http://pubs.acs.

org/journal/acsodf Article

Influences of Hydrogen Blending on the Joule−Thomson Coefficient

of Natural Gas
Jingfa Li, Yue Su, Bo Yu,* Peng Wang, and Dongliang Sun
Cite This: ACS Omega 2021, 6, 16722−16735 Read Online

ACCESS Metrics & More Article Recommendations *

sı Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Blending hydrogen into the natural gas pipeline is considered as a

feasible way for large-scale and long-distance delivery of hydrogen. However, the
blended hydrogen can exert major impacts on the Joule−Thomson (J−T) coefficient
Downloaded via SUNGKYUNKWAN UNIV on May 11, 2023 at 06:49:18 (UTC).

of natural gas, which is a significant parameter for liquefaction of natural gas and
formation of natural gas hydrate in engineering. In this study, the J−T coefficient of
natural gas at different hydrogen blending ratios is numerically investigated. First, the
theoretical formulas for calculating the J−T coefficient of the natural gas−hydrogen
mixture using the Soave−Redlich−Kwong (SRK) equation of state (EOS), Peng−
Robinson EOS (PR-EOS), and Benedict−Webb−Rubin−Starling EOS (BWRS-EOS)
are, respectively, derived, and the calculation accuracy is verified by experimental data.
Then, the J−T coefficients of natural gas at six different hydrogen blending ratios and
thermodynamic conditions are calculated and analyzed using the derived theoretical
formulas and a widely used empirical formula. Results indicate that the J−T
coefficient of the natural gas−hydrogen mixture decreases approximately linearly with the increase of the hydrogen blending ratio.
When the hydrogen blending ratio reaches 30% (mole fraction), the J−T coefficient of the natural gas−hydrogen mixture decreases
by 40−50% compared with that of natural gas. This work also provides a J−T coefficient database of a methane−hydrogen mixture
with a hydrogen blending ratio of 5−30% at a pressure of 0.5−20 MPa and temperatures of 275, 300, and 350 K as a reference and a
benchmark for interested readers.

