GasinPlace 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 (CH _{4} ). The effects of temperature and pressure on adsorption were observed. As pressure increases, CH _{4} adsorption increases. However, as temperature increases, CH _{4} adsorption decreases. Moreover, by using Langmuir isotherm and OnoKondo models, experimental adsorption results were evaluated and adsorption isotherms were constructed. Although OnoKondo and Langmuir isotherm models have similar ﬁ ttings to the experimental adsorption data of Dadas shale, OnoKondo models have several advantages. Different from Langmuir isotherms, the volume of adsorbed ﬂ uid, absolute adsorption data, and surface area of Dadas shale sample were predicted by OnoKondo models. By comparing the results of the OnoKondo monolayer and threelayer models, the adsorption type of the Dadas shale sample was found as a monolayer (Type I). It was concluded that the OnoKondo monolayer model is capable of ﬁtting adsorption isotherms, especially at high pressures for shale samples. For initial gasinplace calculations, the equations derived using the Langmuir isotherm were modi ﬁed by the OnoKondo monolayer model. For the ﬁ rst time, the OnoKondo monolayer model was used in the formula of initial gasinplace calculation. This formula provides better adsorption data evaluation, initial gasinplace 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, gasinplace, CH _{4} adsorption, adsorption models, OnoKondo model
INTRODUCTION
T he amount of technically recoverable shale gas in the world is 200 730 m ^{3} (7795 trillion cubic feet (tcf)) according to the Energy Information Administration. ^{[}^{1}^{]} This amount is
crucial to ful ﬁ l the world’ s natural gas demand in the future. In shale gas reservoirs, signi ﬁ cant amounts of natural gas exist as conventional “free ” gas in porous spaces as well as “adsorbed ” gas on the shale matrix. ^{[}^{2}^{]} When a gas and a solid interact, there are intermolecular attractive forces between them. If these intermo lecular attractive forces are greater than those existing between molecules of the gas itself, gas accumulates on the solid surface. This phenomenon is called adsorption of gas on solid. ^{[}^{3}^{]} Adsorption capacities of shale gas reservoirs range from 20 –85 %. ^{[}^{2}^{]} Although shale gas reservoirs have low porosity and extremely low permeability values (9.869 10 ^{} ^{2}^{1} –9.869 10 ^{} ^{2}^{0} m ^{2} (10 – 100 nanodarcies)), hydraulic fracturing and horizontal drilling operations make gas production feasible from these reservoirs. ^{[}^{4}^{,}^{5}^{]} Hence, understanding adsorption capacities and behaviours of shale gas reservoirs is vital in exploitation and resource evaluation. To calculate initial gasinplace, determining adsorp tion capacity of a shale gas reservoir is also very crucial. However, initial gasinplace calculations of shale gas reservoirs are quite different from other conventional gas reservoirs, because gas is stored as both a free phase and adsorbed phase. ^{[}^{5}^{,}^{6}^{]} Adsorption experiments are important for understanding the amount of gasinplace and adsorbed gas ratio in shale formations. Chareonsuppanimit et al. ^{[}^{7}^{]} measured adsorption capacities of methane (CH _{4} ), nitrogen (N _{2} ), and carbon dioxide (CO _{2} ) on New Albany shales at 328.2 K and pressures up to 12.4 MPa. The adsorption capacities of CO _{2} on samples are higher than CH _{4} adsorption capacities. The lowest adsorption capacities were obtained for N _{2} . For the evaluation of adsorption data, a simpliﬁ ed
localdensity (SLD) model was applied for CH _{4} and CO _{2} . Similarly, Lu et al. ^{[}^{8}^{]} determined the adsorption capacity of CH _{4} on 24 samples of Devonian shale. It was proposed that the CH _{4} adsorption capacity is > 50 % of the total gas stored. Moreover, the adsorption capacity of shales depends mainly on total organic carbon content (TOC) and clay content such as illite. ^{[}^{7}^{,}^{8}^{,}^{9}^{,}^{1}^{0}^{]} There are two different experimental procedures to measure adsorption capacities: the gravimetric and volumetric methods. The volumet ric method is the most common method for adsorption experi ments. ^{[}^{7}^{,}^{8}^{,}^{9}^{,}^{1}^{0}^{,}^{1}^{1}^{,}^{1}^{2}^{,}^{1}^{3}^{]} In the volumetric method, adsorption capacity is determined by measuring pressure changes in a reference cell and a sample cell. In this study, the volumetric method was also used to measure adsorption, because it is cheap and easy to apply compared to the gravimetric method. ^{[}^{1}^{1}^{,}^{1}^{2}^{]} There are many adsorption models, such as the Langmuir isotherm, BET isotherm, Freundlich Isotherm, OnoKondo model, etc. ^{[}^{1}^{3}^{,}^{1}^{4}^{]} However, the Langmuir isotherm is commonly used for evaluating adsorption data, because it is easy to use and practical for engineering purposes. ^{[}^{1}^{1}^{,}^{1}^{4}^{,}^{1}^{5}^{]} After determining the adsorp tion data of a shale gas reservoir, the constants of adsorption models are found. These constants and adsorption models are integrated into the simulators. These simulators are mainly used to predict ﬂ ow type and gas production from shale gas reservoirs. Adsorption data and models provide information about the amount of gasinplace and the adsorbed gas ratio at different
* Author to whom correspondence may be addressed. Email address: merey@metu.edu.tr Can. J. Chem. Eng. 94:1683 – 1692, 2016 _{©} 2016 Canadian Society for Chemical Engineering DOI 10.1002/cjce.22538 Published online 22 June 2016 in Wiley Online Library (wileyonlinelibrary.com).
