ë (

m 1atm = 10 - 3 êé 1.709 ´ 10 - 5 - 2.062 ´ 10 - 6 g g )(1.8T - 459.67 ) + 8.188 ´ 10 - 3 - 6.15 ´ 10 - 3 lg g g ùú .

û (73)

A correlation method for this calculation was proposed by Londono et al. [92] as follows:
ê
m1atm = 10- 3 exp ê
( g) ( g)
é - 6.39821 - 0.6045922 ln g + 0.749768 ln (1.8T ) + 0.1261051 ln g ln (1.8T )ù
ú
ú. (74)
ê 1 + 0.069718 ln ( g g ) - 0.1013889 ln (1.8T ) - 0.0215294 ln (g g ) ln (1.8T ) ú
Energies 2020, 13, 5427 ë û 37 of 50
Meanwhile, the coefficient K in the Sutton method above is also equivalent to the low-pressure
gas viscosity, the value of which is 104 cp in the original work [93].
Figure 28a shows the relationship between gas viscosity at low pressure (p = 0.1 MPa). The Dempsey
Figure 28a shows the relationship between gas viscosity at low pressure (p = 0.1 MPa). The
method [96] leads to much higher values than the other three models, while the Londono method [92]
Dempsey method [96] leads to much higher values than the other three models, while the Londono
values are slightly higher than those from the Standing method [96] and Sutton method [93].
method [92] values are slightly higher than those from the Standing method [96] and Sutton method
The Standing method [96] and Sutton method [93] produce basically the same viscosity results.
[93]. The Standing method [96] and Sutton method [93] produce basically the same viscosity results.
Figure 28b displays gas viscosity variance with temperature at different pressures. For pressure lower
Figure 28b displays gas viscosity variance with temperature at different pressures. For pressure lower
than 14 MPa, the gas viscosity increases as temperature increases, which is the opposite situation to
than 14 MPa, the gas viscosity increases as temperature increases, which is the opposite situation to
that of liquids. With temperature increasing, the gas characteristics become more similar to those of
that of liquids. With temperature increasing, the gas characteristics become more similar to those of
liquids, and gas viscosity decreases as temperature increases.
liquids, and gas viscosity decreases as temperature increases.
0.018

0.016
Gas viscosity μatm, cP

0.014

0.012

0.01 Dempsey method Standing method

Londono method Sutton method
0.008
270 280 290 300 310 320 330 340 350 360
Temperature
Energies 2020, 13, 5427 38 of 51
(a)
0.035

0.03

0.025
Gas viscosity, cP

0.02

0.015

0.01
p=0.1 MPa p=5 MPa p=10 Mpa
0.005 p=14 Mpa p=20 Mpa p=30 MPa
p=40 Mpa
0

270 290 310 330 350

Temperature, K

(b)
Figure 28.
Figure Gas viscosity
28. Gas viscosity variance
variance with
with temperature
temperature at
atdifferent
differentpressure
pressureconditions.
conditions.(a)
(a)Gas
Gasviscosity
viscosity
calculated from different methods at atmospheric pressure. (b) Gas viscosity calculatedfrom
calculated from different methods at atmospheric pressure. (b) Gas viscosity calculated fromthe
the
Standing method
Standing method atat different
different pressures.
pressures.

In Figure 29, the gas viscosity from different models is compared with the experimental data for
In Figure 29, the gas viscosity from different models is compared with the experimental data for
pressures ranging from 0.1 MPa to 3.3 MPa at a temperature of 293.15 K. The experimental data were
pressures ranging from 0.1 MPa to 3.3 MPa at a temperature of 293.15 K. The experimental data were
chosen from the study of Hurly et al. [101]. As we can see, the calculation results vary: some match
chosen from the study of Hurly et al. [101]. As we can see, the calculation results vary: some match the
the experimental data well, while others deviate from the experimental data significantly, such as
experimental data well, while others deviate from the experimental data significantly, such as the H‒J
the H-J [94] and H-E-M methods [96]. To quantitatively evaluate the different models, the relative
[94] and H‒E‒M methods [96]. To quantitatively evaluate the different models, the relative deviation
and average absolute relative deviation (AARD), in terms of the experimental data, are given in Figures
30 and 31, respectively. Figure 30 illustrates that the H‒J [94] and H‒E‒M methods [94] have poor
performance for gas viscosity prediction for pressures ranging from 0.1 MPa to 3.3 MPa, while the
Izadmehr method [100] performs badly for both sour and sweet gas viscosity prediction when the
Energies 2020, 13, 5427 38 of 50

