2012-Simulating Effects of Adsorption, Diffusion, and Convection in Tight Formations

UNIVERSITY OF OKLAHOMA
GRADUATE COLLEGE

SIMULATING EFFECTS OF ADSORPTION, DIFFUSION, AND CONVECTION IN TIGHT
FORMATIONS

A THESIS

SUBMITTED TO THE GRADUATE FACULTY

in partial fulfillment of the requirements for the

Degree of

MASTER OF SCIENCE IN NATURAL GAS ENGINEERING AND MANAGEMENT

By

JIAZUN LI
Norman, Oklahoma
2012

SIMULATING EFFECTS OF ADSORPTION, DIFFUSION, AND CONVECTION IN TIGHT
FORMATIONS

A THESIS APPROVED FOR THE
MEWBOURNE SCHOOL OF PETROLEUM AND GEOLOGICAL ENGINEERING

BY

______________________________
Dr. Maysam Pournik, Chair

______________________________
Dr. Ahmad Jamili

______________________________
Dr. Deepak Devegowda

Copyright by JIAZUN LI 2012
All Rights Reserved.

To Mom, Dad, Grandma, and Grandpa

I love you so much!
iv
Acknowledgements
I wish to express my sincere appreciation and thanks to my advisors Dr. Pournik and
Dr. Jamili for their infinite support and guidance throughout my thesis studies. I will
always remember their help and encouragement in my most difficult time. I also want to
thank my committee member Dr. Devegowda for his interest in my work and attention
on my project. Their religious attitude to science will impact my whole life.
I would like to thank Dr. Sharma for offering me the opportunity to study in our
department. I can feel his warm care in all my study life in OU. I would like to thank
Dr. Vaughn and Lori Stevens for their help in my difficult time.
I would like to extend my thanks to all professors teach me courses: Dr. Callard, Dr.
Samuel, Dr. Civan, Dr. Akkutlu, and Dr. Ahmed. The knowledge I learned in their
classes are solid academic foundation for my future study and work. Special thanks to
Srinivasan for giving me advice when I started using ECLIPSE* to study my thesis
project.
Last but most importantly, I would like to thank my family and friends. The infinite
love, support, and trust my parents gave me are always the strongest encouragement for
me to study abroad. And my dear friends, Yue, C.Chen, Yuqi, Yuntao, Yijia, Xinya,
Ronald, Eric, Darren, Ali, Jide, Busayo, Mitchell, Kiersten, Hannah, Panyu, Z.Jian,
Wanwei, Shuoshi, Jiangang, Liqiang, Luding, thank you all for accompanying and
helping me since I came to OU. I will never forget the happy time we spent together.
v
Table of Contents
Acknowledgements .......................................................................................................... iv
Table of Contents .............................................................................................................. v
List of Tables .................................................................................................................... vii
List of Figures .................................................................................................................... ix
Abstract .......................................................................................................................... xvi
Chapter 1: Introduction .................................................................................................... 1
1.1 Properties of shale formations ............................................................................. 2
1.2 Adsorption in shale formations ............................................................................ 5
1.3 Gas flow mechanisms in shale formations ........................................................... 7
1.3.1 Flow in micropores ...................................................................................... 7
1.3.2 Flow in nanopores ....................................................................................... 8
Chapter 2: Modeling of Gas Transport in Conventional Gas Reservoirs and Tight Gas
Reservoirs/Shales ............................................................................................... 16
2.1 Objective ............................................................................................................. 16
2.2 Model specification ............................................................................................ 17
Chapter 3: Results and Discussion .................................................................................. 24
3.1 Grid size .............................................................................................................. 24
3.2 Adsorption .......................................................................................................... 37
3.3 Molecular diffusion............................................................................................. 50
3.4 Adsorption and diffusion .................................................................................... 64
Chapter 4: Conclusions and Suggestions ........................................................................ 72
vi
4.1 Conclusions ......................................................................................................... 72
4.2 Suggestions for future work ............................................................................... 73
Nomenclature ................................................................................................................. 74
References ...................................................................................................................... 77
Appendix A: Estimation of Diffusion Coefficients .......................................................... 81
Appendix B: Relationship between Two Diffusion Coefficients ..................................... 85
B.1 Concentration gradient driving diffusion model ................................................ 85
B.2 Chemical potential gradient driving diffusion model......................................... 85
Appendix C: Estimation of Knudsen Number and Apparent Permeability .................... 87

vii
List of Tables
Table 1-1: The distribution of worldwide unconventional gas resources. (Holdith, 2006)
.......................................................................................................................................... 2
Table 2-1: Model parameters in this study. .................................................................... 22
Table 2-2: Critical properties of methane for running the one component compositional
model. ............................................................................................................................. 22
Table 2-3: Specifications of simulation cases in this study. ........................................... 23
Table 3-1: Grid size effects on conventional gas reservoirs and shale formations. ....... 27
Table 3-2: Langmuir isotherm data of methane in shale formations from literature
review. ............................................................................................................................ 40
Table 3-3: Adsorption/desorption effects on conventional gas reservoirs and shale
formations. ...................................................................................................................... 41
Table 3-4: Methane self-diffusion coefficients from literature review and empirical
model calculations. ......................................................................................................... 54
Table 3-5: Molecular diffusion driven by concentration gradient effects on conventional
gas reservoirs and shale formations. ............................................................................... 55
Table 3-6: Molecular diffusion driven by chemical potential gradient effects on
conventional gas reservoirs and shale formations. ......................................................... 56
Table 3-7: Effects of different mechanisms on conventional reservoirs and shale
formations. ...................................................................................................................... 66
Table A-1: Parameters for estimating binary gas diffusion coefficients by empirical
models..82
viii
Table A-2: Models of estimating self-diffusion coefficients..84
Table A-3: Diffusion coefficients of methane self-diffusion system estimated by
empirical models.........................84
Table C-1: Knudsen number estimation in this study. ...89
Table C-2: Apparent permeability estimation in this study. ...89
ix
List of Figures
Figure 1-1 Pore distribution in conventional gas reservoirs and shale formations.
(Javadpour et al., 2007) .................................................................................................... 3
Figure 1-2: Frequency versus permeability of 152 shale gas samples from nine
reservoirs. (a) permeability distribution, (b) cumulative frequency distribution.
(Javadpour et al., 2007) .................................................................................................... 4
Figure 1-3: A typical Langmuir isotherm curve. (Das et al., 2012) ................................. 6
Figure 1-4: Gas molecules movements in shale formations. (Javadpour, 2009) .............. 8
Figure 2-1: Simulation and experimental results showing the impact of pore pressure on
the interactions between gas molecules and pore wall. (Fathi et al., 2012) ................... 20
Figure 2-2: Dimensions and grid blocks for reservoir models; using grid blocks of
(11x11x1) and (110x110x10); (X, Y, Z) orders. ............................................................ 20
Figure 2-3: The relative permeability curve (top) and capillary pressure curve (bottom)
used in this study. ........................................................................................................... 21
Figure 3-1: gas production rate in different models ....................................................... 28
Figure 3-2: Pressure gradient in different grid size models. .......................................... 28
Figure 3-3: Impact of grid size on gas production rate with time (100 days) for
conventional gas reservoirs. ........................................................................................... 29
Figure 3-4: Semi-log plot shows the impact of grid size on cumulative gas production
with time (1000 days) for conventional gas reservoirs. ................................................. 29
Figure 3-5: Impact of grid size on reservoir pressure with time (100 days) for
conventional gas reservoirs. ........................................................................................... 30
x
Figure 3-6: Impact of grid size on gas-in-place with time (100 days) for conventional
gas reservoirs. ................................................................................................................. 30
Figure 3-7: Impact of grid size on gas production rate with time (50 years) for shale
formations. ...................................................................................................................... 31
with time (50 years) for shale formations. ...................................................................... 31
Figure 3-9: Impact of grid size on reservoir pressure with time (50 years) for shale
formations. ...................................................................................................................... 32
Figure 3-10: Impact of grid size on gas-in-place with time (50 years) for shale
formations. ...................................................................................................................... 32
Figure 3-11: Impact of grid size on gas production rate in the first year for shale
formations with fractures. ............................................................................................... 33
Figure 3-12: Impact of grid size on gas production rate with time (50 years) for shale
with time (50 years) for shale formations. ...................................................................... 34
Figure 3-15: Impact of grid size on gas in place with time (50 years) for shale
Figure 3-16: Pressure drop in conventional reservoirs for 100 days .............................. 35
Figure 3-17: Pressure drop in shale formations for 50 years .......................................... 36
Figure 3-18: Pressure drop in shale formations with fractures for 50 years................... 36
xi
Figure 3-19: Langmuir isotherm curve used for this study. ........................................... 42
Figure 3-20: Impact of adsorption on gas production rate with time (100 days) for
conventional gas reservoirs; using grid blocks of (11x11x1) and (110x110x10). ......... 42
Figure 3-21: Semi-log plot showing the impact of adsorption on cumulative gas
production with time (1000 days) for conventional gas reservoirs; using grid blocks of
(11x11x1) and (110x110x10). ........................................................................................ 43
Figure 3-22: Impact of adsorption on gas-in-place with time (100 days) for conventional
gas reservoirs; using grid blocks of (11x11x1) and (110x110x10). ............................... 43
Figure 3-23: Gas-in-place of two states of gas with time (100 days) for conventional gas
reservoirs; using grid blocks of (11x11x1) and (110x110x10). ..................................... 44
Figure 3-24: Impact of adsorption on gas production rate with time (50 years) for shale
formations; using grid blocks of (11x11x1) and (110x110x10). .................................... 44
production with time (50 years) for shale formations; using grid blocks of (11x11x1)
and (110x110x10). .......................................................................................................... 45
Figure 3-26 : Impact of adsorption on gas-in-place with time (50 years) for shale
formations; using grid blocks of (11x11x1) and (110x110x10). .................................... 45
Figure 3-27: Gas-in-place of two states of gas with time (50 years) for shale formations;
using grid blocks of (11x11x1) and (110x110x10). ....................................................... 46
Figure 3-28: Impact of adsorption on gas production rate in the first year for shale
formations with fractures; using grid blocks of (11x11x1) and (110x110x10). ............. 46
Figure 3-29: Impact of adsorption on gas production rate with time (50 years) for shale
xii
production with time (50 years) for shale formations with fractures; using grid blocks of
(11x11x1) and (110x110x10). ........................................................................................ 47
Figure 3-31: Impact of adsorption on gas-in-place with time (50 years) for shale
Figure 3-32: Gas-in-place of two states of gas with time (50 years) for shale formations
with fractures; using grid blocks of (11x11x1) and (110x110x10). ............................... 48
Figure 3-33: Comparison of adsorption effects on gas production rate with time (100
days) for conventional gas reservoirs and shale formations; using grid size of (11x11x1)
and (110x110x10). .......................................................................................................... 49
Figure 3-34: Impact of molecular diffusion by concentration gradient on gas-in-place
with time (100 days) for conventional gas reservoirs; using grid blocks of (11x11x1)
and (110x110x10). .......................................................................................................... 57
with time (50 years) for shale formations; using grid blocks of (11x11x1) and
(110x110x10). ................................................................................................................ 57
with time (50 years) for shale formations with fractures; using grid blocks of (11x11x1)
and (110x110x10). .......................................................................................................... 58
Figure 3-37: Impact of molecular diffusion on gas production rate with time (100 days)
for conventional gas reservoirs; using grid blocks of (11x11x1) and (110x110x10). .... 58
Figure 3-38: Impact of molecular diffusion on gas in place with time (100 days) for
conventional gas reservoirs; using grid blocks of (11x11x1) and (110x110x10). ......... 59
xiii
Figure 3-39: Impact of molecular diffusion on cumulative gas production with time
(1000 days) for conventional gas reservoirs; using grid blocks of (11x11x1) and
(110x110x10). ................................................................................................................ 59
Figure 3-40: Impact of molecular diffusion on gas production rate with time (50 years)
for shale formations; using grid blocks of (11x11x1) and (110x110x10). ..................... 60
Figure 3-41: Impact of molecular diffusion on gas in place with time (50 years) for
shale formations; using grid blocks of (11x11x1) and (110x110x10). .......................... 60
Figure 3-42: Semi-log plot showing the impact of molecular on cumulative gas
production with time (50 years) for shale formations; using grid size of (11x11x1) and
(110x110x10). ................................................................................................................ 61
Figure 3-43: Impact of molecular diffusion on gas production rate in the first year for
shale formations with fractures; using grid blocks of (11x11x1) and (110x110x10). ... 61
Figure 3-44: Impact of molecular diffusion on gas production rate with time (50 years)
for shale formations with fractures; using grid blocks of (11x11x1) and (110x110x10).
........................................................................................................................................ 62
shale formations with fractures; using grid blocks of (11x11x1) and (110x110x10). ... 62
Figure 3-46: Impact of molecular diffusion on cumulative gas production with time (50
years) for shale formations with fractures; using grid blocks of (11x11x1) and
(110x110x10). ................................................................................................................ 63
Figure 3-47: Comparison of molecular diffusion effects on gas production rate with
time (100 days) for conventional gas reservoirs and shale formations; using grid size of
(11x11x1) and (110x110x10). ........................................................................................ 63
xiv
Figure 3-48: Impacts of different transport mechanisms on gas production rate with time
(100 days) for conventional gas reservoirs; using grid blocks of (110x110x10). .......... 67
Figure 3-49: Impact of different transport mechanisms on gas in place with time (100
days) for conventional gas reservoirs; using grid blocks of (110x110x10). .................. 67
Figure 3-50: Semi-log plot showing the impact of different transport mechanisms on
cumulative gas production with time (1000 days) for conventional gas reservoirs; using
grid blocks of (110x110x10). ......................................................................................... 68
(50 years) for shale formations; using grid size of (110x110x10). ................................ 68
Figure 3-52: Impact of different transport mechanisms on gas-in-place with time (50
years) for shale formations; using grid size of (110x110x10). ....................................... 69
Figure 3-53: Semi-log plot showing the impact of different transport mechanism on
cumulative gas production with time (50 years) for shale formations; using grid size of
(110x110x10). ................................................................................................................ 69
Figure 3-54: Impacts of different transport mechanisms on gas production rate in the
first year for shale formations with fractures; using grid size of (110x110x10). ........... 70
(50 years) for shale formations with fractures; using grid size of (110x110x10). ......... 70
Figure 3-56: Impacts of different transport mechanisms on gas in place with time (50
years) for shale formations with fractures; using grid size of (110x110x10). ................ 71
Figure 3-57: Impacts of different transport mechanisms on cumulative gas production
with time (50 years) for shale formations with fractures; using grid size of
(110x110x10). ................................................................................................................. 71
xv
Figure C-1: gas production rate for different permeability cases.90
Figure C-2: reservoir pressure for different permeability cases.90