1. INTRODUCTION For gas transportation, consideration must be given to the

With the increasingly serious global warming and the depletion
of traditional fossil fuels, clean renewable energy has attracted
considerable attention in recent years.1 However, due to the
uneven distribution of renewable resources, system-wide
oversupply, and other reasons, renewable energy has not
been fully utilized and consumed. The waste of surplus
renewable energy generation is commonly seen in many
countries. As a kind of clean energy carrier, hydrogen has the
advantages of wide sources and zero-carbon emission. It can be
produced from renewable energies such as wind energy,
nuclear energy, electric energy, etc. Through the power-to-gas
(P2G) technology, surplus renewable energy generation can be
converted to gaseous hydrogen; thus, it is viewed as an
effective way to solve the wastage of renewable energy
generation.2−5 The research of P2G technology can date
back to earlier years in countries such as Germany and the
United States. For example, in Europe alone there are more
than 45 P2G projects in operation and under construction.
Between hydrogen generation by P2G projects and hydrogen
consumption by users, hydrogen delivery is a key link. For
larger economic benefits and shorter transportation periods,
blending hydrogen into natural gas is considered as one of the
best feasible ways to achieve large-scale, long-distance
transport of hydrogen using existing natural gas pipelines or
pipe networks.6
© 2021 The Authors. Published by
American Chemical Society
16722
Joule−Thomson (J−T) effect (also known as the throttling
effect). The J−T effect was first observed in an experiment
conducted by James Prescott Joule and William Thomson in
1852 and is a thermodynamic process that occurs when a fluid
expands from high pressure to low pressure at constant
enthalpy.7 If the J−T coefficient is positive, then the fluid cools
upon expansion, and if it is negative, the fluid warms upon
expansion. The cooling produced in J−T expansion has been a
double-edged sword in natural gas engineering. For example,
the temperature drop caused by the J−T effect during natural
gas transportation can cause gas hydrate blockage at the
pipeline valves;8,9 in the production of natural gas hydrate, the
temperature change induced by the J−T effect has significant
impacts on the production efficiency;10 in natural gas
liquefaction, the cooling produced in the J−T expansion can
be used to liquefy natural gas,11 etc. Therefore, it is of great
engineering significance to study the J−T effect of natural gas.
Received: January 14, 2021
Accepted: June 9, 2021
Published: June 21, 2021
https://doi.org/10.1021/acsomega.1c00248
ACS Omega 2021, 6, 16722−16735
ACS Omega http://pubs.acs.org/journal/acsodf
Compared with traditional natural gas without hydrogen, the
composition and relative content of natural gas are changed
upon hydrogen blending, resulting in variations in its physical
and thermodynamic properties. Thus, for the natural gas−
hydrogen mixture, hydrogen blending can exert great
influences on the J−T effect. Accurately calculating the J−T
coefficient of the natural gas−hydrogen mixture and revealing
the influences of hydrogen blending on the J−T effect are of
great importance. At present, the widely used methods for
predicting the J−T coefficient include experimental measure-
ment,12−16 pressure−enthalpy chart,7 empirical formula,7
molecular simulation,17−19 theoretical calculation using equa-
tion of state (EOS),20−24 etc.
In the aspect of experimental measurements, many scholars
measured the J−T coefficient of different gases via experi-
ments. The basic experimental principle of J−T expansion can
be summarized as follows: a gas with volume V1, pressure p1,
and temperature T1 flows through a porous membrane, pushed
by a piston at pressure p1; the gas expands against a piston at a
lower pressure p2 until all of the gas has been transferred to the
other side of the membrane with a final volume V2 and
temperature T2, and then the J−T coefficient can be calculated
by the pressure and temperature changes before and after
expansion. From the 1970s to the 1990s, Francis et al.12−14
designed flow calorimeters to measure the specific heat
capacity and the J−T coefficient. The J−T coefficients of
ethanol, benzene, and cyclohexane vapors at different temper-
atures and pressures were measured in their study. Cuscó et
al.15 applied an improved flow calorimeter to measure the J−T
coefficients of N2 and CO2 at high temperature and high
pressure. Ernst et al.16 measured the J−T coefficients of CH4,
CH4−C2H6 mixture, and natural gas at different conditions,
and the experimental results provide an important reference
and contribute to the experimental basis for the formulation of
an EOS.
In terms of numerical calculation, current calculation
methods for the J−T coefficient mainly include the
pressure−enthalpy chart,7 empirical formula,7 molecular
simulation,17−19 and theoretical calculation using EOS.20−24
When the temperature and pressure before expansion and the
pressure after expansion are known, the temperature after
expansion can be obtained by reading the pressure−enthalpy
chart, and the J−T coefficient can be calculated.7 This
pressure−enthalpy chart is simple to read and is commonly
used in engineering practice. However, it is worth noting that
this method is not a general approach because the pressure−
enthalpy chart is usually plotted for a specific natural gas
mixture. Compared with the pressure−enthalpy chart, the
empirical formula for calculating the J−T coefficient of natural
gas is a general method with wide application scopes.7 When
the specific heat capacity, the reduced temperature and
pressure, and the critical temperature and pressure of natural
gas are known, the J−T coefficient can be calculated using the
empirical formula. However, the calculation accuracy of the
empirical formula is relatively low. For the mechanism study,
molecular simulation is a valuable tool for investigating the J−
T effect from a microscopic point of view. For example, Vrabec
et al.17 applied molecular simulation and four equations of
state to calculate the J−T coefficients of six different natural
gas mixtures. It was found that the molecular simulation is
competitive with state-of-the-art EOS in predicting J−T
inversion curves. Figueroa-Gerstenmaier et al.18 carried out
molecular simulations on the J−T coefficient of various
16723
Article
refrigerants over a wide range of thermodynamic conditions,
and the simulation results were compared with pseudo-
experimental-results obtained from the REFPROP software
package. Zhang et al.19 analyzed the throttling mechanism of
CO2 at different states from a molecular perspective, and a
method for predicting the J−T coefficient of pipeline CO2 was
put forward using the multivariate nonlinear regression
method. It is worth pointing out that although molecular
simulation can reveal the mechanism of the J−T effect and
calculate the J−T coefficient from a microcosmic perspective,
the application of this method is always limited by the high
computational costs. In addition, the molecular simulation
system is usually simplified and it cannot fully reproduce the
real physical system of natural gas.
For theoretical calculation of the J−T coefficient using the
EOS, the accuracy depends on the selected EOS, and there
have been extensive related studies. Tay et al.20 applied the
population balance model to simulate the condensation
process of nonequilibrium water, and the influence of the J−
T effect on the dehydration process of natural gas was analyzed
using SRK-EOS. Haghighi et al.21 compared the performance
of five EOSs to predict the J−T inversion curve. Results
illustrated that the selected EOSs can well predict the low-
temperature branch of the J−T inversion curve, except for the
Mohsennia−Modarres−Mansoori EOS. In addition, the high-
temperature branch and peak value of the inversion curve
turned out to be sensitive to the adopted EOS. Abbas et al.22
calculated the J−T coefficients of CO2, Ar, CO2−Ar mixture,
and CH4−C2H6 mixture by the group contribution equation of
state VTPR, and the computed J−T coefficients were in good
agreement with the experimental data. Ghanbari and Check23
applied the J−T inversion curve data of CH4 and CO2 to
adjust the supercritical cohesion parameters for SRK-EOS. The
modified SRK-EOS was verified to present good predictions of
J−T inversion curve data. Regueira et al.24 compared the
performance of SRK, PR, perturbed chain statistical associating
fluid theory (PC-SAFT), and Soave−Benedict−Webb−Rubin
(SBWR) EOSs in modeling the specific heat capacity and the
J−T coefficient. Results demonstrated that the PC-SAFT-EOS
is most accurate in predicting the specific heat capacity, and
the SBWR-EOS has the best performance in calculating the J−
T coefficient. Generally speaking, the theoretical calculation of
the J−T coefficient using the EOS can be well applied to
practical engineering as it is based on a real gas model, and the
calculated J−T coefficient is more accurate than that obtained
from pressure−enthalpy chart, empirical formula, or the
molecular simulation method.
For hydrogen transportation using existing natural gas
pipelines, blending hydrogen into natural gas may produce
different J−T effects, which unfortunately has rarely been
reported. As the physical and thermodynamic properties of
hydrogen and natural gas are quite different, the influence of
hydrogen blending on the J−T coefficient of the natural gas−
hydrogen mixture is still unclear. In this research, the effect of
hydrogen blending on the J−T coefficient of natural gas is
numerically investigated, and the mechanism of J−T
coefficient variation with the hydrogen blending ratio is
revealed. This work is expected to provide a beneficial
reference for natural gas engineering, such as for prevention
and control of gas hydrate in pipeline transport of the natural
gas−hydrogen mixture, liquefaction of hydrogen-enriched
natural gas, etc.
https://doi.org/10.1021/acsomega.1c00248
ACS Omega 2021, 6, 16722−16735
ACS Omega http://pubs.acs.org/journal/acsodf Article