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production pressures. For ﬂ ow and diffusivity equations, these data are very important. LeahyDios et al. ^{[}^{1}^{6}^{]} proposed two different transport models to model the ﬂ ow through shale gas and coalbed methane (CBM). They developed a new multicomponent adsorption model. The difference in cumulative gas production between the model and ﬁ eld data is 10 %. Similarly, Feast et al. ^{[}^{1}^{7}^{]} developed their simulator using BET and the Langmuir isotherm. They compared their model data with the actual ﬁ eld data of the Marcellus shale ﬁ eld and a good history match was obtained. Generally, it is assumed that natural gas includes 100 % CH _{4} during the adsorption studies. However, Hartman et al. ^{[}^{1}^{8}^{]} extended the Langmuir model to calculate the initial gasinplace 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 in ﬂ uenced by the gas mixture composition, a signi ﬁ cant adsorbed amount could be predicted incorrectly by considering the gasinplace as pure CH _{4} 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. ^{[}^{1}^{8}^{]} However, the adsorption layer effect is generally ignored. Different than the study of Hartman et al., ^{[}^{1}^{8}^{]} for determining the volume of adsorbed ﬂ uid, OnoKondo models were used in this study. This model was used in a few studies for the evaluation of adsorption data. ^{[}^{1}^{9}^{,}^{2}^{0}^{,}^{2}^{1}^{]} None of these studies try to use the model data to predict initial gasinplace amounts and adsorbed gas ratios in shale gas reservoirs by using OnoKondo 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 OnoKondo models. In this study, MATLAB codes were written for OnoKondo monolayer and threelayer models, which are used for the evaluation of experimental adsorption data and layered structure of adsorption. Moreover, the OnoKondo model was used to calculate the surface area of the shale sample. Finally, using the OnoKondo monolayer model and taking into account the adsorbed volume on the surface of the adsorbent, a formula was proposed for initial shale gasinplace calculations after modifying Ambrose et al.’ s ^{[}^{2}^{2}^{]} 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 gasphase 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. ^{[}^{2}^{3}^{]} Shale and BPL samples were dried in a vacuum oven at 105 8C for 24 h until constant mass was achieved before each
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 ﬁ lled 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 nonadsorbing gas. ^{[}^{1}^{2}^{]} 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 ﬁ lled 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, ﬁ ttings, and valves are evacuated from air by a vacuum. As seen in Figure 1, the sample and reference cells are separated by closing the shutoff valve V _{1} . In the next step, the desired amount of gas is admitted to the reference cell by opening the gas access valves V _{2} and V _{4} . Desired pressure values in the reference cell are supplied by a syringe pump. After the desired pressure is achieved in the reference cell, valve V _{2} 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 (CH _{4} ), ^{[}^{2}^{4}^{]} 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 V _{1} between the reference and sample cells is opened. Adsorbate gas (CH _{4} , 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 satis ﬁ ed, 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 ^{[}^{2}^{4}^{]} 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: ^{[}^{1}^{2}^{]}
n
Gibbs
ads
¼ n _{i}_{n}_{j} n
Gibbs
unads
^{ð}^{1}^{Þ}
The amount of gas injected from the reference cell to the sample cell can be determined using the following formula:
n inj ¼ V ^{r}^{e}^{f}
RT
P ref 1 P ref 2
z ref 1
z ref 2
ð2Þ
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Figure 1 . Schematic diagram of the adsorption experimental apparatus.