xvi
Abstract
Production from tight formations introduces different flow mechanisms, which
makes the prediction of production more complex than conventional reservoirs. The
much smaller pore diameters in the range of mostly nanometers rather than micrometers
results in an extremely low formation permeability in range of nanodarcy. As a result
of such small pore diameter, large surface area is exposed in the porous media with
larger volume of gas adsorbing on the pore surface, which in turn allows more gas
production from desorption mechanism if the pressure change is favorable.
Furthermore, due to the tight nature of permeability, flow from pressure gradient due to
convection is limited. As a result, flow contribution from diffusion becomes more
significant. Some new flow mechanisms like Knudsen diffusion and surface diffusion
also come into play in these smaller pore size reservoirs.
While it is clearly understood that flow mechanisms in tight formations differs
significantly from conventional reservoirs, most studies on tight formations have not
accurately incorporated these new flow mechanisms. Furthermore, there has been no or
very limited study on the impact of each of these flow mechanisms on the total
production in order to determine the relative importance of each mechanism.
In this study, we focus on determining the relative importance of convection,
desorption and molecular diffusion on the production from tight formations and
compare these contributions to those in conventional reservoirs. In order to focus on the
impact of flow mechanisms, we use single gas component (methane) system with a
single porosity model to simulate flow. Convection is defined by Darcys Law, as is
defined in conventional reservoirs. For adsorption/desorption mechanism, Langmuir
xvii
isotherm model is applied to describe the process. Two models for describing molecular
diffusion are used, one based on concentration drive and another based on chemical
potential drive. In addition, we also study the effect of grid size on the flow simulations
as numerical dispersion becomes more significant as the pore size becomes smaller.
The results indicate that adsorption/desorption mechanism plays an important role in
shale formations only when the reservoir pressure drops to a low values. Secondly, the
contribution of molecular diffusion in shale formations is significant because the low
permeability and pressure drop cause a small amount of convection and desorption.
Thirdly, the grid size effects are very important in this simulation work, especially be
significant for shale formation model because of numerical dispersion. Finally,
molecular diffusion driven by concentration gradient model is not applicable to this
single gas component system study.
1
Chapter 1: Introduction
As a result of the high development of modern society, more fossil energy resources are
required to meet the basic demand of human beings. In most of the world, the petroleum
industry produces oil and gas from conventional reservoirs. However, unconventional
resources, including tight-sand, coalbed methane, and shale formations, have drawn
considerable attention in recent years due to the vast reserve and long-term production
potential (Kawata et al., 2001; Holditch, 2006). Table 1-1 shows the World distribution
of unconventional gas resources (Holdith, 2006). It shows that there is extensive amount
of gas in unconventional reservoirs with more emphasis in shale formations, especially
in the United States. While there are considerable challenges in producing from these
resources, recent technological development in geological evaluation, drilling,
stimulation, and production operations are enabling engineers to overcome many of
these challenges to allow economical production from these resources. These resources
have boosted natural gas production by 30% in the United States. In 2009, gas
production, in the United States, from unconventional resources exceeded the gas
production from conventional reservoirs.
After investigating a large sample of shale rocks over 10 years, Bustin et al. (2008) gave
the definition of shale as: shale has come to refer to any very fine-grained rocks
capable of storing significant amount of gas and as such strata referred to as gas shales
range from rocks that are true shales sensu stricto to rocks that grade into tight sands.
Rock property, pore structure, and flow characteristics vary significantly between
different shale formations due to the wide definition of shale. To date, there are no
standard experimental methods and simulation models specific to shale. Some recent
2
researches have estimated the shale gas-in-place (Ambrose et al., 2012; Hartman, et al.,
2011; Das et al., 2012), the gas flow in shale (Javadpour et al., 2007; Javadpour, 2009;
Freeman et al., 2010; Blasingame, 2008), and shale gas production (Biswas, 2011;
Wattenbarger et al., 1998). However, these methods all have their assumptions which
present limitations to their application.
Region
Coalbed
Methane
(Tcf)
Shale Gas
(Tcf)
Tight-
sand Gas
(Tcf)
Total
(Tcf)
North America
3,017 3,840 1,371 8,228
Latin America
39 2,116 1,293 3,448
Western Europe
157 509 353 1,019
Central and Eastern Europe
118 39 78 235
Former Soviet Union
3,957 627 901 5,485
Middle East and North Africa
0 2,547 823 3,370
Sub-Saharan Africa
39 274 784 1,097
Centrally planned
1,215 3,526 353 5,094
Asia and China Pacific
(Organization for Economic
Cooperation and Development)
470 2,312 705 3,487
Other Asia Pacific
0 313 549 862
South Asia
39 0 196 235
World
9,051 16,103 7,406 32,560
Table 1-1: The distribution of worldwide unconventional gas resources. (Holdith,
2006)
1.1 Properties of shale formations
Unlike conventional gas reservoirs, the pore size in shale formations range from a few
nanometers to a few micrometers, and the number of nanopores (diameter smaller than
1 m) is much higher than micropores (diameter is larger than 1 m). The combination
of nano-scale pore network with micro-scale pore network dominates the gas flow in
3
shale. Figure 1-1 shows the comparison of pore distribution between conventional gas
reservoirs and shale formations, which indicates shale is composed mainly of nanopores
with small distribution of micropores, while conventional reservoirs show an opposite
trend with majority of micropores and small amount of nanopores.

Figure 1-1 Pore distribution in conventional gas reservoirs and shale formations.
(Javadpour et al., 2007)
This pore distribution gives rise to three different features of shale formations:
1. These nanopores cause very low permeabilities. Bustin et al. (2008) measured
a large sample of shale permeabilities which fell within the range of 1 to 10
3

nd. Their samples were from a large range of formations, including soft clay-
rich Colorado Group shales from the Western Canadian Sedimentary Basin
and brittle, silica-rich shale from Muskwa Formation in Northeastern British
Columbia and Woodford. Javadpour et al. (2007) measured permeability of
152 shale samples from nine reservoirs by pulse decay technique (Figure 1-2)
showing that 90% of measured permeabilities are less than 150 nd and the
mode of the permeability is 54 nd.
2. Nano-scale pores have a larger-exposed area compared to micropores, and will
allow more gas adsorption on pore surfaces. Beliveau (1993) indicates that the
ratio of free gas to adsorbed gas storage capacity decreases as pore size
4
decreasing. When the diameter of pore goes down to 0.01 m, the adsorbed
gas will exceed free gas storage.
3. The flow transport mechanisms deviate far from the conventional gas
reservoirs. Convection will not be the only dominant mechanism in gas flow,
and some other transport mechanisms should be considered as well, like gas
adsorption/desorption (desorbing as pressure depletion), molecular diffusion
(significant contribution when convection flow is low), surface diffusion
(happens in adsorption layers of small pores), and Knudsen diffusion (happens
in small pores at low pressures).

Figure 1-2: Frequency versus permeability of 152 shale gas samples from nine
reservoirs. (a) permeability distribution, (b) cumulative frequency distribution.
(Javadpour et al., 2007)
5
1.2 Adsorption in shale formations
Large surface areas of nanopores in shale cause a large fraction of gas to be adsorbed on
the surface. Many recent researches about shale gas-in-place estimation indicate that
there is a large amount of gas in shale existing in the adsorbed state (Das et al., 2012;
Leahy-Dios et al., 2011; Mengal et al., 2011; Hartman et al., 2011). On the other hand,
the desorption process also contributes a large amount of gas to the total gas flow in the
production process (Mengal et al., 2011). Desorption from the surface of shale
formations happens when there is considerable depletion of free gas and pressure drop.
From past study on coalbed methane adsorption mechanism, the Langmuirs isotherm
model is typically applied to calculate the amount of gas adsorption/desorption at
different pressures:
(Equation1-1)
where
is the adsorbed gas volume per rock weight (in e.g., scf / ton) at any pressure
P (psi),
is maximum Langmuir volume, and
is Langmuir pressure, defined as the

pressure value at which the adsorbed gas content is equal to
, (psi). These two

parameters (
) relate the gas storage capacity of a reservoir rock to pressure and

depend on the temperature, rank, and the moisture content. They can be measured in
experiments using core samples. Figure 1-3 shows a typical Langmuir isotherm curve.
As it shows, the amount of adsorbed gas per unit rock weight increases as pressure
increases until it plateaus at a maximum value (V
L
). Nowadays, researchers apply
Langmuir isotherm model to simulate adsorption in both shale formations and coalbed
methane (CBM) because of their similarity in gas storage mechanism (free gas in pore
6
space and adsorbed gas on pore surface). (Economides et al., 2010; Leahy-Dios et al.,
2011)
For the multi-component gas system, it is necessary to consider the effect of the gas
phase composition. The extended Langmuir model is commonly used for the prediction
of mixed gas adsorption behavior in shale:
(Equation 1-2)
where
is the adsorbed volume of component i at partial pressure
and
is
the Langmuir volume constant and Langmuir pressure constant of component i. which
can be determined by pure gas experiments in the laboratory.