The remainder of this paper is organized as follows: in Substituting eq 4 and the relation between molar volume
Section 2, the theoretical formulas for calculating the J−T and molar density υ = 1/ρ into eq 3, the following J−T

ÅÄÅ ÑÉÑ
coefficient of natural gas using SRK-EOS, PR-EOS, and coefficient of component i can be obtained

1 ÅÅÅ T ij ∂p yz ijj ∂p yzz 1 ÑÑÑ

μi = ÅÅÅ 2 jj zz /jj zz − ÑÑÑ
BWRS-EOS are mathematically derived; in Section 3, the

predicted J−T coefficients by EOSs and empirical formula are
validated by experimentally measured J−T coefficients of pure
methane, methane−ethane mixture, and natural gas at different
pressures and temperatures; in Section 4, the J−T coefficient
of natural gas at six different hydrogen blending ratios and
thermodynamic conditions is calculated, and the effect of
hydrogen blending on the J−T coefficient is analyzed in detail.
To provide a valuable reference and a benchmark for future
research on the natural gas−hydrogen mixture, the J−T
coefficient database of the methane−hydrogen mixture at
different hydrogen blending ratios, pressures, and temperatures
is presented; and in Section 5, concluding remarks of this study
are summarized and the future study is discussed.
2. JOULE−THOMSON COEFFICIENT OF THE
NATURAL GAS MIXTURE
2.1. Derivation of the Joule−Thomson Coefficient.
The J−T effect can be described by means of the J−T
coefficient, which is the partial derivative of temperature with
respect to pressure at constant enthalpy. For a pure component
i, the isenthalpic J−T coefficient can be expressed as follows
cp ÅÅ ρ k ∂T { ρ k ∂ρ {T ρ ÑÑ
ÅÇ ÑÖ
(5)
It should be noted that eq 5 represents the J−T coefficient
of the natural gas mixture provided that the parameters ρ and
cp in eq 5 adopt the values of the natural gas mixture. For
calculation convenience, accuracy, and efficiency in engineer-
ing practice, the J−T coefficient can also be predicted by the
pressure−enthalpy chart, empirical formulas, and molecular
simulation. To comprehensively explore the influences of
hydrogen blending on the J−T coefficient of the natural gas−
hydrogen mixture, in this study, one widely used empirical
formula and three commonly used EOSs in engineering
practice, i.e., SRK-EOS, PR-EOS, and BWRS-EOS, are chosen
as representatives to calculate the J−T coefficient of the natural
gas−hydrogen mixture.
2.2. Joule−Thomson Coefficient by the Empirical
Formula. In an empirical formula, the J−T coefficient of the
natural gas−hydrogen mixture is closely related to critical
parameters, reduced parameters, and the molar specific heat
capacity at constant pressure. The following presents a widely

ij ΔT yz ij ∂T yz
used empirical formula for calculating the J−T coefficient7

μi = lim jjj zzz = jjj zzz

Δp → 0j Δp z j z
4.1868f (pr , Tr )Tc
k { H k ∂p { H
μEF =
(1) pc cp (6)

where μi is the J−T coefficient of pure component i; T is the
temperature; p is the pressure; and the subscript H denotes an
isenthalpic process. The thermodynamic parameters use SI
units unless otherwise specified.
Based on the relation of thermodynamic parameters, eq 1
can be reformulated as
where f(pr,Tr) = 2.343T−2.04
r − 0.071pr + 0.0568; Tr and pr are
the reduced temperature and pressure, respectively; Tc and pc
denote the critical temperature and pressure, respectively; and
cp is the molar specific heat capacity of a gas at constant
pressure. For the mixture of natural gas and hydrogen, the
parameters in eq 6 are those of the natural gas−hydrogen

ij ∂T yz ij ∂H yz i ∂H y i y
zz /jj zz = − 1 jjj ∂H zzz
mixture.

μi = jjj zzz = −jjj

j ∂p z j ∂p zz jk ∂T z{ cp k ∂p zz{
j
j
2.3. Joule−Thomson Coefficient by SRK-EOS. SRK-

k {H k {T
EOS25 is a cubic-type equation of state that has been widely
p T (2) used in natural gas engineering in the past. It is a modification
of RK-EOS26 by correcting the a/√T term of RK-EOS using a
where cp is the molar specific heat capacity of component i at function α involving the temperature and the acentric factor
constant pressure.
Equation 2 can be further rearranged as7 follows (see the RT a
p= −

ÄÅ ÑÉÑ ÅÄÅ
Supporting Information) υ−b υ(υ + b) (7)

Å
1 jij ∂H zyz 1 ÅÅÅ ij ∂υ yz ÑÑ
Ñ 1 ÅÅÅ ij ∂υ yz
μi = − jj z = − ÅÅÅ−T jj zz + υÑÑÑ = ÅÅÅT jj zz
cp jk ∂p zz{
where p is the system pressure, kPa; T is the system

cp ÅÅ k ∂T { p ÑÑ cp ÅÅ k ∂T { p
temperature, K; υ is the molar volume, m3/kmol; R is the
ÅÇ ÑÖ ÅÇ
ÑÉÑ
universal gas constant, R = 8.3145 kJ/(kmol·K); the attraction
ÑÑ
T