The amount of unadsorbed gas (free gas) in the sample cell at equilibrium pressure is calculated using the following formula:
n
Gibbs unads ^{¼} V void
RT
P
void 2
z
void2
ð3 Þ
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. ^{[}^{2}^{0}^{]} At lower pressures, the volume of adsorbed phase is negligible. Hence:
He _{v}_{o}_{i}_{d} V unads
_{V}
_{n}
abs
ads ^{¼} ^{n} ads
Gibbs
¼
n _{i}_{n}_{j} r _{g}_{a}_{s} V ^{H}^{e} void
ð4
^{ð}^{5}
Þ
^{Þ}
At higher pressures, the volume of adsorbed phase is signi ﬁ cant:
He _{v}_{o}_{i}_{d} ¼ V unads V ads
_{V}
_{n}
abs
_{a}_{d}_{s} ¼ n _{i}_{n}_{j} r _{g}_{a}_{s} V ^{H}^{e}
_{v}_{o}_{i}_{d} r _{a}_{d}_{s} V _{a}_{d}_{s}
ð6
ð7
Þ
Þ
By combining the adsorption formulas above, the following formula is obtained for absolute adsorption:
_{n}
abs
ads ^{¼}
n
Gibbs
ads
1
^{r}
^{r}
gas
ads
ð8 Þ
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 accurate equations of state, Angus ’ s EOS for CH _{4} ^{[}^{2}^{4}^{]} were used in this study to analyze experimental adsorption data. These equations are considered the most reliable equations of state. ^{[}^{2}^{4}^{]}
Adsorption Models
In this study, to evaluate raw experimental adsorption data, Langmuir isotherm and OnoKondo 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: ^{[}^{1}^{4}^{]}
1) The surface of an adsorbent is homogenous. This means that all the adsorption sites are energetically equivalent. 2) Adsorbed molecules do not interact with neighbouring adsorbed molecules. 3) Each site can hold one adsorbate molecule. 4) At the maximum adsorption, only a monolayer is formed.
The Langmuir equation describes the adsorption capacity of rock as pressure changes under isothermal conditions:
V ads ¼ ^{V} ^{L} ^{P}
_{P} L _{þ} _{P}
ð9Þ
OnoKondo lattice model
Adsorption occurs in shale gas and coalbed methane reservoirs at high pressures. However, there are not enough studies and models to represent adsorption at high pressures, especially for shales.
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The Langmuir isotherm is widely used but it is not suitable for especially high pressure adsorption. In the Langmuir isotherm, the volume of the adsorbed phase is ignored and there is no correction for adsorbed phase volume. Considering the drawbacks of adsorption models such as the Langmuir isotherm and other traditional methods, the OnoKondo lattice model is based on lattice theory and was proposed originally by Ono and Kondo in 1960 ^{[}^{1}^{1}^{,}^{2}^{0}^{]} and further developed by Donohue ^{[}^{1}^{1}^{,}^{2}^{0}^{]} and recently by Sudibandriyo. ^{[}^{2}^{0}^{]} In this model, the adsorption system is composed of layers of lattice cells that contain ﬂ uid molecules and vacancies. For the case of adsorption, more ﬂ uid molecules reside in the cells of the adsorbedphase layers than in the cells of the bulkphase layers. ^{[}^{2}^{1}^{]} The OnoKondo model has several advantages: ^{[}^{2}^{0}^{,}^{2}^{1}^{]}
1) It is used to describe multilayer adsorption. 2) It is able to describe adsorption behaviour based on the physical properties of the adsorbate and adsorbent. 3) It can estimate adsorbedphase densities, which provide a calculation of absolute gas adsorption. 4) It can be used to incorporate accurate density calculations from EOS models, which reduce the correlative burden on the adsorption model.
In the OnoKondo model, the ﬂ uid system consists of lattice cells occupied by ﬂ uid molecules or just empty cells. When adsorption occurs, more molecules will occupy cells in the adsorbedphase layer than the gasphase (bulk). When equilibrium exists between the gasphase and multilayer adsorbed phase, the expression for thermodynamic equilibrium for purecomponent adsorption under the mean ﬁ eld approxima tion can be written as follows: ^{[}^{2}^{0}^{]}
ln

x 
t 
ð Þ 1 x b 
þ ^{z} ^{0} 
ð x _{t} x _{b} 

x 
b 
ð x 1 t 
Þ 
kT 
Þe ii _{þ} z 2 x t þ 1 2x t þ x t 1 Þe ii
ð
kT
¼ 0
ð 10Þ
For t ¼ 2, 3, layer:
ln
x
1
ð
1 x
b
Þ
x
b
ð
1 x
1
Þ
þ
, m, number of the layer, and for 1 ^{s}^{t} adsorbed
ð z _{1} x _{1} þ z _{2} x _{2} z _{0} x _{b} kT
Þe ii
þ _{k}_{T} ¼ 0
e
is
ð 11Þ
For a hexagonal con ﬁ guration of lattice cells, the coordination numbers z _{0} and z _{1} are 8 and 6, respectively, and by de ﬁ nition, z _{2} ¼ (z _{0} z _{1} )/2. The analytical expression for the excess (Gibbs) adsorption from this model is as follows:
m
G ¼ C ^{X} ðÞ
x
t
x
b
t
ð 12Þ
where x _{t} ¼ r _{t} / r _{m}_{c} and x _{b} ¼ r _{b} / r _{m}_{c} To simplify the model, it is assumed that the adsorption occurs within a slit. For monolayer adsorption inside a slit, the equilibrium expression is written as follows:
ln
x
ads
ð
1 x
b
Þ
x
b
ð
1 x
ads
Þ
þ
ð
ð
z
1
þ 1Þx _{a}_{d}_{s} z _{0} x _{b} kT
Þe ii
þ _{k}_{T} ¼ 0
e
is
ð 13Þ
where z _{1} ¼ 6 and z _{0} ¼ 8 for the hexagonal lattice cell.