Figure 1-3: A typical Langmuir isotherm curve. (Das et al., 2012)
In summary, adsorption exists mostly in the very small pores (nanopores), because the
larger exposed areas allow more gas adsorbing on the surface. In addition, the adsorbed
gas storage capacity of reservoir rocks depends on reservoir pressure and the type of
reservoir rocks (rank, temperature of reservoir, moisture content). The gas desorption is
determined by the extent of change in pressure, actual pressures, and Langmuir
7
isotherm pressure-volume relationship. Hence, there is very limited amount of adsorbed
gas in conventional reservoirs. While unconventional reservoirs have large amount of
adsorbed gas due to existence of nanopores, due to their low permeability, there might
not be sufficient change in pressure to allow the large amount of adsorbed gas to be
produced.
1.3 Gas flow mechanisms in shale formations
1.3.1 Flow in micropores
In micropores of shale, gas flow is dominated by convective pressure-driven flow which
can be treated as in conventional gas reservoirs. The flow flux is caused by a pressure
gradient, and dominates all other forms of transport in magnitude. Darcys equation can
describe the gas flow in the large pore system.

(Equation 1-3)
where Q is the gas flow rate (m
3
/s), k is Darcys permeability (m
2
), A is the cross-
sectional area to flow (m
2
), is flow viscosity (Pa s), and is the pressure gradient
(Pa/m).
From equation 1-3, one can see that convection flow is determined by pressure gradient,
permeability, and viscosity. Viscosity of gas only is related to the temperature, so there
are only two factors determine the convection flow in isothermal gas systempressure
gradient and permeability. Because the permeability of shale formations is much less
than conventional gas reservoirs, the magnitude of convection flow in shale formations
will be much smaller at the same pressures.
8
1.3.2 Flow in nanopores
Javadpour (2009) described the gas molecules transportation in tight gas formations.
There are three forms of gas existing in the shale pore system: freely compressed gas in
pore space, adsorbed gas on the pore surface, and dissolved gas in the kerogen
materials. These three types of gas are in an equilibrium state in the pore system. Figure
1-4 shows the three types of gas and how they are transported in the production process.
When production starts, the equilibrium will be disturbed and gas molecules start
flowing toward the low pressure zone. Free gas is firstly produced and the pressure
draws down (process 1 in Figure 1-4). Then the adsorbed gas desorbs from the surface
to the pore space which cause the pressure to increase (process 2 in Figure 1-4). At last,
concentration equilibrium changes between the kerogen bulk and surface, and gas
molecules will move from kerogen bulk to its surface (process 3 in Figure 1-4).
Potential gas transportation mechanisms in this process involve convective flow,
molecular diffusion in pore space, Knudsen diffusion, and surface diffusion.

Figure 1-4: Gas molecules movements in shale formations. (Javadpour, 2009)
9
1.3.2.1 Knudsen number
Before discussing these distinctive mechanisms in detail, it is necessary to introduce the
concept of Knudsen number. Due to the extremely small pore volume in shale
formations, conventional Darcys law cannot describe gas flow transport in shale
formations. The Knudsen number
can be used for measuring the degree of

rarefaction of gases in porous media. It is defined by the ratio of the gas molecular
mean-free-path and the pore diameter d
pore
.

(Equation 1-4)
The mean-free-path is given by Cunnigham and Williams (1980):

(Equation 1-5)
where
is the Boltzmann constant, and is the collision diameter.

(Equation 1-6)
where V
c
is the critical volume of gas components in cm
3
/mol.
For Knudsen number:
- less than 0.001: viscous flow, which can be described by the conventional
Darcys law;
- from 0.001 to 0.1: slip flow. The flow velocity near the pore walls is not zero
and the viscous flow model needs to incorporate Klinkenberg slippage factor to
account for this phenomena;
- from of 0.1 to 10: transition flow where the molecular-wall collision becomes
significant;
10
- larger than 10, the gas flow should be recognized as a swarm of discrete
particles which is called free-molecular flow.
When Knudsen number is larger than 0.001 (not viscous flow), the Darcy-permeability
should be corrected into apparent permeability to estimate gas flow in reservoirs.
Florence et al. (2007) studied the apparent permeability prediction for low-permeability
sands. The methods are shown in appendix C.
1.3.2.2 Molecular diffusion
Molecular diffusion is the most well-understood diffusion type for gas transportation in
porous media. Dutta et al. (2009) and Poling et al. (2000) summarize that molecular
diffusion can be caused by different types of driving forces, including pressure
gradients (pressure diffusion), temperature gradients (thermal diffusion), external force
fields (forced diffusion), and concentration gradients.
In general, concentration gradient is considered in gas transportation in porous media
and Ficks Law is applied to model this process:
(Equation 1-7)
is the molar flux of component i per unit area; c is the total molar concentration given
by
is the molar volume of the mixture;
is the mole fraction of

component i;
is the gradient in the direction of flow;
is the diffusion coefficient of

component i in mixtures. The diffusion coefficient presents the proportional relationship
between the flux J
i
relative to a plane of no net molar flow and the gradient
. For
the mixtures system with n components, the independent diffusion fluxes are
and diffusion coefficients are
(Cussler, 1984; Taylor and Krishna, 1993).

11
When
, where
is the self-diffusion coefficient of component i in

pure i. Self-diffusion can model the one component gas transportation process.
Gas diffusion coefficients used in diffusion calculations can be determined from
experimental studies where possible. Dawson et al. (1970) and Helbaek et al. (1996)
measured the self-diffusion coefficient of methane at different pressures and
temperatures using Nuclear Magnetic Resonance technique. Several investigations of
diffusion coefficients of the multi-component gas system in porous media condition
were conducted in laboratory (Sigmund, 1976; Sigmund, 1976; Grogan et al., 1988;
Islas-Juarez et al., 2004).
On the other hand, it is possible to use kinetic theory to describe molecular diffusion in
binary gas. The Chapman-Enskog model (Chapman and Cowling, 1970), resulting from
solving the Boltzmann equation, is usually used for the theoretical estimation of
gaseous diffusion coefficients as:
(Equation 1-8)
where
is the binary diffusion coefficient in cm

2
/s, T is temperature in K, P is
pressure in atm,
is the collision diameter in and
is the diffusion collision

integral, and
*(
) (
)+
(Equation 1-9)
where
and
are the molecular weights of A and B in gm/mol. The above model is

only accurate at low to moderate pressure range usually below 1 MPa (Wesselingh
and Krishna, 2000). The key to applying Equation 1-7 is to estimate the value of

and
which usually causes the complexity of Chapman-Enskog model.

12
Several proposed methods for coping with the complexity were developed with
empirical constants based on experimental data. One method is developed by Wilke and
Lee (1955):
*(
)+
(Equation 1-10)
where

2
pressure in bar,
is the collision diameter in and
is the diffusion collision

integral,
and
are the molecular weights of A and B in gm/mol. M

AB
=
2[(1/M
A
)+(1/M
B
)]
-1
.

Fuller, et al. (1965, 1966, 1969) modified Equation 1-8 to
(Equation 1-11)
where

2
pressure in bar,
is the sum of atomic diffusion volumes for each component (Fuller

et al., 1969),
and
are the molecular weights of A and B in gm/mol. M

AB
=
2[(1/M
A
)+(1/M
B
)]
-1
.
Pollin et al. (2001) shows the comparison of diffusion coefficients between
experimental results and these theoretical methods. Values of the diffusion coefficient
determined by the theoretical methods generally have an average absolute error within 4
to 10%. Other evaluations by Elliott and Watts (1972), Gotoh et al., (1973), (1974), and
Lugg (1968) have demonstrated that both Fuller and Wilke-Lee method yields the
smallest average error.
Ficks law is widely used to model tight gas/shale gas diffusion due to its simplicity.
For the single component gas system, the concentration gradient is very small at high
13
pressure condition. So Ficks law fails to describe the gas molecular diffusion in these
situations. A more accurate model is used to describe the molecular diffusion in some
commercial software (ECLIPSE* technical description, 2011).
] (Equation 1-12)
is the activity-corrected diffusion coefficient of component i,
is the thermal
diffusion coefficient of component i,
is the molecular weight of component i, is

the gravitational acceleration,
is the mole fraction of component i, is the height,

is the reference height, is the gas constant, is the temperature, and
is the chemical
potential of component i, given by
(Equation 1-13)
where
is the reference chemical potential, and
is the component fugacity.

At high pressure conditions, it is necessary to consider the component chemical
potential (the first term in Equation 1-12), gravity potential which drives the heavy
species to the bottom of the reservoir (the second term in Equation 1-12), and the
temperature gradient which drive those species with a low enthalpy / high entropy to the
hottest parts of the reservoir (the last term in Equation 1-12). When the first two terms
are equal, equilibrium will reach. The last term accounts for the diffusion caused by a
temperature gradient in reservoirs. The activity-corrected diffusion coefficient can be
expressed as:

(Equation 1-14)
is the concentration
gradient driving diffusion coefficient for component i,

14
component i, and
is the component fugacity. The detail of the relationship between

the two diffusion coefficients is presented in appendix B.
In summary, molecular diffusion happens in both conventional gas reservoir and shale
formations. For the single gas component and isothermal system, pressure and diffusion
coefficients are factors to determine gas diffusion. However, as the experimental
measurements of diffusion coefficients indicate, the molecular diffusion is small and its
contribution mainly depends on the magnitude of other mechanisms.
1.3.2.3 Knudsen diffusion
Knudsen diffusion occurs in very small pores, usually in order of 10nm to 100nm and at
very low pressures. Under this condition, the mean free path (the distance between
molecular collisions) is greater than the nanopore diameter, which will cause gas
molecules to collide with the pore wall and not frequently collide with other molecules.
In shale formations, Knudsen diffusion is significant at the low pressures because the
pore diameter is very small which falls into the level of nanometers. But it can hardly
happen in conventional gas reservoirs due to the micropore system.
The Knudsen diffusion coefficient
can be expressed as (Javadpour, 2007):
(Equation 1-15)
where d
pore
is the diameter of the nanopore, is the gas constant, is the temperature,
is the gas molecular weight.
1.3.2.4 Surface diffusion
If there are gas layers adsorbing on the surface of small pore walls, the gas molecules
will transport primarily through the physically adsorbed layer other than the pore space.
15
This is because gas molecules, in small pores, can barely escape the adsorption layer
and the diffusion process is relatively fast. This type of transport is called surface
diffusion (Cussler, 1984). Shale formations are known for adsorbed gas on the kerogen
surface and the nanopore system. In shale gas production process, the surface diffusion
includes rapid gas desorption, rapid transport along the surface layer, and rapid gas
adsorption. Some research work showed that surface diffusion may be an important
contribution to the total gas flow (Fathi and Akkutlu, 2009). However, due to the
complexity of surface diffusion, no proper model is available to describe this
phenomenon.