− υÑÑÑ
0.42748R2Tc2

ÑÑ
parameter a = a(T c )α, where a(Tc) = and

ÑÑÖ
pc
0.08664RTc
(3) α = [1 + κ(1 − Tr )]2 ; b = b(Tc) = pc
; T c and p c
are the critical temperature and critical pressure, respectively;
where υ is the molar volume. The term ( ∂∂Tυ )p in eq 3 can be T
Tr is the reduced temperature, Tr = T ; and κ = 0.48508 +
c
written as 0.55171ω − 0.15613ω2, where ω is the acentric factor.
i y
ij ∂υ yz i ∂p y i ∂p y i ∂p y jj ∂p zz 1 i ∂p y
jj zz = jjj zzz /jjj zzz = jjj zzz /jjjj 1 zzzz = 2 jjj zzz
For the natural gas−hydrogen mixture, the above

k ∂T { p k ∂T {υ k ∂υ {T k ∂T { ρ jj ∂ ρ zz
coefficients a and b in eq 7 are obtained by mixing the
ρ k ∂T { ρ
k {T
corresponding coefficients of included components. The
commonly used mixing rules are defined as follows
i ∂p y
/jjjj zzzz
C C C

k ∂ρ {T
a= ∑ ∑ yyi j (aiaj)0.5 (1 − kij), b = ∑ yb
i i
(4) i=1 j=1 i=1 (8)

16724 https://doi.org/10.1021/acsomega.1c00248
ACS Omega 2021, 6, 16722−16735
ACS Omega http://pubs.acs.org/journal/acsodf Article

where C is the total number of components; yi is the mole Similarly, the partial derivative of PR-EOS (eq 13) to
fraction of component i; and kij is the binary interaction temperature T and density ρ can be derived as follows

ij ∂p yz
coefficient between components i and j, kij =kji and kii = 0. The
jj zz
da
value of kij for different components can be obtained in refs 7, ρ 2 dT
k ∂T { ρ ,PR
ρR
27. = −
For the convenience of calculation, the molar volume υ in eq 1 − ρb 1 + 2ρb − ρ2 b2 (14)

ij ∂p yz
7 can be expressed by molar density. Substituting υ = 1/ρ into
jj zz
j ∂ρ z
eq 7 yields

k {T ,PR
RT 2ρ(1 + ρb)a
= 2
−
ρRT ρ a 2 (1 − ρ b) (1 + 2ρb − ρ2 b2)2 (15)
p= −
1 − ρb 1 + ρb (9)
daj
According to eq 5, the partial derivative of SKR-EOS (eq 9) where
da
dT
C C
= 0.5 ∑i = 1 ∑ j = 1 xixj ( dai −0.5 0.5
a aj
dT i
+ ai0.5aj−0.5 dT . )
to temperature T and density ρ should be derived to calculate
the J−T coefficient of the natural gas mixture. However, it (1 − kij)
should be pointed out that the attraction parameter a of SRK- Finally, substituting eqs 14 and 15 into eq 5 yields the J−T
EOS is a function of system temperature T; thus, special coefficient μPR of the natural gas−hydrogen mixture by PR-
attention should be paid to the partial derivative of SRK-EOS, EOS.
eq 9, to T 2.5. Joule−Thomson Coefficient by BWRS-EOS.

ij ∂p yz
BWRS-EOS29 is currently the most widely used real gas
jj zz
2 da
ρ dT model for describing the state of natural gas in engineering
k ∂T { ρ ,PR
ρR
= − practice. It is a multiparameter equation of state, which is
1 − ρb 1 + ρb (10) commonly written as

i E y
jij ∂p zyz p = ρRT + jjjB0 RT − A 0 − 02 + 30 − 04 zzzρ2
jj zz
k T {
C D

k {T ,PR
RT ρ(2 + ρb)a
= −
ij d yz 3 ij d yz 6
2
(1 + ρb)2 T T

+ jjbRT − a − zzρ + αjja + zzρ

∂ρ (1 − ρb) (11)
daj
k T{ k T{
where
da
dT
C C
= 0.5 ∑i = 1 ∑ j = 1 xixj ( dai −0.5 0.5
a aj
dT i
+ ai0.5aj−0.5 dT .) cρ 3 2

(1 − kij) + 2 (1 + γρ2 )e(−γρ )