Excess (Gibbs) adsorption then simpli ﬁ es to the following:
G ¼ 2C ð x
ads
x
b
Þ¼ 2C
^{r}
ads
^{r}
mc
^{r} ^{b}
^{r}
mc
ð14Þ
The parameters of the model r _{m}_{c} , e _{i}_{i} /k, e _{i}_{s} /k, and C are obtained by ﬁ tting the model with experimental adsorption isotherm data. The parameters are ﬁ t when the average absolute percent deviation (AAD) in each isotherm is at a minimum. The AAD is calculated using the following equation:
N
ADD ¼ ^{X}
i
n exp n model
n
exp
_{} 100 %
ð15Þ
The ﬂ uidﬂ uid energy parameter, e _{i}_{i} /k, is estimated as being proportional to the LennardJones well depth energy parameter. ^{[}^{2}^{0}^{]} The following estimate for the ﬂ uidﬂ uid energy parameter is used in the OnoKondo model:
e _{i}_{i} ¼ 0: 432 e
ð16Þ
TwoParameter OnoKondo Model
For the twoparameter OnoKondo model, the ﬂ uidsolid energy parameter, e _{i}_{s} /k, is regressed for each speci ﬁ c adsorption system, and the parameter C is regressed for each adsorption isotherm using experimental adsorption data. Hence, it is called the two parameter OnoKondo model. ^{[}^{2}^{0}^{]} In this study, the twoparameter OnoKondo model was preferred to evaluate experimental adsorption data for both OnoKondo monolayer and threelayer
models. A MATLAB program for the OnoKondo monolayer and threelayer models was written in this study.
RESULTS AND DISCUSSION
Verification of Adsorption Experiments and Models
Before carrying out the CH _{4} adsorption experiments on the shale
sample, it is very important to prove the reliability of the adsorption experiments and calculation procedures. In this study, BPL activated carbon was used for this purpose by following Reich et al. ’s ^{[}^{2}^{5}^{]} experimental procedure. In Runs #1 and #2, CH _{4} adsorption experiments on BPL at 28.3 8C were performed. In Lancaster et al., ^{[}^{2}^{]} the adsorption isotherm experiments on Antrim Shale were conducted by different laboratories and their results were compared. However, different results were obtained due to different sample treatments, calibration mistakes in pressure transducers and thermocouples, and mistakes in adsorption calculations. To avoid similar mistakes, BPL activated carbon was used in this study. In the literature, several experimental data sets of BPLactivated carbon are available. Figure 2 shows the experimental results of Run #1, Run #2, and Reich et al.’ s ^{[}^{2}^{5}^{]} results. As can be seen, all adsorption isotherms agree closely. Therefore, it can be concluded that the experimental setup and calculation procedure used in this study are suitable for adsorption experiments.
In this study, to evaluate raw experimental adsorption data, Langmuir isotherm and OnoKondo models (monolayer and threelayer) were used. An algorithm was written for the OnoKondo monolayer and threelayer models using MATLAB
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Figure 2 . Comparison of CH _{4} adsorption isotherms on BPL for Reich et al.'s ^{[}^{2}^{5}^{]} adsorption experiments and Runs #1 and #2.
to ﬁ nd the adsorbed phase densities at different layers, surface areas, ^{[}^{1}^{9}^{]} and OnoKondo model parameters. The written algo rithm is checked using Sudibandriyo et al.’ s ^{[}^{2}^{0}^{]} experimental CH _{4} adsorption results for BPL. As shown in Table 1, the model parameters in this study and Sudibandriyo et al.’ s ^{[}^{2}^{0}^{]} study were compared. The values of the model parameters are quite close to each other. Small differences in the results are due to different initial guesses and different regression methods used.