16
Chapter 2: Modeling of Gas Transport in Conventional Gas
Reservoirs and Tight Gas Reservoirs/Shales
2.1 Objective
The basic principle of gas flow in conventional gas reservoirs and shale formations was
introduced in chapter 1. In the large pore space of conventional gas reservoir, the gas
flow is dominated by convective flow which can be described by Darcys equation.
When it comes to shale formations, the nanopore system introduces other transport
mechanisms, including gas adsorption/desorption, and molecular diffusion. The
mechanisms of adsorption/desorption and molecular diffusion can be modeled by some
commercial software, like ECLIPSE* by Schlumberger.
Nowadays, researchers start to incorporate adsorption/desorption, molecular diffusion,
and Knudsen diffusion in their work. (Javadpour et al., 2007; Javadpour et al., 2009;
Freeman et al., 2010; Mengal et al., 2011) Multi-porosity and/or dual permeability
models are typically applied in their works to account for reservoir fractures.
Researchers usually incorporate these transport mechanisms into their multi-component
gas system models. Consequently, the effects of fractures, gas content and components
are brought in their works which do not allow the effect of each transport mechanism to
be clearly.
In our study, we first use ECLIPSE 300* to build up a single porosity model for
conventional reservoirs and shale formations. Then we will simulate the effects of
transport mechanisms: adsorption/desorption, diffusion driven by concentration
gradient, and diffusion driven by chemical potential gradient. All of these are included
with the base case where only the convective flow in the single component gas system
17
is present. In such system, the effects of gas content and component will be eliminated.
The grid block numbers of (11x11x1) and (110x110x10) in x, y, and z directions will be
applied for studying the grid size effects on our models. At last, we will incorporate the
effect of grid size on each single transport mechanism.
The objectives of this study include:
- Comparing grid size effects on conventional reservoirs and shale formations due
to numerical dispersion;
- Simulating and comparing pure adsorption/desorption mechanism and pure
molecular diffusion mechanism (two different models) impacts on conventional
reservoirs and shale formations;
- Comparing grid size effects on adsorption/desorption mechanism and molecular
diffusion mechanism in conventional reservoirs and shale formations;
- Simulating the multi-mechanisms of convection, adsorption and diffusion on
conventional reservoirs and shale formations.
2.2 Model specification
The following assumptions are made as the basic characteristics applying for this
research work:
1. Single gas component (methane) system with water component;
2. Homogeneous reservoir matrix with uniform rock properties in single porosity
models;
3. No gas condensate in the system;
4. Isothermal system;
18
5. The same Langmuir isotherm values to both conventional gas reservoirs and
shale formations;
6. Knudsen diffusion is ignored because gas molecule-wall collision only happens
in low pressures (Fathi et al., 2012), while the pressure in our model (5000 psia)
is much higher. Figure 2-1 shows that when pressure is larger than 1000 psia
(less than 0.001 in the x-axis), the effect of wall-molecular collisions will
become nearly zero. In addition, we can estimate the Knudsen number and
apparent permeability of our models to see whether Knudsen diffusion is
important. The Knudsen numbers of shale formation models at different
conditions are 0.747, 0.0779, and 0.112; the apparent permeabilities are 86.27,
86.63, 102.4 nd. We also simulated our shale gas models in these three models,
and show the gas production rate in Figure C-1 and C-2. Although the gas rates
change as much as twice, the magnitude of the gas rate is still very small. The
changes do not show an apparent difference for different mechanisms effects.
The details are presented in appendix C. Thus, it is reasonable for our study to
ignore Knudsen diffusion. To keep consistency, we still use the permeability of
54 nd for shale formations.
7. There is only one vertical producing well located in the corner of the reservoir
and penetrating through all the reservoir thickness. The reservoir physical model
is shown in Figure 2-2;
8. The well produces at constant-BHP constraint. It has been completed in the first
year and started to produce from the 2nd year for 50 years.
19
The assumptions 1 to 4 are made for simplification. The reason for using the same
Langmuir isotherm values in all cases is to keep the same original gas in place when
adding adsorption mechanism in our models. With the same initial conditions, the effect
of adsorption/desorption can be observed and compared more straightforwardly. We use
the typical relative permeability and capillary pressure curves for tight reservoir, shown
in Figure 2-3. The model parameters are listed in Table 2-1. These data were first
obtained from literature reviews (Bahrami et al., 2011; Ambrose et al., 2010, Leahy-
Dios et al., 2011; Economides et al., 2010; Das et al., 2012) and then modified to fit our
model. We reduced the irreducible water and gas saturations, and increase initial gas
saturation, to enhance the gas production rate from shale formations. We use
compositional mode in ECLIPSE 300* and choose to use the Peng-Robinson equation
of state. The detail of Peng-Robinson equation of state is demonstrated in ECLIPSE*
Technical Description (2011). The critical properties for running the EOS model are
listed in Table 2-2.
Due to the very small gas rate in shale formations, we added hydraulic fracture in our
shale formation models to enhance the production rate and pressure drop. We first
rearrange the grid size in our models to keep the production well in the same location.
Then keeping the same number of grid blocks, we changed the entire row of grid
cellswhere the production well locatedalong x-axis into fracture cells. Finally, the
permeability of fracture is updated. The specifications of cases which we simulated in
our study are listed in Table 2-3.

20

Figure 2-1: Simulation and experimental results showing the impact of pore
pressure on the interactions between gas molecules and pore wall. (Fathi et al.,
2012)

Figure 2-2: Dimensions and grid blocks for reservoir models; using grid blocks of
(11x11x1) and (110x110x10); (X, Y, Z) orders.
21

Figure 2-3: The relative permeability curve (top) and capillary pressure curve
(bottom) used in this study.

0
0.2
0.4
0.6
0.8
1
0 0.2 0.4 0.6 0.8 1
R
e
l
a
t
i
v
e

p
e
r
m
e
a
b
i
l
i
t
y

Water saturation
krw
krg
0
100
200
300
400
500
600
700
0 0.2 0.4 0.6 0.8 1
P
c

,

p
s
i

Water saturation
Pc
22
SI units Field units
depth of reservoir top D
r
1253.6 m 4113 ft
x 51 m 167.3 ft
reservoir dimensions y 51 m 167.3 ft
z 18 m 59 ft
conventional reservoir permeability k
c
5.4 md
shale matrix permeability k
s
54 nd
shale fracture permeability k
f
15000 md
porosity | 8%
fracture width width 0.08 m 3.15 in
reservoir temperature T
r
82
o
C 179.6
o
F
initial reservoir pressure P
initial
345 bar 5003.8 psia
bottom hole pressure BHP 50 bar 725.2 psia
skin factor s 0
initial gas saturation S
gi
0.75
initial water saturation S
wi
0.25
diffusion coefficient D
i
0.0078 m
2
/day
Langmuir isotherm
Langmuir pressure P
L
44.816 bar
Langmuir volume V
L
0.00299654 sm
3
/kg
Table 2-1: Model parameters in this study.
component name
gas molecular weight
methane
16.043 g/mol
OmegaA 0.45723553
OmegaB 0.07779607
critical temperature 215.66 K
critical pressure 81.296 bar
critical volume 0.065588 m
3
/mol
critical z-factor 0.29738
shift parameters 0.0742789
acentric factors 0.46931
binary interaction coefficients 0
component parachor 74.92
Lorentz-Bray-Clark viscosity correlation coefficients
a 0.1023
b 0.023364
c 0.058533
d -0.040758
e 0.0093324
Table 2-2: Critical properties of methane for running the one component
compositional model.
23

case
Number of
grid blocks in
x, y, and z
directions
Permeability Adsorption
concentration
gradient
driving
diffusion
chemical
potential
gradient
driving
diffusion
C
o
n
v
e
n
t
i
o
n
a
l

g
a
s

r
e
s
e
r
v
o
i
r
s

Case 1 11111 5.4 md

Case 2 11111 5.4 md yes

Case 3 11111 5.4 md

yes

Case 4 11111 5.4 md

yes
Case 5 11111 5.4 md yes

yes
S
h
a
l
e

f
o
r
m
a
t
i
o
n
s

Case 6 11111 54 nd

Case 7 11111 54 nd yes

Case 8 11111 54 nd

yes

Case 9 11111 54 nd

yes
Case 10 11111 54 nd yes

yes
S
h
a
l
e

f
o
r
m
a
t
i
o
n
s

w
i
t
h

f
r
a
c
t
u
r
e
s

Case 11 11111 54 nd
Case 12 11111 54 nd yes
Case 13 11111 54 nd yes
Case 14 11111 54 nd yes
Case 15 11111 54 nd yes yes
C
o
n
v
e
n
t
i
o
n
a
l

g
a
s

r
e
s
e
r
v
o
i
r
s
Case 16 11011010 5.4 md

Case 17 11011010 5.4 md yes

Case 18 11011010 5.4 md

yes

Case 19 11011010 5.4 md

yes
Case 20 11011010 5.4 md yes

yes
S
h
a
l
e

f
o
r
m
a
t
i
o
n
s

Case 21 11011010 54 nd

Case 22 11011010 54 nd yes

Case 23 11011010 54 nd

yes

Case 24 11011010 54 nd

yes
Case 25 11011010 54 nd yes

yes
S
h
a
l
e

f
o
r
m
a
t
i
o
n
s

w
i
t
h

f
r
a
c
t
u
r
e
s

Case 26 11011010 54 nd
Case 27 11011010 54 nd yes
Case 28 11011010 54 nd yes
Case 29 11011010 54 nd yes
Case 30 11011010 54 nd yes yes
Table 2-3: Specifications of simulation cases in this study.

24
Chapter 3: Results and Discussion
Results are analyzed by plotting charts of gas production rate vs. time, cumulative gas
production vs. time, and gas-in-place vs. time. For conventional gas reservoirs, the gas
production rate drop to 0.1% of initial value after 100

day of

production, and continues
to drop around 0.007% per day. This indicates that gas flow has become steady-state
flow after 100 producing days. As a result, presenting results up to 100 production day
is enough for conventional gas reservoirs. For shale formations, we use the typical life
for production well of 50 years to compare the results due to its very low production
rates. For shale formations with fractures, because the initial gas rate is so high that
cannot be presented in the same charts with the gas rate after 1-year production, we plot
the production rate in the first year, and the following 49 years separately. As figure 3-1
shows the gas production rate of different models base cases are not in the same
magnitude, we normalize the data by dividing the larger initial or ultimate value among
all the comparing cases for each plot in order to be able to compare results.
3.1 Grid size
Among various parameters affecting the simulation results in the compositional model
of ECLIPSE 300*, grid size is one of the most important. The reason is that ECLIPSE*
uses the numerical finite-difference scheme to perform simulation which are
intrinsically affected by numerical dispersion. And the finite difference in the numerical
simulations is first order. In Figure 3-1, for example, we show the pressure gradient in
our reservoir model of different grid sizes at the 40
th
day. The pressure drop faster with
time in larger grid size model, but the pressure gradient is smaller than smaller grid size
25
model. As a result, gas will move faster in smaller grid size model. In this section, we
compare the 121 (11111) grid blocks model with the 121000 (11011010) grid
blocks model for conventional gas reservoirs and shale formations. Table 3-1 shows
some results of case 1 and case 16 (conventional reservoirs); case 6 and case 21 (shale
formations); case 11 and case 26 (shale formations with fractures).
Figure 3-2 to 3-5 show the impact of grid size on conventional gas reservoirs. First, the
initial gas production rate of smaller grid size model is 14% larger than the larger grid
size. However, the production rate of smaller grid size model drops faster than larger
grid size, and such that the larger grid size produces faster after the 8
th
day. Second, grid
size effects do not change the initial gas-in-place and total gas production, although
smaller grid size reach the ultimate recovery faster by about 10 days. In addition, the
gas-in-place curves have almost the same trends as pressure curve because there is only
convection flow in the base cases.
Figure 3-6 to 3-9 show that the grid size effects on shale formations are much more
significant than conventional gas reservoirs. The initial gas production rate of smaller
grid size is 57% larger than larger grid size. It also drops much faster in the first 5 years
than the gas rate of larger grid size model. At the last day of the 50
th
year, the difference
of their gas production rates reduced to 16%. Consequently, the smaller grid size
produced 19% more natural gas than the larger grid size after 50 years. Similarly, the
original gas-in-place does not change in different grid size of shale formation models,
and the trends of pressure drop curves and the gas-in-place curves are the same.
One can see the grid effects on shale formations with fractures from Figure 3-10 to 3-
14. The initial gas production rate of smaller grid size is 19% higher than larger grid
26
size. However, the gas rate of smaller grid size drops drastically at the very beginning
time, and they would surpass each other after 150 days production. At the last day, the
difference becomes to -6%. As a result, they will produce the same amount of gas at the
6th year and finally larger grid size can produce 4% more gas after 50 years
production, and 4% more pressure drop. And the grid size does not change the original
gas-in-place as well. Some noisy production data can be observed in the last several
years. The reason is that the iteration in ECLIPSE* does not converge when adding
small grid block of fractures into the shale formation models.
In Figure 3-16 to 3-18, we plot all pressure curves of each model in the same chart. And
the results indicate that the differences of pressure drops are not very large in the same
model when adding diffusion and/or adsorption mechanism. For conventional
reservoirs, the pressure drop from 5004 psia to 780 psia; for shale formations, the
pressure goes from 5004 psia to average 4860 psia and average 3400 psia (with
fractures).

