adsorbed gas is
considered in the final form of the initial gas-in-place equation
(Equation (21)), the adsorbed gas amount was calculated to be
higher than that from previous equations. Moreover, with
Equation (21), the free gas amount was calculated to be lower
than that from previous equations. The exact prediction of
adsorbed and free gas amounts in shale gas reservoirs is quite

1690 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 94, SEPTEMBER 2016
important for reservoir management studies. Therefore, the Vads gas volume that can be adsorbed by a rock of unit
modified equation including the volume of adsorbed gas correction mass (0.028 316 85 m3STP/ton (scf/ton))
(Equation (21)) in this study is suggested for shale gas-in-place VL Langmuir volume, maximum gas volume that can
calculations. By using this equation and the Ono-Kondo monolayer be adsorbed (0.028 316 85 m3STP/ton (scf/ton))
model parameters of experimental adsorption data, the adsorbed xt reduced density or fraction of sites occupied by
and free gas amounts at initial conditions and different production adsorbed molecules in layer t
pressures can be calculated. The parameters of the Ono-Kondo xb fraction of sites occupied by fluid molecules in the
monolayer can be used in shale gas reservoir simulators. As well as bulk
gas-in-place calculations, free gas amounts in pores at different xads fraction of rads to rads
production pressures are important for diffusivity equations during zref1 compressibility factor of gas in the reference cell
the simulation of gas production from shale gas reservoirs. before expansion
zref2 compressibility factor of gas in the reference cell
after expansion
NOMENCLATURE
zvoid2 compressibility factor of gas in the void spaces of
Bg gas formation volume factor the sample cell after expansion
C pre-factor related to capacity of the adsorbent for a
specific gas (mmol/g)
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Manuscript received July 30, 2015; revised manuscript received

November 30, 2015; accepted for publication December 7, 2015.

1692 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 94, SEPTEMBER 2016