CH _{4} Adsorption Isotherms
Before carrying out CH _{4} adsorption experiments on the shale sample, the data in Table 2 were obtained and used for adsorption calculations. In Figure 3, CH _{4} adsorption isotherms of the shale sample at 25 8C (Run #3), 50 8C (Run #5), and 75 8C (Run #6) are shown. As seen in Figure 3, adsorption capacities of CH _{4} on the shale sample decrease with increasing temperature, as expected. It is known that adsorption is exothermic, because heat is released as new bonds form. ^{[}^{1}^{4}^{]} Hence, the bonds between adsorbate (CH _{4} ) and adsorbent (shale sample) are weakened and desorption occurs when temperature increases. The adsorption capacities increase linearly with pressure in Figure 2. However, after certain pressures, this increase stops and there is even a small decrease in the adsorption capacities. Shales have nanoporous 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 CH _{4} molecules, which causes an increase in adsorption and may cause complete ﬁ lling of pores at low pressures. This is a typical behaviour of a Type I adsorption isotherm which depicts monolayer adsorption on the adsorbent surface. ^{[}^{1}^{4}^{]} Hence, after ﬁ lling 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, CH _{4} 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 CH _{4} Adsorption Experimental Data using Langmuir Isotherm and OnoKondo Models
After obtaining adsorption isotherms with the help of the experiments, it is very important to ﬁ t the data to adsorption
Table 1. Comparision of OnoKondo monolayer and threelayer model results
Model 
Parameters Monolayer Threelayer 

Model in this study 
%AAD e _{f}_{s} /k (K) 
0.8 
2.9 

1381 
1721 

C 
(mmol/g) %AAD e _{f}_{s} /k (K) 
3.14 
4.34 

Model in Sudibandriyo et al.'s ^{[}^{2}^{0}^{]} study 
0.6 
2.8 

1385 
1690 

C 
(mmol/g) 
3.26 
4.53 
Table 2 . Experimental data for the adsorption experiments with Dadas shale sample
Parameters
Runs #3, #4, #5, #6
Reference cell volume Sample mass Sample cell volume (empty) Mesh size of the sample Average void volume in the sample cell
44.3 cm ^{3} 121.7 g 122.4 cm ^{3} (20/35) or 841 – 500 mm 58.61 cm ^{3}
models. As seen in Figure 5, experimental CH _{4} adsorption data from shale samples at 25, 50, and 75 8C were ﬁ tted well by the Langmuir isotherm and OnoKondo models. The parameters of these models are listed in Tables 3–4. As seen in Table 4, model parameters of the OnoKondo threelayer model are close to the parameters of the OnoKondo monolayer model. Small differences in adsorption parameters for the OnoKondo models are mostly related to the regression model used in the program, and differences in initial guesses of ﬂ uidsolid energy parameters. Adsorption occurred as a monolayer in Runs #3, #5, and #6 because the ﬁ rst layer’ s adsorbed densities are higher than the bulk phase densities of CH _{4} . However, the second and third layer ’ s adsorbed densities are close to CH _{4} gas densities. This means that adsorption occurred as a monolayer in Runs #3, #5, and #6. It is also known that the Type I adsorption isotherm happens as a monolayer because of microporous structure. ^{[}^{1}^{4}^{]} This supports the results of the OnoKondo models in this study.
Figure 3 . Comparison of CH _{4} adsorption isotherms of Dadas shale sample for Runs #3, #5, and #6.
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Figure 4 . Comparison of CH _{4} adsorption isotherms of Dadas shale sample for Runs #3 and #4.
Adsorption is expected to occur as a monolayer because of the small molecule sizes of shale samples in pore networks. Therefore, for evaluating the adsorption data of shale samples, the OnoKondo monolayer model is sufﬁ cient and there is no need to use the OnoKondo threelayer model. Another advantage of OnoKondo models is the prediction of the surface area of shale samples. As shown in Table 4, the surface area values of shale samples at 25, 50, and 75 8C are between 13.376– 16.070 m ^{2} /g by applying the method of Sudibandriyo. ^{[}^{1}^{9}^{]} Therefore, OnoKondo models are capable of approximately predicting the surface area of shale samples with their experimental adsorption data. The adsorption capacity is calculated by ignoring the volume of 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 high pressures, it is very important to make void volume corrections in order to calculate absolute adsorption. In adsorp tion, adsorbed molecules form a layer on the adsorbent. At low pressures, the volume of the adsorbed layer is negligible. However, with increasing pressure, the volume of the adsorbed layer becomes important. The Langmuir model is not capable of calculating the volume of the adsorbed layer using adsorbed phase
Figure 5. Comparision of CH _{4} excess adsorption data and adsorption model predictions for Runs #3, #5, and #6.
Table 3 . Langmuir isotherm parameters for Runs #3, #5, and #6
Model parameters Run #3 (25 8C) Run #5 (50 8C) Run #6 (75 8 C)
V _{L} (mmol/g) 
0.0545 
0.0463 
0.0293 
P _{L} (psia (MPa)) 
387.9 (2.67) 
965 (6.65) 
992 (6.84) 
R ^{2} 
0.995 
0.996 
0.994 
densities. In contrast, using adsorbed phase densities obtained with the OnoKondo 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 signi ﬁ cant differences between absolute adsorption and excess adsorption for all temperatures, indicating the high capability of OnoKondo models compared to the Langmuir isotherm.