27
model case
initial gas
production
rate
(ft
3
/day)
gas
production
rate at 8
th

day
(ft
3
/day)
cumulative
gas
production
(ft
3
)
reservoir
pressure
drop after
100 days'
production
(psia)
conventional
gas reservoirs
case 1 3,083,846 938,266 24,270,670 4253
case 16 3,588,277 928,639 24,269,388 4269
grid size
effects
14% -1% 0% 0.4%
model case
initial gas
production
rate
(ft
3
/day)
gas
production
rate at last
day
(ft
3
/day)
cumulative
gas
production
(ft
3
)
reservoir
pressure
drop after
50 years'
production
(psia)
Shale
formations
case 6 93 36.56 756,089 143
case 21 220 43.54 934,646 177
grid size
effects
57% 16% 19% 19%
model case
initial gas
production
rate
(ft
3
/day)
gas
production
rate at last
day
(ft
3
/day)
cumulative
gas
production
(ft
3
)
reservoir
pressure
drop after
50 years'
production
(psia)
Shale
formations
with fractures
case 11 59,633 205 8,133,276 1472
case 26 73,500 192 7,801,123 1408
grid size
effects
19% -6% -4% -4%
Table 3-1: Grid size effects on conventional gas reservoirs and shale formations.

28

Figure 3-1: gas production rate in different models

Figure 3-2: Pressure gradient in different grid size models.
800
1,000
1,200
1,400
1,600
1,800
0 10 20 30 40 50
R
e
s
e
r
v
o
i
r

p
r
e
s
s
u
r
e
,

p
s
i
a

Distance, m
110x110x10
11x11x1
29

Figure 3-3: Impact of grid size on gas production rate with time (100 days) for
conventional gas reservoirs.

Figure 3-4: Semi-log plot shows the impact of grid size on cumulative gas
production with time (1000 days) for conventional gas reservoirs.
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
1 10 100 1000
N
o
r
m
a
l
i
z
e
d

c
u
m
u
l
a
t
i
v
e

g
a
s

p
r
o
d
u
c
t
i
o
n

Time (day)
110X110X10, k=5.4 md
11X11X1, k=5.4 md
30

Figure 3-5: Impact of grid size on reservoir pressure with time (100 days) for

Figure 3-6: Impact of grid size on gas-in-place with time (100 days) for
0
1,000
2,000
3,000
4,000
5,000
0 25 50 75 100

r
e
s
e
r
v
o
i
r

p
r
e
s
s
u
r
e
,

p
s
i
a

Time (day)
110X110X10, k=5.4 md
11X11X1, k=5.4 md
31

Figure 3-7: Impact of grid size on gas production rate with time (50 years) for
shale formations.

production with time (50 years) for shale formations.
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
o
r
m
a
l
i
z
e
d

g
a
s

p
r
o
d
u
c
t
i
o
n

r
a
t
e

Time (year)
110x110x10, k=54 nd
11X11X1, k=54 nd
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
1 10 100 1000 10000 100000
N
o
r
m
a
l
i
z
e
d

c
u
m
u
l
a
t
i
v
e

g
a
s

p
r
o
d
u
c
t
i
o
n

Time (day)
110x110x10, k=54 nd
11X11X1, k=54 nd
32

formations.

Figure 3-10: Impact of grid size on gas-in-place with time (50 years) for shale
formations.
4800
4840
4880
4920
4960
5000
0 5 10 15 20 25 30 35 40 45 50 55
R
e
s
e
r
v
o
i
r

p
r
e
s
s
u
r
e

(
p
s
i
a
)

Time (year)
110x110x10, k=54 nd
11X11X1, k=54 nd
0.96
0.97
0.98
0.99
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
o
r
m
a
l
i
z
e
d

g
a
s

i
n

p
l
a
c
e

Time (year)
110x110x10, k=54 nd
11X11X1, k=54 nd
33

Figure 3-11: Impact of grid size on gas production rate in the first year for shale
formations with fractures.

Figure 3-12: Impact of grid size on gas production rate with time (50 years) for
shale formations with fractures.
0
10,000
20,000
30,000
40,000
50,000
60,000
70,000
80,000
0 90 180 270 360
G
a
s

p
r
o
d
u
c
t
i
o
n

r
a
t
e

(
f
t
3
/
d
a
y
)

Time (day)
110x110x10, k=54nd+frac
11x11x1, k= 54nd+frac
0.00
0.20
0.40
0.60
0.80
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
o
r
m
a
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Time (year)
110x110x10, k=54nd+frac
34

production with time (50 years) for shale formations.

0.00
0.20
0.40
0.60
0.80
1.00
1 10 100 1000 10000 100000
N
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Time (day)
110x110x10, k=54nd+frac
3000
3500
4000
4500
5000
0 5 10 15 20 25 30 35 40 45 50 55
R
e
s
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r
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(
p
s
i
a
)

Time (year)
110x110x10, k=54nd+frac
35

Figure 3-15: Impact of grid size on gas in place with time (50 years) for shale

Figure 3-16: Pressure drop in conventional reservoirs for 100 days
0.60
0.70
0.80
0.90
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
o
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Time (year)
110x110x10, k=54nd+frac
0
1000
2000
3000
4000
5000
0 25 50 75 100
R
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(
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s
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)

Time (day)
case 1
case 2
case 3
case 4
case 5
case 16
case 17
case 18
case 19
case 20
36

Figure 3-17: Pressure drop in shale formations for 50 years

Figure 3-18: Pressure drop in shale formations with fractures for 50 years
4,750
4,800
4,850
4,900
4,950
5,000
0 5 10 15 20 25 30 35 40 45 50 55
R
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)

Time (year)
case 6
case7
case 8
case 9
case 10
case 21
case 22
case 23
case 24
case 25
3,000
3,500
4,000
4,500
5,000
0 5 10 15 20 25 30 35 40 45 50 55
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)

Time (year)
case 11
case 12
case 13
case 14
case 15
case 26
case 27
case 28
case 29
case 30
37
3.2 Adsorption
As discussed in chapter 1, adsorption/desorption is a contributing mechanism of gas
flow in shale. ECLIPSE 300* applies Langmuir isotherm model (Equation 1-1) to
simulate adsorption/desorption of a single component system. For our one component
gas (methane) system, we obtained the Langmuir isotherm data of methane in shale
formations by doing literature review (Jacobi et al. 2008; Mengal et al., 2011; Das et al.,
2012; Economides, 2010). They used experimental methods to measure the Langmuir
isotherm data from various shale samples. The data measured in these researches are
listed in Table 3-2. Finally, we decided to use the Langmuir isotherm pressure of 44.82
bars (650 psia) and the Langmuir isotherm volume of 0.00299654 sm
3
/kg (Mengal et
al., 2011) because it is close to the average value of experimental results of Das et al.
(2012). The Langmuir isotherm curve in our study is shown in Figure 3-19.
From Figure 3-20 to 3-23, one can see the grid size and adsorption/desorption effects on
conventional gas reservoirs. First of all, around 17% more original gas-in-place results
from gas adsorption for both grid sizes due to the Langmuir isotherm data in this study.
The remaining part is the free gas existing in pore space, which has the same volume as
the free gas in models without adsorption. When pressure drops, the adsorbed gas will
desorb from the pore surface which will enhance the initial gas flow rate for 1%. As
pressure depletion, more and more gas will be released from the pore surface which will
increase the gas production rate. Consequently, approximately 6% more gas was
produced in 100 days. Grid size effects are close to the base case: the smaller grid size
results in larger initial gas production rates (14%), faster gas rate drop, and shorter time
(10 days) to achieve the ultimate recovery.
38
Figure 3-24 to 3-27 show that the adsorption mechanism has very little impacts on shale
gas production. The reason is that the very small pressure drop inside reservoir pores
cannot cause significant gas desorbing from reservoir rock, see Figure 3-18. Even after
50 years production, pure adsorption mechanism only enhances 1% gas production.
Considering the grid size effects, the smaller grid size can cause 58% larger initial gas
production rate and 19% more cumulative gas production after 50 years, which are the
same as the base case.
One can see, as hydraulic fractures were induced in shale formations, the gas production
rate and pressure drop become larger which lead to adsorption gas releasing from shale
formations. Figure 3-28 to 3-32 show the adsorption/desorption effects on shale
formations with fractures. When adding adsorption/desorption mechanism, one can see
that initial gas production rates are enhanced by 1% and the rate keeps higher in the
entire production life for both grid sizes. The free gas in pore space was first produced
which cause the reservoir pressure depletion. Then, the desorption process happens and
increases pore pressure. As a result, 3% more gas is produced, and pressure drops 1%
less after 50 years production. However, as the reservoir pressure decreases from 5003
psia to 3500 psia, the desorption gas is still in a small amount when compared to free
gas production, see figure 3-19 and 3-32. For the grid size effects, the initial gas
production rate is enhanced by 17% in smaller grid size, but the cumulative pressure is
4% less due to numerical dispersion.
Figure 3-33 shows the comparison of adsorption effects between conventional gas
reservoirs and shale formations. In order to be able to compare them in one chart, we
normalized every curve by dividing the initial number of each curve. The adsorption
39
effects are most significant on conventional gas reservoirs. And for shale formations,
more obvious effects can be observed for models with fractures. This results from the
pressure drop difference among the three models. As we assume the adsorption gas
storage capacity is the same in all cases by giving the same Langmuir isotherm value,
pressure gradient become the only factor to affect gas desorption. Thus, the smaller is
the final reservoir pressure, the desorption mechanism is more significant. This result
accords with the theory we discussed in chapter 1.

40

sample
P
L
V
L

psia bar scf/ton sm
3
/kg
Das et al., 2012 1 900 62.05 70 0.002185

2 800 55.16 70 0.002185

3 525 36.20 73 0.002279

4 650 44.82 78 0.002435

5 800 55.16 78 0.002435

6 900 62.05 81 0.002528

7 750 51.71 69.5 0.002169

8 900 62.05 67.5 0.002107

9 780 53.78 45 0.001405

10 1000 68.95 52 0.001623

11 600 41.37 42 0.001311

12 850 58.61 118 0.003683

13 800 55.16 44 0.001373

14 1080 74.46 49 0.001529

15 650 44.82 43 0.001342

16 930 64.12 102 0.003184
average 807 55.65 68 0.002111
Economides et al.,
2010
930 64.12 46 0.001436
Mengal et al., 2011 650 44.82 96 0.002997
Table 3-2: Langmuir isotherm data of methane in shale formations from literature
review.

41
model case
initial gas
production
(ft
3
/day)
original
gas-in-
place
(ft
3
)
cumulative
gas
production
for 100 days
(ft
3
)
reservoir pressure
drop after 100 days'
production (psia)
conventional
gas
reservoirs
case 1 3,083,846 28,298,220 24,118,937 4253
case 2 3,102,376 34,082,973 25,747,637 4278
adsorption
effects
1% 17% 6% 1%
case 16 3,588,277 28,298,216 24,216,618 4269
case 17 3,614,046 34,082,969 26,401,379 4254
adsorption
effects
1% 17% 8% -0.4%
grid size
effects
14% 0% 2.5% -0.6%
model case
initial gas
production
(ft
3
/day)
original
gas-in-
place (ft
3
)
cumulative
gas
production
for 50 years
(ft
3
)
reservoir pressure
drop after 50 years'
production (psia)
shale
formations
case 6 93 28,298,220 756,088 143
case 7 93 34,082,973 758,776 140
adsorption
effects
0% 17% 0.4% -2%
case 21 220 28,298,216 934,646 177
case 22 220 34,082,969 939,112 173
adsorption
effects
0% 17% 0.5% -2%
grid size
effects
58% 0% 19% 19%
model case
initial gas
production
(ft
3
/day)
original
gas-in-
place (ft
3
)
cumulative
gas
production
for 50 years
(ft
3
)
reservoir pressure
production (psia)
shale
formations
with
fractures
case 11
59,663 28,298,220 8,133,276 1472
case 12 60,065 34,082,973 8,378,384 1453
adsorption
effects
0.7% 17% 3% -1.3%
case 26
73,500 28,298,216 7,801,123 1408
case 27 72,510 34,082,973 8,060,926 1392
adsorption
effects
-1.3% 17% 3% -1.1%

Grid size
effects
17% 0% -4% -4%
Table 3-3: Adsorption/desorption effects on conventional gas reservoirs and shale
formations.
42

Figure 3-19: Langmuir isotherm curve used for this study.