T (16)
Substituting eqs 10 and 11 into eq 5 yields the J−T
coefficient μSRK of the natural gas−hydrogen mixture by SRK- where p is the system pressure, kPa; T is the system
EOS. temperature, K; ρ is the molar density of natural gas, kmol/
2.4. Joule−Thomson Coefficient by PR-EOS. Similar to m3; R is the universal gas constant, R = 8.3145 kJ/(kmol·K);
SRK-EOS, PR-EOS is a kind of cubic equation of state and A0, B0, C0, D0, E0, a, b, c, d, α, and γ are coefficients of
developed in 1976 at the University of Alberta by Peng and BWRS-EOS, which can be calculated based on the critical
Robinson.28 It is commonly used to describe the state of temperature, critical density, and the acentric factor for a pure
natural gas and can be written as follows component i
RT a ρci A 0i
p= − ρci B0i = A1 + B1ωi , = A 2 + B2 ωi ,
υ−b υ(υ + b) + b(υ − b) (12) RTci
ρci C0i
where p is the system pressure, kPa; T is the system = A3 + B3ωi , ρci2 γi = A4 + B4 ωi ,
temperature, K; υ is the molar volume, m3/kmol; the attraction RTci3
p a r a m e t e r a = a(Tc)[1 + κ(1 − Tr )]2 , w h e r e ρci2 ai
ρci2 bi = A5 + B5ωi , = A 6 + B6 ωi ,
0.45724R2Tc2 0.0778RTc RTci
a(Tc) = ; b = b(Tc) = ; Tc and pc are the
pc pc ρci2 ci
critical temperature and critical pressure, respectively; κ = ρci3 αi = A 7 + B7 ωi , = A8 + B8ωi ,
RTci3
0.37464 + 1.54226ω − 0.26992ω2, where ω is the acentric
ρci D0i ρci2 di
3 log10(pc / patm ) = A 9 + B9ωi , = A10 + B10 ωi ,
factor defined as ω = 7 [ ] − 1; Tb is the boiling
Tc / Tb − 1 RTci4 RTci2
temperature; and patm denotes the atmospheric pressure. ρci E0i
For the natural gas−hydrogen mixture, the mixing rules of = A11 + B11ωi exp( −3.8ωi)
RTci5 (17)
PR-EOS for calculating parameters a and b are the same as
those of SRK-EOS. However, it should be noted that the where Ai and Bi are the universal gas constants of component i;
binary interaction coefficient kij for PR-EOS is different from ρci is the critical density of component i; and ωi is the acentric
that of SRK-EOS.7,27 For the convenience of calculation, the factor of component i. The value of the above parameters for
molar volume can be expressed by molar density, and eq 12 different components can be obtained in refs 7, 27.
can be reformulated as For the natural gas−hydrogen mixture, the above 11
ρRT ρ2 a coefficients of BWRS-EOS are obtained by mixing the
p= − corresponding coefficients of included components. The
1 − ρb 1 + 2ρb − ρ2 b2 (13) mixing rules are defined by
16725 https://doi.org/10.1021/acsomega.1c00248
ACS Omega 2021, 6, 16722−16735
ACS Omega http://pubs.acs.org/journal/acsodf Article

C C C
the J−T coefficient is validated and analyzed. First, J−T
A0 = ∑ ∑ yyi j A 01/2 1/2
i A 0j (1 − k ij), B0 = ∑ yB
i 0i
, coefficients of three different samples experimentally measured
i=1 j=1 i=1 by Ernst et al.16 are used to validate the calculation results of
C C
empirical formula, SRK-EOS, PR-EOS, and BWRS-EOS. Table
C0 = ∑ ∑ yyi j C01/2 1/2 3
i C 0j (1 − k ij) , 1 presents the experimental conditions, compositions of
i=1 j=1
C C
D0 = ∑ ∑ yyi j D01/2 1/2 4 Table 1. Compositions of Investigated Samples16
i D0j (1 − k ij) ,
i=1 j=1 sample substance purity mole fraction
C C
CH4 CH4 0.999995 1
E0 = ∑ ∑ yyi j E01/2 1/2 5
i E0j (1 − k ij) , ±

ij C y i C y
CH4 + C2H6 CH4 0.999995 0.84874 0.0001

1/3z zz , b = jjj ∑ yb1/3zzz ,

a = jjjj ∑ ya
i=1 j=1
C2H6 0.9995 0.15126 ± 0.001

z
zz j
jj zz
3 3

j i=1 i z
natural gas CH4 0.99995 0.79942 ± 0.00004

k { k i=1 {
i i C2H6 0.9995 0.05029 ± 0.00001

ij C yz ij C yz
i

j z j z
±

c = jjj ∑ yc zz , d = jj ∑ ydi zz ,
C3H8 0.9995 0.03000 0.00001

j i = 1 i i zz jj zz
3 3
CO2 0.999993 0.02090 ± 0.00001

k { k i=1 {
1/3 1/3
N2 0.999999 0.09939 ± 0.00001

ij C yz ij C yz
i

j z
α = jjj ∑ yi αi zzz , γ = jjj ∑ yi γi zzz j z
3 2

j i=1 z j i=1
k { k {
1/3 1/2
where C, yi, and kij have similar meanings as in SRK-EOS and
PR-EOS.
Different from SRK-EOS and PR-EOS, the coefficients of
BWRS-EOS depend only on the critical parameters and
acentric factors, and they have nothing to do with the system
temperature and density. Therefore, the partial derivative of
BWRS-EOS (eq 16) for natural gas to temperature T and
density ρ is the same as that for the pure component. The only
distinction is that the coefficients of the partial derivative of
BWRS-EOS are obtained according to the mixing rules. The
partial derivative of BWRS-EOS for the natural gas−hydrogen
mixture to T and ρ can be, respectively, derived as
ij ∂p yz i 4E y
z
sample gases, purity, and mole fraction of each substance in
the experiments by Ernst et al.16 In this experiment, the J−T
(18) coefficients of pure methane, methane−ethane mixture, and
natural gas were measured at various pressures and temper-
atures. Due to the limitation of the measuring accuracy, the
uncertainty of the mole fraction of different substances is also
provided in Table 1.
3.2. Analysis of Validation Results. The J−T coefficients
of three investigated samples in Table 1 are calculated using
empirical formula (EF), SRK-EOS, PR-EOS, and BWRS-EOS
at different experimental temperatures and pressures. The
calculation results are compared with the experimental
measurement data (EX) from Ernst et al.,16 and the relative
error e between calculation results and the experimental data is
μcalculation − μEX