Initial GasinPlace Calculations in Shale Gas Reservoirs
Shale gas reservoirs are classiﬁ ed as unconventional reserves. Hence, initial gasinplace calculation equations for conventional reserves cannot be used for shale gas reservoirs. Ambrose et al. ^{[}^{2}^{2}^{]} proposed a new technique to calculate shale gasinplace. However, in Ambrose et al. ’ s ^{[}^{2}^{2}^{]} equations, only Langmuir isotherm parameters are used, and volume occupied by adsorbed gas molecules is ignored. In this study, in addition to the Langmuir isotherm, OnoKondo models were used to evaluate experimental adsorption data. Hence, modiﬁ cations were made to Ambrose et al.’ s ^{[}^{2}^{2}^{]} shale gasinplace calculations to take into account the volume of adsorbed gas on the surface of the adsorbent in this study. Ambrose et al.’ s ^{[}^{2}^{2}^{]} initial shale gasinplace formula is given as follows:
^
_{G} st _{¼} 32 : 0368 f 1 S
þ
B
g
G
sL
P
r
rock
w
"
ð
Þ
1 :318 10 M
6
r
s
P þ P _{L}
G
sL
P
P þ
P
L
#
ð17Þ
Instead of the adsorbed gas amount calculated by the Langmuir isotherm as used in Equation (17), the OnoKondo monolayer model parameters (Equation (18)) were preferred to calculate adsorption capacity, as it was indicated that adsorption occurs as a monolayer in shale gas reservoirs.
G a ¼ G sL
P
P þ P _{L}
! G _{a} ¼ 1518 C
^{r}
ads
^{r}
mc
^{r} gas
^{r}
mc
ð18Þ
The initial shale gasinplace calculation formula (Equa tion (19)) is obtained using the OnoKondo monolayer model by inserting Equation (18) into Equation (17):
^
_{G} st _{¼} 32 : 0368 f 1 S
B
g
r
^{r}
rock
ads
^{r}
mc
w
^{r} gas
^{r}
mc
"
ð
Þ
2 :001 10 M
3
r
ads
þ 1518 C
C
r
ads
r
mc
^{r}
gas
r
mc
#
ð19Þ
In both Ambrose ’ s equation (Equation (17)) ^{[}^{2}^{2}^{]} and the modiﬁ ed equation (Equation (19)), the volume occupied by the adsorbed phase is ignored. Especially at high pressures, the
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Table 4 . OnoKondo (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 threelayer 
OK monolayer 
OK threelayer 
OK monolayer 
OK threelayer 
parameters 
model 
model 
model 
model 
model 
model 
%AAD e _{f}_{s} /k (K) C (mmol/g) 
2.406 
2.741 
2.177 
2.025 
4.268 
4.093 
785 
765 
540 
540 
490 
490 

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 
(m ^{2} /g)
volume occupied by the adsorbed phase becomes important. Hence, in the following equations (Equations (20– 21)), a correction was done using adsorbed phase density to consider the volume occupied by the adsorbed gas. Excess (Gibbs) adsorption in Equation (18) was converted to absolute adsorption for the OnoKondo monolayer model by Equation (20).
G a absolute ¼ 1518C
r
^{r}
gas
^{r}
r gas ! ! G a absolute
ads
ads
r
mc
r
mc
^{r} ads ^{}
¼ 1518 C
^{r}
ads
^{r}
mc
ð20 Þ
Then, Equation (20) was inserted into Equation (17) to obtain the corrected form of the shale gasinplace equation (Equa tion (21)) which accounts for absolute adsorption.
^
_{G} st _{¼} 32 : 0368 f 1 S
B
g
r
^{r}
rock
ads
^{r}
mc
w
^{r} gas
^{r}
mc
"
ð
Þ
2: 001 10 MC
3
#
r
mc
þ 1518C
ð21 Þ
For the shale gas reservoir, the data in Table 5 were used for initial gasinplace calculations for 25, 50, and 75 8C. Initial gasin place calculations done without considering the volume of adsorbed gas (excess adsorption) using Ambrose’ s equation
Figure 6 . Comparison of CH _{4} excess adsorption data and absolute adsorption data for Runs #3, #5, and #6.