Figure 3-20: Impact of adsorption on gas production rate with time (100 days) for
conventional gas reservoirs; using grid blocks of (11x11x1) and (110x110x10).
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
0 25 50 75 100
N
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Time (day)
11X11X1, k=5.4 md
11X11X1, k= 5.4 md, pure adsp
110X110X10, k=5.4 md
110X110X10, k=5.4 md, pure adsp
43

production with time (1000 days) for conventional gas reservoirs; using grid blocks
of (11x11x1) and (110x110x10).

Figure 3-22: Impact of adsorption on gas-in-place with time (100 days) for
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
1 10 100 1000
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Time (day)
11X11X1, k=5.4 md
110X110X10, k=5.4 md
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
0 25 50 75 100

N
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Time, day
11X11X1, k=5.4 md
110X110X10, k=5.4 md
44

Figure 3-23: Gas-in-place of two states of gas with time (100 days) for conventional
gas reservoirs; using grid blocks of (11x11x1) and (110x110x10).

Figure 3-24: Impact of adsorption on gas production rate with time (50 years) for
shale formations; using grid blocks of (11x11x1) and (110x110x10).
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
0 25 50 75 100
N
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Time (day)
Total gas, 11x11x1, pure adsp
Free gas, 11x11x1, pure adsp
Adsorbing gas, 11x11x1, pure adsp
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
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Time (day)
11X11X1, k=54 nd
11X11X1, k= 54 nd, pure adsp
110x110x10, k=54 nd
110x110x10, k=54 nd, pure adsp
45

production with time (50 years) for shale formations; using grid blocks of
(11x11x1) and (110x110x10).

Figure 3-26 : Impact of adsorption on gas-in-place with time (50 years) for shale
formations; using grid blocks of (11x11x1) and (110x110x10).
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
1 10 100 1,000 10,000 100,000
N
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Time (day)
11X11X1, k=54 nd
110x110x10, k=54 nd
0.70
0.75
0.80
0.85
0.90
0.95
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
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Time (year)
11X11X1, k=54 nd
110x110x10, k=54 nd
46

Figure 3-27: Gas-in-place of two states of gas with time (50 years) for shale
formations; using grid blocks of (11x11x1) and (110x110x10).

Figure 3-28: Impact of adsorption on gas production rate in the first year for shale
formations with fractures; using grid blocks of (11x11x1) and (110x110x10).
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
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Time (year)
0
10,000
20,000
30,000
40,000
50,000
60,000
70,000
80,000
0 90 180 270 360
G
a
s

p
r
o
d
u
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i
o
n

r
a
t
e
,

f
t
3
/
d
a
y

Time (day)
110x110x10, k=54nd+frac 110x110x10, k=54 nd+frac, adsp
11x11x1, k= 54nd+frac 11x11x1, k=54 nd+frac, adsp
47

Figure 3-29: Impact of adsorption on gas production rate with time (50 years) for
shale formations with fractures; using grid blocks of (11x11x1) and (110x110x10).

production with time (50 years) for shale formations with fractures; using grid
blocks of (11x11x1) and (110x110x10).
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
o
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Time (year)
11x11x1, k=54 nd+frac, adsp
110x110x10, k=54nd+frac
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
1 10 100 1000 10000 100000
N
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t
i
o
n

Time (day)
110x110x10, k=54nd+frac
48

Figure 3-31: Impact of adsorption on gas-in-place with time (50 years) for shale

Figure 3-32: Gas-in-place of two states of gas with time (50 years) for shale
0.50
0.60
0.70
0.80
0.90
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
o
r
m
a
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p
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a
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Time (year)
110x110x10, k=54nd+frac
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
o
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a
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a
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Time (year)
Total gas, 11x11x1, k=54 nd+frac, adsp
Free gas, 11x11x1, k=54 nd+frac, adsp
Adsorbing gas, 11x11x1, k=54 nd+frac, adsp
Total gas, 110x110x10, k=54 nd+frac, adsp
Free gas, 110x110x10, k=54 nd+frac, adsp
Adsorbing gas, 110x110x10, k=54 nd+frac, adsp
49

Figure 3-33: Comparison of adsorption effects on gas production rate with time
(100 days) for conventional gas reservoirs and shale formations; using grid size of
(11x11x1) and (110x110x10).

0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
0 25 50 75 100
N
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a
t
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Time (day)
11X11X1, k=5.4 md
110X110X10, k=5.4 md
11X11X1, k=54 nd
110x110x10, k=54 nd
110x110x10, k=54nd+frac
50
3.3 Molecular diffusion
In this section, we will study the molecular diffusion effects on gas production of
conventional gas reservoirs and shale formations. ECLIPSE 300* provides two
diffusion models to describe gas molecular diffusion. The first one is the diffusion
driven by the concentration gradient which is defined by Ficks Law of Equation 1-7.
However, when the system pressure is high in single gas component system,
concentration gradient of gas molecules will become zero. Instead, the second
molecular diffusion driven by chemical potential gradient is applied, see Equation 1-12.
Appendix B shows the relationship between the two diffusion models and their
diffusion coefficients. When using ECLIPSE 300* to model molecular diffusion, it is
only required to input gas diffusion coefficient values into models: inputting
DIFFCGAS to activate the concentration gradient driving diffusion model, or
inputting DIFFAGAS to activate the chemical potential driving diffusion model.
Whats more, for the second diffusion model, ECLIPSE 300* can calculate the activity-
corrected diffusion coefficient automatically by inputting the value of concentration
gradient driving diffusion coefficient determined by Equation 1-7.
Two ways are applied to determine the diffusion coefficients in this study. The first way
is getting experimental data from others researches (Dawson et al., 1970; Helbaek et
al., 1996; Woessner et al., 1969). And the other one is calculating values according to
empirical models from Equation 1-7 to 1-10. The results are compared and listed in
Table 3-4. Finally, we decided to use the average value 0.0078 m
2
/day of the Wilke-Lee
model and Fuller model. The reason is that these two models are more accurate than the
51
Chapman-Enskog model, and the average estimated value is close to the experimental
value.
Diffusion mechanism is considered for both our conventional gas reservoir model and
shale formation model in this section. First, we will test concentration gradient driving
diffusion model in ECLIPSE 300* to see if it works at high pressure conditions. Then
molecular diffusion by chemical potential gradient will be studied in conventional gas
reservoirs and shale formation models. Table 3-5 and 3-6 summarize the results of these
diffusion study cases.
Figure 3-34 to 3-36 indicate that molecular diffusion caused by concentration gradient
does not have any effects on our models. This result reflects the basic theory discussed
in chapter 1.
From Figure 3-37 to 3-39, one can see molecular diffusion driven by chemical potential
has very limited impacts on conventional gas reservoirs. This is because dominate flow
in conventional gas reservoirs is the convective flow. In other words, the magnitude of
convection flow is far more than molecular diffusion (3,000,000 ft
3
/day vs. 8 ft
3
/day).
The same grid size effects as the base case are shown on molecular diffusion: smaller
grid size increase the initial gas production by 14%; use shorter time to achieve the
ultimate recovery; and make gas production rate drop faster.
Figure 3-40 to 3-42 indicate that molecular diffusion caused by chemical potential has
significant effects on shale formations. In the first 5 years, the production rates drop
drastically, and then molecular diffusion makes gas rates keep 7% (smaller grid size) or
3% (larger grid size) higher than models with no diffusion. As a result, diffusion
enhances 24% (smaller grid size) or 16% (larger grid size) of the ultimate gas recovery
52
after 50 years production. Comparing the different grid size curves, one can see smaller
grid size has 57% higher initial gas production rate (same as the base case) and produce
27% more gas after 50 years (19% for base case).
Figure 3-43 to 3-46 show the molecular diffusion effects on shale formations with
fractures. When large permeability fractures are induced to shale formation models, gas
in fracture cells will be produced first. Then, gas in the matrix cells will move to
fracture cells to be produced. So when adding molecular diffusion, the effects are
different for the two different grid size models. For small grid size, the initial gas
production rate is increased by 13%, and then keeping higher in the entire production
life. At the last production day, the difference reduces to 2% and 23% more cumulative
gas production can be observed. The pressure drop is 23% more. For large grid size
cases, the initial gas production rate is 53% less, but it will become much larger after
the first production day. As a result, 24% more gas will be produced and pressure will
drop 25% more.
In Figure 3-47, we normalized the gas production rates by dividing their own initial gas
production rate values. This shows the significant difference of diffusion effects on
conventional gas reservoirs and shale formations. Molecular diffusion only plays an
important role in shale formation models. The gas production rates are higher and drop
slower. For conventional gas reservoirs, the diffusion has no impacts on gas production.
The reason is the small magnitude of molecular diffusion: the convection and
desorption flow rate is large in conventional gas reservoirs due to the large permeability
and pressure drop, the contribution of molecular diffusion is so small that can hardly
impact the gas production. In shale formations, the convection and desorption is much
53
smaller because of the small permeability and pressure drop, the contribution of
molecular diffusion become larger compared to the total flow.

54
Data resources
T P D
i, methane

(K) (psia) (m
2
/day)
Experiments
Dawson et al.
353.8 6025 0.0062
353.8 4699 0.0076
Helbak et al.
333.1 5802 0.0052
333.1 4351 0.0065
Woessner et al. 353.8 2138 0.0159
Empirical
models
Chapman-Enskog 355 5003 0.0054
Wilke-Lee 355 5003 0.0080
Fuller 355 5003 0.0076
Table 3-4: Methane self-diffusion coefficients from literature review and empirical
model calculations.

55
model case
initial gas
production
rate
(ft
3
/day)
cumulative gas
production for
100 days
(ft
3
)
reservoir pressure
drop after 100
days' production
(psia)
conventional
gas
reservoirs
case 1 3,083,846 24,118,937 4253
case 3 3,083,846 24,118,941 4253
diffusion
effects
0% 0% 0%
case 16 3,588,277 24,216,618 4269
case 18 3,588,277 24,216,621 4269
diffusion
effects
0% 0% 0%
model case
initial gas
production
rate
(ft
3
/day)
cumulative gas
production for
50 years
(ft
3
)
reservoir pressure
production
(psia)
shale
formations
case 6 93 756,089 143
case 8 93 756,089 143
diffusion
effects
0% 0% 0%
case 21 220 934,646 177
case 23 220 934,646 177
diffusion
effects
0% 0% 0%
Shale
formations
with
fractures
case 11 59,663 8,133,276 1472
case 13 59,663 8,133,276 1472
diffusion
effects
0% 0% 0%
case 26 73,500 7,801,123 1408
case 28 73,500 7,801,123 1408
diffusion
effects
0% 0% 0%
Table 3-5: Molecular diffusion driven by concentration gradient effects on
conventional gas reservoirs and shale formations.

56
model case
initial gas
production
rate
(ft
3
/day)
cumulative gas
production for
100 days
(ft
3
)
reservoir pressure
drop after 100
days' production
(psia)
conventional
gas
reservoirs
case 1 3,083,846 24,270,670 4253
case 4 3,083,854 24,270,670 4253
diffusion
effects
0% 0% 0%
case 16 3,588,277 24,269,388 4269
case 19 3,588,291 24,269,388 4269
diffusion
effects
0% 0% 0%
grid size
effects
14% 0% 0.4%
model case
initial gas
production
rate
(ft
3
/day)
cumulative gas
production for
50 years
(ft
3
)
reservoir pressure
production
(psia)
shale
formations
case 6 93 756,089 143
case 9 93 898,297 171
diffusion
effects
0% 16% 16%
case 21 220 934,646 177
case 24 222 1,231,675 233
diffusion
effects
1% 24% 24%
grid size
effects
59% 27% 27%
shale
formations
with
fractures
case 11 59,663 8,133,276 1472
case 14 28,117 10,765,866 1951
diffusion
effects
-53% 25% 25%
case 26 73,500 7,801,123 1408
case 29 84,141 10,177,107 1837
diffusion
effects
13% 23% 23%

grid size
effects
67% -5.5% -5.8%
Table 3-6: Molecular diffusion driven by chemical potential gradient effects on
conventional gas reservoirs and shale formations.
57

Figure 3-34: Impact of molecular diffusion by concentration gradient on gas-in-
place with time (100 days) for conventional gas reservoirs; using grid blocks of
(11x11x1) and (110x110x10).

place with time (50 years) for shale formations; using grid blocks of (11x11x1) and
(110x110x10).
0.96
0.97
0.98
0.99
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
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Time (year)
11X11X1, k=54 nd
11X11X1, k=54 nd, pure diffC
110x110x10, k=54 nd
110x110x10, k=54 nd, pure diffC
58

place with time (50 years) for shale formations with fractures; using grid blocks of
(11x11x1) and (110x110x10).