= ρR + jjjB0 R + 30 − 40 + 50 zzzρ2
also obtained (e is defined as × 100%), as shown
jj zz
μEX

k ∂T { ρ ,BWRS k T {
2C 3D
in Figures 1−3 and Tables 2−4.

i d y
T T In Figures 1−3, the different colors denote the different

+ jjjbR + 2 zzzρ3 − 2 ρ6
methods adopted to calculate the J−T coefficient, and the
k T {
αd
symbol height stands for the relative error. It can be clearly
T seen from Figures 1−3 that for all samples, i.e., pure CH4, CH4
3
2cρ 2 + C2H6, and natural gas, the height of BWRS-EOS is the
− 3
(1 + γρ2 )e(−γρ ) smallest in almost all of the conditions, indicating that the
T (19)

ij ∂p yz i E y
= RT + 2jjjB0 RT − A 0 − 02 + 30 − 04 zzzρ
relative error of BWRS-EOS is the smallest, and the J−T
jj zz
j ∂ρ z
coefficient calculated using BWRS-EOS agrees best with the
k T {
C D
k {T ,BWRS
experimental data under the same condition. From Tables
T T
i dy i dy
+ 3jjjbRT − a − zzzρ2 + 6αjjja + zzzρ5
2−4, it is seen that the average relative error eave of the J−T
coefficient between BWRS-EOS and the experimental data is
k T{ k T{
only 1.07, 1.05, and 1.15% for the three investigated samples,

3cρ2 i y
+ 2 jjj1 + γρ2 − γ 2ρ 4 zzze(−γρ )
respectively. It is inferred that BWRS-EOS is the most accurate

T k {
2 2
3 (20)
Based on the above analysis, substituting eqs 19 and 20 into
eq 5 yields the J−T coefficient μBWRS of the natural gas−
hydrogen mixture by BWRS-EOS.
3. VALIDATION
3.1. Experimental Conditions. In this study, the
empirical formula, SRK-EOS, PR-EOS, and BWRS-EOS are
applied to investigate the influences of hydrogen blending on
the J−T coefficient of the natural gas−hydrogen mixture.
However, due to the distinctions in model assumption and
basic theory, the J−T coefficients calculated by these methods
possess different accuracies. Here, the calculation accuracy of
16726
among these methods in predicting the J−T coefficient.
Figures 1−3 and Tables 2−4 also imply that the calculation
accuracy of PR-EOS is slightly lower than that of BWRS-EOS,
and the average relative error for the three investigated samples
is 5.89, 4.0, and 5.09%, respectively. Compared with BWRS-
EOS and PR-EOS, SRK-EOS and empirical formula have
relatively low calculation accuracies; especially, the average
relative error of the empirical formula for the three investigated
samples is around 10% on the whole. Furthermore, as the
carbon number of the sample increases, the calculation
accuracy of the empirical formula decreases obviously.
As with the influences of temperature and pressure on the
calculation accuracy, Tables 2−4 demonstrate that for SRK-
EOS and PR-EOS, under the same pressure, a higher
temperature provides a larger relative error of the J−T
https://doi.org/10.1021/acsomega.1c00248
ACS Omega 2021, 6, 16722−16735
ACS Omega http://pubs.acs.org/journal/acsodf Article

Figure 1. Relative error of the J−T coefficient of CH4 using the empirical formula, SRK-EOS, PR-EOS, and BWRS-EOS compared with the
experimental data.16

Figure 2. Relative error of the J−T coefficient of the CH4−C2H6 mixture using the empirical formula, SRK-EOS, R-EOS, and BWRS-EOS
compared with the experimental data.16

Figure 3. Relative error of the J−T coefficient of the natural gas mixture using the empirical formula, SRK-EOS, PR-EOS, and BWRS-EOS
compared with the experimental data.16

coefficient, while at the same temperature, the relative error of
the J−T coefficient is much larger at low pressure than that at
high pressure. This indicates that SRK-EOS and PR-EOS can
provide a much better prediction of the J−T coefficient at high
16727
pressure and low temperature. By contrast, the calculated J−T
coefficient is more accurate at low-pressure and high-
temperature conditions for BWRS-EOS and the empirical
formula. Thus, BWRS-EOS and the empirical formula are
https://doi.org/10.1021/acsomega.1c00248
ACS Omega 2021, 6, 16722−16735
ACS Omega http://pubs.acs.org/journal/acsodf Article