deviation and average absolute relative deviation (AARD), in terms of the experimental data, are
given in Figures 30 and 31, respectively. Figure 30 illustrates that the H-J [94] and H-E-M methods [94]
have poor performance for gas viscosity prediction for pressures ranging from 0.1 MPa to 3.3 MPa,
while the Izadmehr method [100] performs badly for both sour and sweet gas viscosity prediction
when the pressure is smaller than 1.4 MPa. This is because this method is obtained based on the
regression of different kinds of gases, while the experimental data are for the gas viscosity of pure
methane. Although the H-J method [97] predicts gas viscosity accurately when p < 1 MPa, its deviation
from the experimental data becomes more and more obvious as pressure increases. The Lee method,
Energies 2020,
Improved Lee13, method,
5427 Londono method, Sutton method, A-K method, Sanjari method, and Izadmehr 39 of 51

sweet gas method can predict gas viscosity for 0.1 MPa < p < 3.3 MPa with a relative deviation smaller
than 0.3%. 15 Among these methods, the Izadmehr sweet gas, Sanjari, A-K, and Sutton methods perform
Energies 2020, 13, 5427 39 of 51
the best, with AARD equalingLee methodto 0.57%, 0.68%, 0.88%,
Improved Lee 0.95%,
and method respectively,
Londono
asmethod
shown in Figure 31.
Sutton method H-J method A-K method
14
15 Sanjari H-E-M method J-H method
Lee method Improved Lee method Londono method
Gas viscosity, μPa s

Izadmehr-sour or sweet Izadmehr- sweet gas Experimental data

1314 Sutton method H-J method A-K method
Sanjari H-E-M method J-H method
Gas viscosity, μPa s

Izadmehr-sour or sweet Izadmehr- sweet gas Experimental data

1213

1112

1011

910

89
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
8 Pressure, MPa
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
Pressure,asMPa
Figure 29. Model comparison for gas viscosity calculations well as compared with experimental data
at 293.15 K.
Figure Model
29.29.
Figure Modelcomparison forgas
comparison for gasviscosity
viscosity calculations
calculations as well
as well as compared
as compared with experimental
with experimental data
data at 293.15
at 293.15 K. K.

15

1015

510

05
Relative error, %

-5 0
Relative error, %

-10-5 Lee method Improved Lee method

Londono method Sutton method
-10
-15 Leemethod
method Improved Lee method
H-J A-K method
Londono method Sutton method
Sanjari H-E-M method
-15 H-J method A-K method
-20 J-H method Izadmehr-sour or sweet
Sanjari H-E-M method
Izadmehr- sweet gas
-20 J-H method Izadmehr-sour or sweet
-25
Izadmehr- sweet gas
-25
-30
-300 0.5 1 1.5 2 2.5 3 3.5
0 0.5 1 1.5 2 2.5 3 3.5
Pressure, MPa
Pressure, MPa
Figure 30.Relative
Figure30. Relativedeviation
deviation of
of different
different models for gas
models for gas viscosity
viscositycalculation
calculationatat293.15
293.15K.K.
Figure 30. Relative deviation of different models for gas viscosity calculation at 293.15 K.
 Energies 2020, 13, 5427 40 of 51

Energies 2020, 13, 5427 39 of 50

Energies 2020, 13, 5427
18.00 40 of 51
16.07
16.00
18.00
16.07
14.00
16.00 12.50
12.00
14.00
12.50
AARD, %

10.00
12.00

8.00
AARD, %

10.00

6.00
8.00
3.81 4.15
4.00 2.78
6.00
1.58 1.42 3.81 4.15
2.00
4.00
0.95 0.88 0.68 0.57
2.78
0.00 1.58 1.42
2.00 0.95 0.88 0.68 0.57
0.00

Figure 31. The AARD of different models for gas viscosity calculation at 293.15 K.