Figure 3-37: Impact of molecular diffusion on gas production rate with time (100
days) for conventional gas reservoirs; using grid blocks of (11x11x1) and
(110x110x10).
0.70
0.75
0.80
0.85
0.90
0.95
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
o
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Time (year)
11x11x1, k= 54nd+frac, diffC
110x110x10, k=54nd+frac
110x110x10, k=54nd+frac, diffC
59

Figure 3-38: Impact of molecular diffusion on gas in place with time (100 days) for

(1000 days) for conventional gas reservoirs; using grid blocks of (11x11x1) and
(110x110x10).
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
1 10 100 1000
N
o
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m
a
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c
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i
o
n

Production time (day)
11X11X1, k=5.4 md
11X11X1, k=5.4 md, pure diffA
110X110X10, k=5.4 md
60

years) for shale formations; using grid blocks of (11x11x1) and (110x110x10).

shale formations; using grid blocks of (11x11x1) and (110x110x10).
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
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Time (year)
11X11X1, k=54 nd
11X11X1, k=54 nd, pure diffA
110x110x10, k=54 nd
110x110x10, k=54 nd, pure diffA
0.95
0.96
0.97
0.98
0.99
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
o
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p
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Time (year)
11X11X1, k=54 nd
110x110x10, k=54 nd
61

Figure 3-42: Semi-log plot showing the impact of molecular on cumulative gas
production with time (50 years) for shale formations; using grid size of (11x11x1)
and (110x110x10).

Figure 3-43: Impact of molecular diffusion on gas production rate in the first year
for shale formations with fractures; using grid blocks of (11x11x1) and
(110x110x10).
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
1 10 100 1,000 10,000 100,000
N
o
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t
i
o
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Time (day)
11X11X1, k=54 nd
110x110x10, k=54 nd
0
10,000
20,000
30,000
40,000
50,000
60,000
70,000
80,000
0 90 180 270 360
G
a
s

p
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r
a
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(
f
t
3
/
d
a
y
)

Time (day)
11x11x1, k= 54nd+frac, diffA
110x110x10, k=54nd+frac
110x110x10, k=54nd+frac, diffA
62

years) for shale formations with fractures; using grid blocks of (11x11x1) and
(110x110x10).

shale formations with fractures; using grid blocks of (11x11x1) and (110x110x10).
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
o
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p
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i
o
n

r
a
t
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Time (year)
110x110x10, k=54nd+frac
0.50
0.60
0.70
0.80
0.90
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
o
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m
a
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a
s

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p
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Time (year)
110x110x10, k=54nd+frac
63

(50 years) for shale formations with fractures; using grid blocks of (11x11x1) and
(110x110x10).

Figure 3-47: Comparison of molecular diffusion effects on gas production rate
with time (100 days) for conventional gas reservoirs and shale formations; using
grid size of (11x11x1) and (110x110x10).
0.00
0.20
0.40
0.60
0.80
1.00
1 10 100 1000 10000 100000
N
o
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v
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p
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d
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t
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o
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Time (day)
110x110x10, k=54nd+frac
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 25 50 75 100
N
o
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r
a
t
e

Time (day)
11X11X1, k=54 nd 11X11X1, k=54 nd, pure diffA
110x110x10, k=54 nd 110x110x10, k=54 nd, pure diffA
11X11X1, k=5.4 md 11X11X1, k=5.4 md, pure diffA
110X110X10, k=5.4 md 110X110X10, k=5.4 md, pure diffA
11x11x1, k= 54nd+frac 11x11x1, k= 54nd+frac, diffA
110x110x10, k=54nd+frac 110x110x10, k=54nd+frac, diffA
64
3.4 Adsorption and diffusion
In this section, adsorption and diffusion mechanisms are added in conventional gas
reservoirs and shale formation models. The Langmuir isotherm and diffusion coefficient
data used here are the same as previous simulations. We compare four different types of
mechanisms here: models without adsorption and diffusion (case 16, 21, and 26);
models with pure adsorption (case 17, 22, and 27); models with pure molecular
diffusion (case 19, 24, and 29); and models with adsorption and diffusion (case 20, 25,
and 30). Table 3-7 summarizes the results for these cases and compares the different
effects on conventional gas reservoirs and shale formations.
Figure 3-48 to 3-50 show that, for conventional gas reservoirs, molecular diffusion has
no impacts on gas production. Thus adsorption is the main mechanism which can affect
gas production from conventional gas reservoirs. The adsorption mechanism enhances
17% of original gas-in-place, 1% of initial gas production rate, and 8% of gas recovery
in 100 days. It is also make the gas production rate decrease slower. The reason is that
the depletion of pressure in reservoir releases a large amount of adsorbed gas into the
production well. Compared to convection and adsorption, the magnitude of molecular
diffusion is so small that can be ignored. For case 15, both adsorption and diffusion
mechanisms are added, but the result shows little changes. This indicates that adsorption
and diffusion do not have combined effects in conventional reservoirs.
From Figure 3-51 to 3-53, one can see that the dominant factor affecting shale gas
production changes from adsorption to diffusion. Adsorption can only increase 17%
adsorbed gas-in-place due to our Langmuir isotherm data. Molecular diffusion increases
1% initial gas production rate and 24% ultimate gas recovery. The gas production rates
65
drop significantly in the first 5 years, and then models with molecular diffusion keep the
gas production rate 7% higher than models without diffusion. Similarly, if we add both
of these two mechanisms into the basic model, the results are much close to the adding
pure diffusion model. This is because the low permeability of tight formations leads to a
very small gas flow rate in reservoirs. Then pressure drops a little which barely cause
gas desorbing from the rock surface. As a result, molecular diffusion becomes an import
factor in shale gas production.
Figure 3-54 to 3-57 show that, for shale formations with fractures, both
adsorption/desorption and diffusion can affect the gas production. Due to the pressure
drop is still not large enough, molecular diffusion has much more effects than
adsorption/desorption. For example, diffusion can increase the cumulative gas
production for 23% while adsorption only for 3%. When adding the two mechanisms
together into the same model, it is obvious to see that the effects are the simple
summation of two single mechanisms for gas production rate, cumulative gas
production, and pressure drop. As a result, there is no combined effects of
adsorption/desorption and molecular diffusion.

66
model case
initial gas
production
rate
(ft
3
/day)
cumulative
gas
production
for 100
days
(ft
3
)
original
gas-in-
place
(ft
3
)
reservoir
pressure
drop after
100 days
production
(psia)
conventional
gas
reservoirs
case 16 3,588,277 24,216,618 28,298,216 4269
case 17 3,614,046 26,401,379 34,082,969 4254
adsorption
effects
1% 8% 17% 0%
case 19 3,588,291 24,216,621 28,298,216 4269
diffusion effects 0% 0% 0% 0%
case 20 3,614,060 26,401,390 34,082,969 4254
multi-effects 1% 8% 17% 0%
model case
initial gas
production
rate
(ft
3
/day)
cumulative
gas
production
for 50
years
(ft
3
)
original
gas-in-
place
(ft
3
)
reservoir
pressure
drop after
50 years'
production
(psia)
shale
formations
case 21 219.78 934,646 28,298,216 177
case 22 220.23 939,112 34,082,969 172
adsorption
effects
0% 0% 17% 3%
case 24 221.90 1,231,675 28,298,216 233
case 25 222.29 1,236,485 34,082,969 228
shale
formations
with
fractures
case 26 73,500 7,801,123 28,298,216 1408
case 27 72,510 8,060,926 34,082,969 1392
adsorption
effects
1% 3% 17% 1%
case 29 84,141 10,177,107 28,298,216 1837
case 30 85,681 10,503,309 34,082,969 1813
Table 3-7: Effects of different mechanisms on conventional reservoirs and shale
formations.
67

Figure 3-48: Impacts of different transport mechanisms on gas production rate
with time (100 days) for conventional gas reservoirs; using grid blocks of
(110x110x10).

Figure 3-49: Impact of different transport mechanisms on gas in place with time
(100 days) for conventional gas reservoirs; using grid blocks of (110x110x10).
68

Figure 3-50: Semi-log plot showing the impact of different transport mechanisms
on cumulative gas production with time (1000 days) for conventional gas
reservoirs; using grid blocks of (110x110x10).

with time (50 years) for shale formations; using grid size of (110x110x10).
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
1 10 100 1000
N
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t
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n

Time (day)
110X110X10, k=5.4 md
110x110x10, k=5.4 md, adsp+diff
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
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o
n

r
a
t
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Time (year)
110x110x10, k=54 nd
110x110x10, k=54 nd, adsp+diffA
69

Figure 3-52: Impact of different transport mechanisms on gas-in-place with time
(50 years) for shale formations; using grid size of (110x110x10).

Figure 3-53: Semi-log plot showing the impact of different transport mechanism
on cumulative gas production with time (50 years) for shale formations; using grid
size of (110x110x10).
0.75
0.80
0.85
0.90
0.95
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
o
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m
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p
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Time (year)
110x110x10, k=54 nd
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
1 10 100 1,000 10,000 100,000
N
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t
i
o
n

Time (day)
110x110x10, k=54 nd
70

Figure 3-54: Impacts of different transport mechanisms on gas production rate in
the first year for shale formations with fractures; using grid size of (110x110x10).

with time (50 years) for shale formations with fractures; using grid size of
(110x110x10).
0
10,000
20,000
30,000
40,000
50,000
60,000
70,000
80,000
90,000
0 90 180 270 360
G
a
s

p
r
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d
u
c
t
i
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n

r
a
t
e

(
f
t
3
/
d
a
y
)

Time (day)
110x110x10, k=54nd+frac
110x110x10, k=54nd+frac, Adsp+diffA
0.00
0.20
0.40
0.60
0.80
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
o
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a
t
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Time (year)
110x110x10, k=54nd+frac
71

Figure 3-56: Impacts of different transport mechanisms on gas in place with time (50
years) for shale formations with fractures; using grid size of (110x110x10).

Figure 3-57: Impacts of different transport mechanisms on cumulative gas
production with time (50 years) for shale formations with fractures; using grid size of
(110x110x10).
0.50
0.60
0.70
0.80
0.90
1.00
0 5 10 15 20 25 30 35 40 45 50 55
N
o
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m
a
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Time (year)
110x110x10, k=54nd+frac
0.00
0.20
0.40
0.60
0.80
1.00
1 10 100 1000 10000 100000
N
o
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Time (day)
110x110x10, k=54nd+frac
72
Chapter 4: Conclusions and Suggestions
4.1 Conclusions
The conclusions of this study are as follows:
1. For adsorption/desorption mechanism, pressure is the dominant factor for the
same shale rocks. In conventional gas reservoirs, desorption is significant due to
the large pressure drop (from 5004 psia to 780 psia in 100 days). In shale
formations, because the pressure drop is very small, adsorption/desorption plays
an insignificant role in gas production.
2. The contribution of molecular diffusion depends on the magnitude of other
transport mechanisms. Because of the large permeability and pressure drop in
conventional gas reservoir, molecular diffusion shows a little impact. In shale
formations, as the very small permeability and pressure drop lead to the small
amount of convection and desorption flow, the contribution of molecular
diffusion become larger.
3. Grid size effect is an important factor in this simulation study. It is more
significant in shale formations because of numerical dispersion. The smaller
grid size model produces faster although the ultimate gas recovery will be the
same among different grid size models.
4. Molecular diffusion model described by concentration gradient does not affect
any production results in this single component system.
73
4.2 Suggestions for future work
This work mainly focus on the impact of grid size, convection, adsorption, and
molecular diffusion on shale gas production of a single component system. However,
there are still other important parameters which need to be investigated:
1. Studying the effect of gas component, e.g. using binary gas system or gas
mixtures of multi-components;
2. Investigating the effect of inducing fractures in dual porosity model;
3. Exploring the role of matrix-fractures interactions in gas production.