Table 2. Comparison of J−T Coefficients of CH4

experiment empirical formula SRK-EOS PR-EOS BWRS-EOS
p (MPa) T (K) μEX (K/MPa) μEF (K/MPa) eEF (%) μSRK (K/MPa) eSRK (%) μPR (K/MPa) ePR (%) μBWRS (K/MPa) eBWRS (%)
1.0 250 6.139 6.621 7.85 7.205 17.36 6.819 11.08 6.276 2.23
275 5.155 5.443 5.59 6.067 17.69 5.744 11.43 5.150 0.10
300 4.354 4.518 3.77 5.147 18.21 4.874 11.94 4.285 1.58
350 3.085 3.200 3.73 3.763 21.98 3.565 15.56 3.058 0.88
3.0 250 6.013 5.777 3.92 6.796 13.02 6.580 9.43 6.193 2.99
275 5.012 4.896 2.31 5.657 12.87 5.474 9.22 5.048 0.72
300 4.193 4.131 1.48 4.765 13.64 4.613 10.02 4.178 0.36
350 2.958 2.962 0.14 3.455 16.80 3.351 13.29 2.954 0.14
5.0 250 5.710 4.898 14.22 6.204 8.65 6.138 7.50 5.942 4.06
275 4.781 4.349 9.04 5.168 8.09 5.098 6.63 4.840 1.23
300 3.994 3.752 6.06 4.351 8.94 4.293 7.49 4.000 0.15
350 2.811 2.733 2.77 3.153 12.17 3.119 10.96 2.817 0.21
10.0 250 4.048 3.097 23.49 3.959 2.20 4.051 0.07 4.066 0.44
275 3.713 3.192 14.03 3.686 0.73 3.748 0.94 3.736 0.62
300 3.244 2.920 9.99 3.249 0.15 3.306 1.91 3.236 0.25
350 2.353 2.214 5.91 2.443 3.82 2.504 6.42 2.384 1.32
15.0 250 2.043 ± 0.01 2.649 29.03 2.036 0.00 2.095 2.05 2.083 1.46
275 2.389 2.553 6.86 2.299 3.77 2.361 1.17 2.360 1.21
300 2.327 2.358 1.33 2.239 3.78 2.307 0.86 2.285 1.80
350 1.854 1.789 3.51 1.833 1.13 1.915 3.29 1.822 1.73
17.5 275 1.82 ± 0.03 2.397 29.57 1.788 0.61 1.837 0.00 1.846 0.00
300 1.91 ± 0.03 2.166 11.65 1.828 2.77 1.889 0.00 1.874 0.32
20.0 300 1.544 ± 0.023 2.011 28.33 1.489 2.10 1.538 0.00 1.536 0.00
350 1.398 ± 0.021 1.445 1.83 1.346 2.25 1.418 0.00 1.350 1.96
eave 9.43 8.03 5.89 1.07

Table 3. Comparison of J−T Coefficients of the CH4 + C2H6 Mixture

experiment empirical formula SRK-EOS PR-EOS BWRS-EOS
p (MPa) T (K) μEX (K/MPa) μEF (K/MPa) eEF (%) μSRK (K/MPa) eSRK (%) μPR (K/MPa) ePR (%) μBWRS (K/MPa) eBWRS (%)
1.0 250 7.66 7.912 3.29 8.602 12.27 8.040 4.96 7.835 2.28
275 6.251 6.492 3.86 7.178 14.86 6.720 7.50 6.323 1.15
300 5.164 5.369 3.97 6.061 17.35 5.669 9.78 5.189 0.48
350 3.662 3.768 2.89 4.399 20.15 4.114 12.34 3.625 1.01
3.0 250 7.651 6.599 13.75 8.313 8.61 7.943 3.82 7.794 1.87
275 6.176 5.702 7.67 6.812 10.43 6.509 5.39 6.242 1.07
300 5.028 4.848 3.58 5.691 13.17 5.429 7.98 5.094 1.31
350 3.507 3.484 0.66 4.082 16.34 3.894 11.04 3.527 0.57
5.0 250 7.338 5.137 29.99 7.644 4.12 7.492 2.10 7.480 1.94
275 5.924 4.885 17.54 6.278 6.01 6.113 3.19 6.000 1.28
300 4.806 4.327 9.97 5.234 8.82 5.084 5.78 4.895 1.85
350 3.354 3.208 4.35 3.742 11.51 3.639 8.50 3.381 0.81
10.0 250 3.992 ± 0.02 2.715 31.65 3.740 5.79 3.944 0.70 3.750 5.59
275 4.280 3.197 25.30 4.145 3.04 4.202 1.82 4.210 1.64
300 3.789 3.200 15.54 3.804 0.29 3.809 0.53 3.816 0.71
350 2.804 2.590 7.63 2.879 3.07 2.899 3.39 2.814 0.36
12.5 250 2.34 ± 0.012 2.770 17.77 2.423 2.89 2.456 4.42 2.346 0.00
275 3.103 ± 0.016 2.846 7.81 3.041 1.52 3.118 0.00 3.074 0.42
300 3.113 ± 0.016 2.833 8.52 3.045 1.52 3.092 0.16 3.092 0.16
350 2.481 2.335 5.88 2.478 0.00 2.517 1.45 2.464 0.69
15.0 275 2.198 ± 0.015 2.714 22.64 2.202 0.00 2.270 2.58 2.225 0.54
300 2.445 ± 0.012 2.595 5.62 2.389 1.77 2.447 0.00 2.434 0.00
350 2.123 2.117 0.28 2.113 0.61 2.154 1.46 2.113 0.47
20.0 300 1.52 ± 0.04 2.325 49.04 1.463 1.35 1.505 0.00 1.522 0.00
350 1.48 ± 0.04 1.771 16.51 1.491 0.00 1.536 1.05 1.506 0.00
eave 12.63 6.62 4.00 1.05

favorable for predicting the J−T coefficient at low-pressure and

high-temperature conditions. But, overall, BWRS-EOS still
16728 https://doi.org/10.1021/acsomega.1c00248
ACS Omega 2021, 6, 16722−16735
ACS Omega http://pubs.acs.org/journal/acsodf Article