Gas viscosity
Figurecalculation
Figure TheAARD
31.The
31. AARDresults at different
ofofdifferent
different models
models temperatures
forgas
for (273.13
gasviscosity
viscosity K, 293.13
calculation
calculation K, 313.13
at293.15
at 293.15 K. K, and 333.13
K.
K) for 0.1 MPa < p < 73 MPa are compared in Figure 32. The results of the H‒M‒S method vary
Gasviscosity
Gas viscosity
significantly calculation
calculation
as the results
results
temperature at different
at
changes.different temperatures (273.13
(273.13K,K,
temperaturesbetween
The discrepancies 293.13
293.13
the K,K,
313.13
different K,K,
313.13
models and 333.13
and K)
333.13
become more
K)for 0.10.1
for MPa
prominent MPa<asp < 73
p <MPa
<pressure are
73 MPa compared
are compared
increases. in Figure
However, 32.
inthe The results
Figure 32. Theofresults
discrepancies the H-M-S
become method
ofless
the H‒M‒Svaryas
obvious significantly
method vary
temperature
as the temperature
significantly changes. The discrepancies between the different models
increases. as the temperature changes. The discrepancies between the different models become become more prominent
more
as pressureasincreases.
prominent pressure However,
increases.the discrepancies
However, become less obvious
the discrepancies become as temperature
less obvious asincreases.
temperature
increases.
0.1 Lee method Improved Lee method
Londono method Sutton method
0.1 H-J method
Lee method
A-K method
Improved Lee method
0.08 H-M-S method Sanjari
Londono method Sutton method
H-E-M method J-H method
Gas viscosity, cP

H-J method A-K method

0.08 Izadmehr-sour or sweet
H-M-S method
Izadmehr- sweet gas
Sanjari
0.06
H-E-M method J-H method
Gas viscosity, cP

Izadmehr-sour or sweet Izadmehr- sweet gas

0.06
0.04

0.04
0.02

0.02
0
0 10 20 30 40 50 60 70 80
0 Pressure, MPa
0 10 20 30(a) T = 273.13
40 K 50 60 70 80
Pressure, MPa
Figure 32. cont.
(a) T = 273.13 K
 Energies
Energies 2020,
2020, 13,13, 5427
5427 40 of41
50of 51

Lee method Improved Lee method

0.08 Londono method Sutton method
H-J method A-K method
H-M-S method Sanjari
H-E-M method J-H method
0.06
Gas viscosity, cP
Izadmehr-sour or sweet Izadmehr- sweet gas

0.04

0.02

0
0 10 20 30 40 50 60 70 80
Pressure, MPa
(b) T = 293.13 K

Lee method Improved Lee method

Londono method Sutton method
H-J method A-K method
0.06
H-M-S method Sanjari
H-E-M method J-H method
Gas viscosity, cP

Izadmehr-sour or sweet Izadmehr- sweet gas

0.04

0.02

0
0 10 20 30 40 50 60 70 80
Pressure, MPa
(c) T = 323.13 K

Lee method Improved Lee method

Londono method Sutton method
0.06
H-J method A-K method
H-M-S method Sanjari
Gas viscosity, cP

H-E-M method J-H method

Izadmehr-sour or sweet Izadmehr- sweet gas
0.04

0.02

0
0 10 20 30 40 50 60 70 80
Pressure, MPa
(d) T = 353.13 K
Figure
Figure 32. 32. Comparison
Comparison of gasofviscosity
gas viscosity results
results from from models
different different models temperature
at different at differentconditions.
temperature
(a)conditions. (a)293.13
273.13 K. (b) 273.13K.
K.(c)
(b)323.13
293.13K.K.(d)
(c)353.13
323.13K.
K. (d) 353.13 K.
Energies 2020, 13, 5427 41 of 50