(Equation (17)) ^{[}^{2}^{2}^{]} and modiﬁ ed Equation (19) gave similar results, as seen in Figure 7. However, to correct the volume of gas adsorbed in the experiments, Equation (21) was used for initial gasinplace
calculations (Figure 8). As seen in Figure 9 at 75 8 C, between
3447 – 34 470 kPa (500 –5000 psia), the adsorbed gas percentage
calculated by Equation (21) changes from 41.6 % to 26.9 % for the shale reservoir. The results show that the adsorbed gas
percentages using Equation (21) are 1.3– 2.4 times higher than the values calculated by Equation (17). Similar differences were obtained for 25 and 50 8C. These differences are quite large. Therefore, the correction in Equation (21) for absolute adsorption can be suggested for the most accurate shale gasinplace calculations. For the exact initial gasinplace calculations, accurate experi mental adsorption data are needed at different pressures. Although the Langmuir isotherm is commonly used in the experimental adsorption data evaluation, such as in the study of Heller &
Zoback, ^{[}^{1}^{0}^{]} adsorption is calculated lower than its actual value due to ignoring the volume of adsorbed gas. In this and similar
studies, ^{[}^{1}^{9}^{,}^{2}^{0}^{,}^{2}^{1}^{]} it was shown that the OnoKondo monolayer model is useful for predicting the volume of adsorbed gas, and by using this value, absolute adsorption is calculated. For example, using the experimental adsorption data of Heller & Zoback, ^{[}^{1}^{0}^{]} the absolute adsorption is calculated by applying OnoKondo
models. When Langmuir isotherm parameters are used for initial gasinplace calculations as in Equation (17), the adsorbed amount 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 ﬁ nd the density of adsorbed gas on the layer of shale. In Hartmann et al., ^{[}^{1}^{8}^{]} 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 gasinplace 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 
S _{w} , fraction 
0.35 
0.35 
0.35 
r _{b} (g/cm ^{3}^{)} 
2.06 
2.06 
2.06 
C (mmol/g) 
0.0489 
0.0523 
0.0408 
P _{L} (psia (MPa)) 387.9 (2.67)
965 (6.65)
992 (6.84)
G _{s}_{L} (V _{L} ) 41.37 scf/ton 
35.14 scf/ton 
22.24 scf/ton 
(0.0545 mmol/g) 
(0.0463 mmol/g) 
(0.0293 mmol/g) 
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Figure 7. Shale gasin place calculations by Equations (17) and (19) for Runs #3, #5, and #6.
Figure 8 . Shale gasin place calculations by Equation (21) for Runs #3, #5, and #6.
Figure 9. Adsorbed gas (CH _{4} ) percentages for shale gas reservoir for Runs #3, #5, and #6.
predicted using OnoKondo models and experimental adsorption data as well as OnoKondo model parameters C and e _{f}_{s} /k. These parameters are used in Equation (21) (found and proposed in this study) for initial gasinplace 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}^{,}^{1}^{0}^{,}^{1}^{8}^{,}^{2}^{2}^{]} the surface areas of shale samples are approximated using OnoKondo models.
CONCLUSIONS
In this study, experiments were performed to investigate adsorption capacities and behaviours of shale samples for initial shale gasinplace calculations. Adsorption experiments of CH _{4} 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 ﬁ lling 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. OnoKondo and Langmuir equations are capable of modelling adsorption isotherms both at high and low pressures. However, OnoKondo models differ from the Langmuir model, as can be evaluated for different layers of adsorption. In this study, the OnoKondo monolayer and OnoKondo threelayer models were used and compared. By using experimental data with the prepared algorithm which uses the OnoKondo model, it was found that adsorption for the shale sample occurs as a monolayer, as expected, because of nanoporous structures of shale gas reservoirs. It was also seen that the shale sample ’ s adsorption curve ﬁ ts with the Type I isotherm curve, which generally occurs in monolayer adsorption. Hence, for shale gas reservoirs, the OnoKondo monolayer model ﬁ ts adsorption data sufﬁ ciently closely, and there is no need to use the OnoKondo threelayer model. Both the OnoKondo 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, OnoKondo models are capable of calculating absolute adsorption by correcting excess (Gibbs) adsorption values, since they can be used to calculate adsorbed density values. Shale gasinplace equations proposed by Ambrose et al. ^{[}^{2}^{2}^{]} were modi ﬁ ed for the OnoKondo monolayer model with and without considering the volume of adsorbed gas. The original equation with the Langmuir model and modi ﬁ ed equation with the OnoKondo monolayer model resulted in similar excess adsorption data. In contrast, when the volume of adsorbed gas is considered in the ﬁ nal form of the initial gasinplace 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
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important for reservoir management studies. Therefore, the modiﬁed equation including the volume of adsorbed gas correction (Equation (21)) in this study is suggested for shale gasinplace calculations. By using this equation and the OnoKondo monolayer model parameters of experimental adsorption data, the adsorbed and free gas amounts at initial conditions and different production pressures can be calculated. The parameters of the OnoKondo monolayer can be used in shale gas reservoir simulators. As well as gasinplace calculations, free gas amounts in pores at different production pressures are important for diffusivity equations during the simulation of gas production from shale gas reservoirs.