74
Nomenclature
A cross sectional area to flow
b
K
Klinkenberg factor
c total molar concentration
d
pore
pore diameter
D
AB
diffusion coefficient in binary gas system
D
i
diffusion coefficient of component i
D
a
i
activity-corrected diffusion coefficient of component i
D
T
i
thermal diffusion coefficient of component i
D
ii
self-diffusion coefficient
D
k
Knudsen diffusion coefficient
D
r
reservoir depth
f
i
fugacity of component i
G gravitational acceleration
h height
h
0
reference height
J
i
molar flux of component i
k formation permeability
k
a
apparent permeability
k
c
permeability of conventional reservoir models in this study
75
k
f
permeability of shale fracure
k
s
permeability of shale matrix
k
B
Boltzmann constant
K
n
Knudsen number
M molecular weight
P pressure
P
i
partial pressure of component i
P
initial
reservoir initial pressure
P
L
Langmuir pressure
P
L,i
Langmuir pressure of component i
P pressure gradient
Q gas flow rate
R gas constant
s skin factor
s
gi
initial gas saturation
s
wi
initial water saturation
T temperature
T
r
reservoir temperature
T
b
normal boiling temperature
V
a
adsorbed gas volume per rock weight
V
a,i
adsorbed gas volume of component i
76
V
b
liquid molar volume at normal temperature
V
c
critical volume of gas components
V
L
maximum Langmuir volume
V
L,i
maximum Langmuir volume of component i
v
m
molar volume of mixture
x
i
mole fraction of component i

c
AB
energy of interaction between component A and B
| porosity

mean-free-path

flow viscosity

i
chemical potential of component i

i0
reference chemical potential

o collision diameter

the gradient in the direction of flow
O
AB
diffusion collision integral

the sum of atomic diffusion volumes for each component

77
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81
Appendix A: Estimation of Diffusion Coefficients
For the binary gas system, three methods for estimating gaseous diffusion can be used
here. First is the Chapman-Enskog model (Chapman and Cowling, 1991):
(Equation A - 1)
*(
) (
)+
(Equation A - 2)
The collision integral
is defined by Neufeld et al. (1972):
(Equation A - 3)
where
is the Boltzmann constant, and
is the energy of interaction

between component A and B. The term (
) can be expressed as (
).
is the
normal boiling temperature. So
can be defined by the relationship between the

atmosphere temperature and boiling temperature:
(Equation A - 4)
The collision diameter is defined as:

(Equation A - 5)
where
is the liquid molar volume at normal temperature, and is presented as a

function of critical volume (Tyn and Calus, 1975):
(Equation A - 6)
In addition,
and

For example, for a binary gas system of CH
4
(component A) and CO
2
(component B)
under the condition of P= 34.5 bars (500 psia), T = 355 K (82
o
C), the basic data can be
82
found in reference (GPSA Engineering data book, 2004) and are shown in Table A-1
with other calculated parameters.
Component
M
(g/mol)
V
c

(cc/gmol)
V
b

(cc/gmol)
o
T
b

(K)
1.15T
b

=c/k
B

CH
4
16 98.7 35.07 3.86 111.67 128.42
CO
2
44 95 33.69 3.81 194.75 223.96
Table A- 1: Parameters for estimating binary gas diffusion coefficients by
empirical models.
*(
) (
)+
*(
) (
)+
g/mol

The second method is Wilke and Lee (1955) model:
*(
)+
(Equation A - 7)
We have the values for every parameter in this equation, so we can get the result:
[(
)]
*(
)+

The third method is Fuller (1965, 1966, 1969) model
(Equation A - 8)
83
The data of
for CO2 and CH4 can be found in research results by Fuller et al, 1969).

So:

In this work, we consider the molecular diffusion in the single component gas system,
called self-diffusion. The self-diffusion can still be expressed by the above models
which are shown in Table A-2. The parameters and estimated diffusion coefficients are
listed in Table A-3.

84
Model Expression
Chapman-
Enskog

Wilke-Lee

Fuller

Note:

Table A- 2: Models of estimating self-diffusion coefficients.
T
(K)
P
bars
M
g/mol
T
b

(K)
o
1.15Tb
=c/kB
T* O
355 34.5 16 111.67 3.86 128.42 2.76 0.971301
method 1 0.006216 cm
2
/s 0.05371 m
2
/day
D
ii,methane
2
/s
0.08049
m
2
/day
2
/s 0.07572 m
2
/day
Table A- 3: Diffusion coefficients of methane self-diffusion system estimated by
empirical models.

85
Appendix B: Relationship between Two Diffusion Coefficients
B.1 Concentration gradient driving diffusion model
Diffusion for the ideal gas system is driven by the concentration gradient (Ficks law):
(Equation B - 1)
where
is the molar flux of component i per unit area; c is the total molar concentration
given by
is the molar volume of the mixture;

component i;
is the gradient in the direction of flow;
is the diffusion coefficient of

component i in mixtures.
B.2 Chemical potential gradient driving diffusion model
Diffusion for non-ideal mixtures is driven by chemical potential gradient:
] (Equation B- 2)
is the thermal
diffusion coefficient of component i,
is the molecular weight of component i, is

the gravitational acceleration,
is the mole fraction of component i, is the height,

is the reference height, is the gas constant, is the temperature, and
is the chemical
potential of component i, given by
(Equation B- 3)
where
is the reference chemical potential, and
is the component fugacity which is

defined as an effective pressure replacing the true mechanical pressure in accurate
86
chemical equilibrium calculations. Fugacity of a real gas is equal to the pressure of an
ideal gas which has the same chemical potential as the real gas.
The first term in Equation B-2 is the chemical potential gradient; the second term
is gravity potential gradient; and the third term is temperature gradient. For
horizontal flow in isothermal system, the gravity potential gradient and
temperature gradient can be ignored, then the Equation B-2 can be written as:
(Equation B- 4)
Substitute Equation B-3 into Equation B-4, we have:
(Equation B- 5)
where
can be written as:
(Equation B- 6)
Then Equation B-5 can be written as:
(Equation B- 7)
Comparing B-1 and B-7, we can get the relationship between the two diffusion
coefficients:

(Equation B- 8)

87
Appendix C: Estimation of Knudsen Number and Apparent
Permeability
The Knudsen number
is defined by the ratio of the gas molecular mean-free-path

and the pore diameter d
pore
:

(Equation C-1)
The mean-free-path is given by Cunnigham and Williams (1980):

(Equation C-2)
where
is the Boltzmann constant, is the collision diameter.

(Equation C-3)
where V
c
is the critical volume of the gas component in cm
3
/mol. The value of critical
volume of methane is known from GPSA Engineering data book (2004).
The pore diameter is derived by Florence et al. (2007):
(Equation C-4)
k is reservoir permeability in md, is porosity, d is in cm.
With all these data, we can estimate the Knudsen number of our model, see Table C-1.
The Knudsen numbers of shale formations are 0.0747 for initial conditions, 0.0779 for
final conditions, and 0.1120 for final conditions with fractures which indicates there are
molecular-wall effects existing in our cases. In order to determine whether molecules-
wall collisions are important in our system, we can estimate the Klinkenberg factor to
see if the apparent permeability changes too much.
The Klinkenberg factor can be estimated by the following equation (Florence et al.,
2007):
88
(Equation C-5)
where is the mean free path in cm, p is pressure in psia.
Then we can estimate the apparent permeability of our system:
+ (Equation C-6)
where k is formation permeability in md,
is Klinkenberg factor in psi.

The final reservoir pressures of our shale formation models are around 4800 psia and
3336 psia for fractured models. Table C-2 summarizes the results of initial conditions,
final conditions, and bottom-hole-pressure conditions. The apparent permeability values
do not change too much between the initial and final conditions. Although the apparent
permeability for bottom-hole-pressure changes from 86 nd to 277 nd, our system will
never reach the bottom-hole-pressure conditions. In figure C-1 and C-2, we show the
simulation results of these different permeability values at the same condition in shale
formations. The gas rate value will increase twice as the base case, but the rate is still
very low (keep below 100 ft
3
/day in most of the production life) and the pressure drop is
still too small to cause desorption. So it is reasonable to ignore the phenomena caused
by molecule-wall collisions. Whats more, in order to keep the consistence among all
cases, we still use the permeability value of 54 nanodarcy for shale formation cases.

89
model
shale
formations,
initial
conditions
shale
formations,
final conditions
shale formations
with fractures,
final conditions
shale
formations,
BHP conditions
| 8% 8% 8% 8%
k, md 0.000054 0.000054 0.000054 0.000054
d
pore
, nm 3.06 3.06 3.06 3.06
V
c
, cc/mol 99 99 99 99
o
ii
3.7425 3.7425 3.7425 3.7425
P, bar 345 331 230 50
T, K 355.15 355.15 355.15 355.15
, nm 0.2285 0.2381 0.3427 1.5764
K
n
0.0747 0.0779 0.1120 0.5152
Table C- 1: Knudsen number estimation in this study.
model
Shale
formations,
initial
conditions
shale
formations,
final conditions
shale formations
with fractures,
final conditions
Shale
formations,
BHP conditions
P, psia 5004 4800 3336 725
b
k
, psia 2989.71 2989.68 2990.26 206.16
k
a
, nd 86.27 86.63 102.4 276.66
Table C- 2: Apparent permeability estimation in this study.

90

Figure C-1: gas production rate for different permeability cases

Figure C-2: reservoir pressure for different permeability cases

2012-Simulating Effects of Adsorption, Diffusion, and Convection in Tight Formations

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is maximum Langmuir volume, and

is Langmuir pressure, defined as the

, (psi). These two

) relate the gas storage capacity of a reservoir rock to pressure and

is the adsorbed volume of component i at partial pressure

can be used for measuring the degree of

is the Boltzmann constant, and is the collision diameter.

is the molar volume of the mixture;

is the mole fraction of

is the gradient in the direction of flow;

is the diffusion coefficient of

(Cussler, 1984; Taylor and Krishna, 1993).

is the self-diffusion coefficient of component i in

is the binary diffusion coefficient in cm

is the collision diameter in and

is the diffusion collision

are the molecular weights of A and B in gm/mol. The above model is

which usually causes the complexity of Chapman-Enskog model.

is the binary diffusion coefficient in cm

is the collision diameter in and

is the diffusion collision

are the molecular weights of A and B in gm/mol. M

is the binary diffusion coefficient in cm

is the sum of atomic diffusion volumes for each component (Fuller

are the molecular weights of A and B in gm/mol. M

is the activity-corrected diffusion coefficient of component i,

is the molecular weight of component i, is

is the mole fraction of component i, is the height,

is the reference chemical potential, and

is the component fugacity.

is the activity-corrected diffusion coefficient of component i,

is the mole fraction of

is the component fugacity. The detail of the relationship between

can be expressed as (Javadpour, 2007):

the sum of atomic diffusion volumes for each component

is defined by Neufeld et al. (1972):

is the Boltzmann constant, and

is the energy of interaction

can be defined by the relationship between the

is the liquid molar volume at normal temperature, and is presented as a

is the molar volume of the mixture;

is the mole fraction of

is the gradient in the direction of flow;

is the diffusion coefficient of

is the activity-corrected diffusion coefficient of component i,

is the molecular weight of component i, is

is the mole fraction of component i, is the height,

is the reference chemical potential, and

is the component fugacity which is

can be written as:

is defined by the ratio of the gas molecular mean-free-path

is the Boltzmann constant, is the collision diameter.

is Klinkenberg factor in psi.

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