3.4.2. Adsorbed Gas Density

Empirical Formula
(1) Dubinin method: Adsorbed gas density cannot be directly measured by experiments as the free
gas density. As a result, many empirical formulations were proposed to approximately calculate
its value. A temperature-independent formula was proposed by Dubinin [75,102] to approximate
adsorbed gas density as follows:
M
ρad = , (75)
b
where b is the van der Waals covolume, representing the volume occupied by a single gas molecule.
(2) Gas density at critical point (pc , Tc ): The second way to calculate adsorbed phase gas density is
from the critical pressure and critical temperature [72,103]:

8Mpc
ρad = . (76)
RTc

Note that the above two methods are equivalent for calculating adsorbed gas density, which can
be linked by the van der Waals equation:
a
(p + )(V − b) = RT, (77)
V2
where V is the molar volume of real gas; a and b are van der Waals constants, where a is related to
intermolecular forces and b reflects the effects of the molecular volume of a real gas. According to
an experimental study, the first and second derivative of the pressure of pure gases towards molar
volume at the critical point (Tc , pc ) equal 0, i.e.:

∂p
( ) = 0, (78)
∂V Tc

∂2 p
( ) = 0. (79)
∂V 2 Tc
Combining Equations (77)–(79), the values of the constants a and b are solved as follows:

27R2 Tc2
a= , (80)
64pc

RTc
b= . (81)
8pc
Substituting Equation (81) into Equation (75), Equation (76) could be obtained. Therefore, the methods
of Equations (75) and (76) for calculating adsorbed gas density are the same.
(3) Ozawa method: Assuming adsorbed phase gas in a sort of superheated liquid state, Ozawa [75]
calculated the density of adsorbed gas by the following equation [75]:

ρad = ρb exp[−0.0025(T − Tb )], (82)

where ρad is the adsorbed gas density, ρb is the liquid density at normal boiling point, T is the
temperature, and Tb is the normal boiling point.
Although ρb and Tb of gases are functions of pressure, their values are assigned at the atmosphere
pressure, when the pressure dependences of these quantities are negligibly small in the pressure range
of the study. If the effects of pressure on ρb and Tb values cannot be neglected, they as well as the
coefficient −0.0025 should be assigned other values.
 Energies 2020, 13, 5427 42 of 50

Energies 2020, 13, 5427 43 of 51

According to the relationship between absolute adsorption and excess adsorption, the isotherm
recommendedmethod
linearization can also
to calculate thebe used to
virtual obtain adsorbed
saturated phase gasusing
vapor pressure, density.
thisSince it is to
method notobtain
recommended
adsorbed
to calculate
gas the virtual
density will saturated vapor
not be introduced here.pressure,
One of the using this method
conclusions fromtothis
obtain adsorbed
paper [77] is gas
thatdensity willof
the value
not be introduced
adsorbed gas densityhere.
is One of thethe
between conclusions from this
critical density paper
(162.66 [77]3,isatthat
kg/m theMPa
4.59 valueand of 190.53
adsorbed
K) gas
and
density is between the critical density (162.66 kg/m 3 , at 4.59 MPa and 190.53 K) and normal boiling
normal boiling density of liquid phase (422.36 kg/m , at 0.101 MPa and 111.67 K), which can be
3

density offrom
confirmed liquidthephase
calculation kg/m3of
(422.36results , atdifferent
0.101 MPa and as
models, 111.67 K),seen
can be which can be33a.
in Figure confirmed from
Note that the
the calculation
data results of
of the Ono‒Kondo different
method andmodels,
ZGR EOS as are
cancollected
be seen in Figure
from 33a. Note
a previous study that the data of theet
of Sudibandriyo
Ono-Kondo
al. [104]. method and ZGR EOS are collected from a previous study of Sudibandriyo et al. [104].