NOMENCLATURE
B _{g}
prefactor related to capacity of the adsorbent for a specific gas (mmol/g) fluidfluid interaction energy fluidsolid surface interaction energy well depth of the potential
^{e} e _{i}_{s} or e _{f}_{s} e ^{}
G _{a} gas adsorbed on the surface (0.028 316 85 m ^{3} _{S}_{T}_{P} /ton
(scf/ton)) absolute gas adsorbed on the surface (0.028 316 85 m ^{3} _{S}_{T}_{P} /ton (scf/ton)) Langmuir volume (0.028 316 85 m ^{3} _{S}_{T}_{P} /ton (scf/ton)) total gasinplace (0.028 316 85 m ^{3} _{S}_{T}_{P} /ton (scf/ton))
G
G
G
C
gas formation volume factor
_{i}_{i}
_{a}_{_}_{a}_{b}_{s}_{o}_{l}_{u}_{t}_{e}
_{s}_{L}
_{s}_{t}
k 
Boltzman ’ s constant 
m 
maximum number of adsorbed layers in an 
adsorption isotherm 

^ 

M 
apparent natural gas molecular mass (g/mol) 
or G excess (Gibbs) adsorption amount (mmol/g) free gas amount (mmol/g) injected gas amount from reference cell to sample cell (mmol/g) amount of free gas in the sample (mmol/g) absolute adsorption (mmol/g)
n
_{n}
n _{e}_{x}_{p} adsorption capacity of the experimental data
(mmol/g) adsorption capacity calculated from the model (mmol/g)
pressure (6.894 757 kPa (psia)) Langmuir pressure (6.894 757 kPa (psia)) pressure of the reference cell before expansion (6.894 757 kPa (psia)) pressure of the reference cell after expansion (6.894 757 kPa (psia)) pressure in the void volume of the sample cell after expansion (6.894 757 kPa (psia))
n
n
n
Gibbs
n ads
Gibbs
_{u}_{n}_{a}_{d}_{s}
_{i}_{n}_{j}
_{u}_{n}_{a}_{d}_{s}
abs
_{a}_{d}_{s}
_{m}_{o}_{d}_{e}_{l}
P
P
P
P
P
_{L}
_{r}_{e}_{f}_{1}
_{r}_{e}_{f}_{2}
_{v}_{o}_{i}_{d}_{2}
R 
universal gas constant 
F 
porosity fraction 
_{a}_{d}_{s}
_{b}
_{r}_{o}_{c}_{k}
_{g}_{a}_{s}
_{s}
r
S _{w}
T
V
V
V
_{t}
_{r}_{e}_{f}
He
_{v}_{o}_{i}_{d}
_{u}_{n}_{a}_{d}_{s}
r
r
r
r
adsorbedphase density at different pressure (g/cm ^{3} ) r _{m}_{c} adsorbedphase density corresponding to maxi mum adsorption capacity (g/cm ^{3} ) adsorbed density of the adsorbate at layer t
r
adsorbed gas density (g/cm ^{3} ) bulk density of the adsorbate at layer t (g/cm ^{3} ) bulkrock density (g/cm ^{3} ) freegasphase density (g/cm ^{3} )
water saturation
absolute temperature volume of the reference cell (cm ^{3} ) helium void volume in the sample cell (cm ^{3} ) volume of unadsorbed gas in sample cell (cm ^{3} )
V _{a}_{d}_{s} gas volume that can be adsorbed by a rock of unit mass (0.028 316 85 m ^{3} _{S}_{T}_{P} /ton (scf/ton)) V _{L} Langmuir volume, maximum gas volume that can be adsorbed (0.028 316 85 m ^{3} _{S}_{T}_{P} /ton (scf/ton)) x _{t} reduced density or fraction of sites occupied by adsorbed molecules in layer t fraction of sites occupied by fluid molecules in the bulk fraction of r _{a}_{d}_{s} to r _{a}_{d}_{s} compressibility factor of gas in the reference cell before expansion compressibility factor of gas in the reference cell after expansion compressibility factor of gas in the void spaces of the sample cell after expansion
x
x
_{b}
_{a}_{d}_{s}
z
z
z
_{r}_{e}_{f}_{1}
_{r}_{e}_{f}_{2}
_{v}_{o}_{i}_{d}_{2}
REFERENCES
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[11] S. Merey, Experimental Analysis of Adsorption Capacities and Behaviors of Shale Samples , MSc thesis, Middle East Technical University, Ankara 2013. [12] S. A. Mohammad, J. Fitzgerald, R. L. Robinson, K. A. M. Gasem, Energ. Fuel . 2009 , 23, 2810. [13] M. Sudibandriyo, Z. Pan, J. E. Fitzgerald, R. L. Robinson, K. A. M. Gasem, Langmuir 2003, 19, 5323. [14] D. M. Ruthven, Principles of Adsorption and Adsorption Processes , John Wiley & Sons, New York 1984 . [15] H. Haiya, Chinese Journal of Geochemistry 2014 , 33 , 425.
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[16] A. LeahyDios, M. Das, A. Agarwal, R. D. Kaminsky, “Modeling of Transport Phenomena and Multicomponent Sorption for Shale Gas and Coalbed Methane in an Unstructured Grid Simulator,” SPE Annual Technical Confer ence and Exhibition , Denver, 30 October –2 November 2011 .
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[24] S. Angus, B. Armstrong, K. M. de Reuck, International Thermodynamic Tables of the Fluid State– 5: Methane, Pergamon Press, New York 1978. [25] R. Reich, W. T. Ziegler, K. A. Rogers, Ind. Eng. Chem. Proc. D. D . 1980 , 19, 336.
Manuscript received July 30, 2015; revised manuscript received November 30, 2015; accepted for publication December 7, 2015.
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