500
Adsorbed gas density, kg/m3

400

300

200

100 Dubinin method Density at critical point

Ozawa method Ono-Kondo method
Liquid density ZGR EOS
0
273.13 293.13 313.13 333.13 353.13 373.13
Temperature, K
(a)

400 1.8
Gas density Dubinin method
350 Critical density Ozawa method
1.3
Free gas density, kg/m3

Ono-kondo method Liquified gas density

300
ZGR EOS
0.8
250
1-ρg/ρa

200 0.3

150
-0.2
100
-0.7
50

0 -1.2
0 10 20 30 40 50 60 70 80

Pressure, MPa

(b)
Figure
Figure33. 33.Comparison
Comparisonof ofadsorbed
adsorbedgas
gas density
density calculated
calculated from different
different models
models(a)
(a)and
andthe
thechange
changeofof
(1(1−−ρρ g /ρ
g/ρ a)awith increasing
) with increasingpressure
pressure(b).
(b).

The adsorbed gas density is independent of temperature in all methods except the Ozawa model
[75] of Equation (82), which assumed adsorbed gas as a superheated liquid. It seems that the Ozawa
model is more suitable to predict adsorbed gas density since superheated liquid can expand with
increasing temperature. However, the excess adsorption, which is calculated by Equation (25), may
 Energies 2020, 13, 5427 43 of 50

The adsorbed gas density is independent of temperature in all methods except the Ozawa
model [75] of Equation (82), which assumed adsorbed gas as a superheated liquid. It seems that the
Energies
Ozawa 2020, 13, 5427
model is more suitable to predict adsorbed gas density since superheated liquid can expand44with of 51
increasing temperature. However, the excess adsorption, which is calculated by Equation (25), may have
have a negative
a negative value,
value, as can
as can be inferred
be inferred from
from Figure
Figure 33b.
33b. This
This is is
notnot physicallyright.
physically right.As
Aswewementioned,
mentioned,
ρρb and Tb of gases are functions of pressure for superheated liquid. These pressure-dependent
b and Tb of gases are functions of pressure for superheated liquid. These pressure-dependent
characteristics
characteristicsare areignored
ignoredin inthe
the original
original work
work [75],
[75], which
which cannot
cannot be be neglected
neglected inin aa sorption
sorptionstudy
studyofof
shale
shalegasgasreservoirs.
reservoirs.Therefore,
Therefore,corresponding
correspondingresearch
research needs
needs toto be done on
be done on this
this subject
subject to
to develop
developaa
more practical model for shale gas sorption
more practical model for shale gas sorption study. study.

Experimental
ExperimentalMethod
Method
The
Theexperimental
experimentalsurface
surfacesorption
sorptionamount
amount can
can be
be a starting point for the
the calculation
calculation of
ofabsolute
absolute
adsorption
adsorptionandandadsorbed
adsorbedgas
gasdensity.
density. From
From Equations
Equations (24) and (25), we can obtain
obtain another
another expression
expression
ofofexcess
excesssorption:
sorption:
= ((rρad −
GGexex = - ρrgg))vvada d. . (83)
(83)
ad

Forhigh-pressure
For high-pressureadsorption,
adsorption,bulkbulkgasgas is
is more
more compressible
compressible than than adsorbed
adsorbed gas gas andand the
theexcess
excess
sorption isotherm is mainly influenced by bulk gas EOS, where the adsorbed gas volume canbe
sorption isotherm is mainly influenced by bulk gas EOS, where the adsorbed gas volume can beseen
seen
asasaaconstant
constantwith withincreasing
increasingpressure.
pressure. From
From this
this standpoint,
standpoint, the the line
line segment
segment after
after the
the inflection
inflectionpoint
point
onplot
on plotofofexcess
excesssorption
sorption amount
amount versus
versus bulk
bulk gasgas density
density cancanbe be
usedused
for for calculating
calculating the the volume
volume and
and density of adsorbed gas, as we can see from Figure 34. The density and
density of adsorbed gas, as we can see from Figure 34. The density and volume of adsorbed gas after volume of adsorbed gas
after
the the maximum
maximum sorption
sorption amount
amount can can be speculated
be speculated by by
thethe slopeand
slope andintercept
interceptof of line,
line, according
according to to
Equation (83), where the absolute value of the slope is adsorbed gas volume and the intersectionpoint
Equation (83), where the absolute value of the slope is adsorbed gas volume and the intersection point
ofoflinear
linearsegment
segmentand x-axis is
andx-axis is adsorbed
adsorbed gas gas density
density [80,104].
[80,104]. The
The calculated
calculated adsorbed
adsorbed gas gas density
densityof of
methane is between 413.78 kg/m 3 and 433.41 kg/m 3 , which is in the range of liquid density at its boiling
methane is between 413.78 kg/m and 433.41 kg/m , which is in the range of liquid density at its boiling
3 3

pointρρb b==422.36
point kg/m3.3 .The
422.36kg/m Thecalculated
calculatedadsorbed
adsorbedgas gas volume
volume forfor methane
methane is is between
between 0.4230.423cm cm3/g
3 and
/g and
0.467cm 3 /g for 303 K < T < 333 K. Note that, due to data error and the difference in data processing
cm3/g
0.467 for 303 K < T < 333 K. Note that, due to data error and the difference in data processing
methods,there
methods, thereisisaaslight
slightvariation
variation inin the
the results
results between
between our our calculation
calculation (see
(see in
in Figure
Figure35) 35)and
andthat
thatof
of
Moellmer et al.
Moellmer et al. [80]. [80].

200
180
T=333K
Excess sorption amount, mg/g

160
T=318K
140
T=303K
120
100
80
60 y = -0.4672x + 202.49
40 y = -0.448x + 188.14
20 y = -0.4231x + 175.07
0
0 50 100 150 200 250 300
Free gas density,kg/m3

Figure34.
Figure Excesssorption
34.Excess sorptionamount
amountof
of methane
methane in
in three different temperatures
temperatures and
and the
the line
linesegment
segment
after inflection point of maximum [80].
after inflection point of maximum [80].
Energies
Energies 2020, 13, 5427 4445
ofof
5051

435
303, 433.41
430

Free gas demsity, kg/m3 425

318, 419.96
420
333, 413.78
415

410
300 305 310 315 320 325 330 335

Temperature, K
(a)

0.47
303, 0.467
Adsorbed gas volume, cm3/g

0.46

0.45 318, 0.448

0.44
333, 0.423
0.43

0.42
300 305 310 315 320 325 330 335

Temperature, K
(b)
Figure 35. The change in adsorbed gas density (a) and adsorbed gas volume (b) with temperature,
Figure 35. The change in adsorbed gas density (a) and adsorbed gas volume (b) with temperature,
calculated by an experimental method.
calculated by an experimental method.

As we can see from Figure 35a, the adsorbed gas density of methane decreases as temperature
As we can see from Figure 35a, the adsorbed gas density of methane decreases as temperature
increases, showing a similar tendency to the Ozawa prediction [75], but with a higher value. This may
increases, showing a similar tendency to the Ozawa prediction [75], but with a higher value. This may
provide a way to modify the Ozawa model of Equation (82), as we have mentioned that constant values
provide a way to modify the Ozawa model of Equation (82), as we have mentioned that constant
of ρb and Tb for gases as well as the coefficient −0.0025 may not be suitable for methane sorption studies
values of ρb and Tb for gases as well as the coefficient −0.0025 may not be suitable for methane sorption
at high pressure. The calculated adsorbed gas volume of methane also shows a decreasing tendency
studies at high pressure. The calculated adsorbed gas volume of methane also shows a decreasing
with increasing temperature, as shown in Figure 35b, which corresponds to a decreasing amount
tendency with increasing temperature, as shown in Figure 35b, which corresponds to a decreasing
adsorbed at increasing adsorption temperatures [80].
amount adsorbed at increasing adsorption temperatures [80].

4.
4. Concluding
Concluding Remarks
Remarks
Due
Due to
to the
the massive development of
massive development of shale
shalegas
gasreservoirs
reservoirsin inrecent
recentyears,
years,thetheunderstanding
understandingofofshale
shale
formation characteristics and shale gas storage forms has become a research hotspot.
formation characteristics and shale gas storage forms has become a research hotspot. Our increased Our increased
understanding
understandinghas hashelped
helpedtotoextend
extendthethe
application of the
application classical
of the seepage
classical seepagetheory to new
theory to fields, where
new fields,
nanoscale flow spaces, gas sorption behaviors, and real gas properties are taken into account.
where nanoscale flow spaces, gas sorption behaviors, and real gas properties are taken into account. However,
much disagreement
However, and confusion
much disagreement andon this subject
confusion still subject
on this exist, sostill
it requires
exist, socomprehensive investigation
it requires comprehensive
in the future. in the future.
investigation
This
This review includes aa summary,
review includes summary, discussion,
discussion,and
andcomparison
comparisonofofshaleshaleformation
formationcharacteristics,
characteristics,
shale gas occurrence types, and property calculation methods of adsorbed
shale gas occurrence types, and property calculation methods of adsorbed gas and gas and free gas, free
providing
gas,
fundamental support to the deep understanding of shale gas reservoirs. (1) The typical
providing fundamental support to the deep understanding of shale gas reservoirs. (1) The typical mineral mineral
composition and organic geochemical characteristics, as well as pore size distribution, of shale
Energies 2020, 13, 5427 45 of 50

composition and organic geochemical characteristics, as well as pore size distribution, of shale
formations are given based on our measurements and analysis of samples from the Longmaxi
Formation. We found that mesopores are the mainly developed pore types in the Longmaxi Shale
Formation, with the gas-filled porosity of shale samples ranging from 1% to 7.5%, and permeability
usually smaller than 0.1 mD. Three shale gas types are usually classified, free gas, adsorbed gas,
and dissolved gas, where adsorbed gas and dissolved gas are often considered as one type due to the
equilibrium state between them. Therefore, it is claimed that there are two gas types, free gas and
adsorbed gas, in shale gas plays in some research. (2) Methane in shale gas reservoirs is in a supercritical
state, so Gibbs excess sorption models and supercritical state sorption models are employed to capture
the gas adsorption and desorption behaviors. Meanwhile, different models considering not only the gas
adsorption but also the absorption are introduced. Great discrepancies could occur if the supercritical
state and Gibbs excess adsorption characteristics are ignored. Different mechanisms of adsorption in
micropores and macropores may explain the hysteresis between adsorption and desorption, rather than
capillary condensation. (3) Different methods of calculating gas properties, such gas free gas density,
free gas viscosity, and adsorbed gas density considering high-pressure and high-temperature conditions,
are summarized, with recommended approaches given after the comparison. From our review, we can
see that the geological characteristics of shale formations are quite different from those of conventional
ones, and need further assessment using a high-resolution apparatus. Gas adsorption mechanisms
are still not clear, although numerous models have been developed to account for this phenomenon.
For example, current supercritical adsorption models based on the potential theory are modifications
of a previous adsorption theory, which are dependent on empirical parameters and lack of a universal
theoretical basis. Applicable multicomponent gas adsorption models considering high-pressure and
high-temperature conditions and pore size distribution are in demand to describe gas behavior in shale
gas reservoirs. They are a rough way to clarify adsorbed gas and dissolved as one type, since dissolved
gas may play an important role in shale gas production. Therefore, current adsorption and absorption
models should be improved, based on the practical relationship between adsorbed gas and dissolved
gas under in situ conditions.

Author Contributions: Conceptualization, Y.Z. and L.Z.; methodology, B.Z. and B.S.; validation, B.S. and Y.Z.;
formal analysis, B.Z. and B.S.; investigation, B.Z.; resources, L.Z..; writing—original draft preparation, B.Z., B.S.
and Y.Z.; writing—review and editing, L.Z.; supervision, B.S. and L.Z.; All authors have read and agreed to the
published version of the manuscript.
Funding: This work was supported by the National Natural Science Foundation of China (grant nos. 51874251
and 51704247) and the Science and Technology Cooperation Project of the CNPC-SWPU Innovation Alliance.
Acknowledgments: The authors would like to thank the reviewers and editors, whose critical comments were
very helpful in preparing this article.
Conflicts of Interest: The authors declare no conflict of interest.

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