Table 4. Comparison of J−T Coefficients of Natural Gas

experiment empirical formula SRK-EOS PR-EOS BWRS-EOS
p (MPa) T (K) μEX (K/MPa) μEF (K/MPa) eEF (%) μSRK (K/MPa) eSRK (%) μPR (K/MPa) ePR (%) μBWRS (K/MPa) eBWRS (%)
1.0 250 6.922 7.704 11.30 7.767 12.25 7.372 6.50 7.017 1.37
275 5.671 6.328 11.59 6.524 14.97 6.174 8.87 5.688 0.30
300 4.743 5.245 10.58 5.512 16.17 5.216 9.97 4.685 1.22
350 3.333 3.703 11.10 4.013 20.31 3.791 13.74 3.293 1.20
3.0 250 6.841 6.564 4.05 7.356 7.59 7.146 4.46 6.883 0.61
275 5.511 5.610 1.80 6.078 10.32 5.898 7.02 5.553 0.76
300 4.585 4.750 3.60 5.102 11.23 4.941 7.76 4.555 0.65
350 3.205 3.411 6.43 3.656 14.20 3.562 11.14 3.178 0.84
5.0 250 6.431 5.381 16.33 6.691 4.03 6.653 3.45 6.524 1.45
275 5.241 4.898 6.54 5.533 5.51 5.484 4.64 5.284 0.82
300 4.339 4.269 1.61 4.633 6.71 4.591 5.81 4.340 0.02
350 3.032 3.130 3.23 3.321 9.50 3.310 9.17 3.024 0.26
10.0 250 4.082 3.238 20.68 3.903 4.46 4.050 0.78 3.948 3.28
275 3.851 3.443 10.59 3.769 1.58 3.898 1.22 3.862 0.29
300 3.436 3.244 5.59 3.367 1.92 3.468 0.93 3.406 0.87
350 2.504 2.504 0.00 2.533 1.04 2.629 4.99 2.495 0.36
15.0 250 1.774 ± 0.012 2.980 66.85 1.813 1.34 1.916 7.28 1.864 4.37
275 2.283 ± 0.011 2.817 22.80 2.214 2.73 2.318 1.05 2.270 0.09
300 2.358 ± 0.012 2.612 10.21 2.235 4.94 2.337 0.38 2.293 2.26
350 1.926 ± 0.010 2.007 3.67 1.846 2.92 1.978 2.17 1.892 1.25
20.0 300 1.520 ± 0.015 2.249 46.51 1.423 5.65 1.509 0.00 1.492 0.86
350 1.417 ± 0.014 1.614 12.79 1.334 5.69 1.439 0.56 1.372 2.21
eave 13.08 7.50 5.09 1.15

Table 5. Comparison of the J−T Coefficients of the CH4 + H2 Mixture

experiment empirical formula SRK-EOS PR-EOS
p (atm) T (K) μEX (K/atm) μEF (K/atm) eEF (%) μSRK (K/atm) eSRK (%) μPR (K/atm) ePR (%)
68.03 199.54 0.2617 0.1979 24.38 0.2367 9.57 0.2551 2.52
61.57 198.68 0.2715 0.2100 22.65 0.2491 8.26 0.2678 1.36
57.47 196.09 0.2807 0.2330 16.99 0.2606 7.17 0.2802 0.18
50.15 194.96 0.3023 0.2379 21.30 0.2699 10.7 0.2955 2.25
43.89 192.59 0.3264 0.2553 21.78 0.2815 13.7 0.3119 4.44
38.82 191.21 0.3496 0.2690 23.05 0.3122 10.7 0.3241 7.29
71.43 181.63 0.2846 0.2283 19.78 0.2633 7.49 0.2827 0.67
63.27 178.71 0.3094 0.2491 19.49 0.2887 6.69 0.3076 0.58
55.45 176.62 0.3383 0.2694 20.37 0.2978 11.9 0.3309 2.19
47.62 173.86 0.3723 0.2934 21.19 0.3423 8.07 0.3566 4.22
40.15 170.96 0.4095 0.3200 21.86 0.3723 9.09 0.3823 6.64
51.02 204.00 0.2735 0.2169 20.69 0.2584 5.53 0.2743 0.29
43.21 202.00 0.3001 0.2349 21.73 0.2706 9.83 0.2908 3.10
35.38 199.12 0.3268 0.2564 21.54 0.2891 11.5 0.3096 5.26
30.28 197.61 0.3442 0.2703 21.47 0.3006 −12.6 0.3211 6.71
24.15 195.72 0.3652 0.2883 21.06 0.3150 13.7 0.3350 8.27
18.37 193.17 0.3850 0.3326 13.61 0.3309 14.0 0.3501 9.06
eave 20.76 10.03 3.79

delivers results of better accuracy compared to the other two
EOSs and the empirical formula at the same given pressure and
temperature.
Based on the above comparison, it can be concluded that
BWRS-EOS is most accurate in predicting the J−T coefficient
within a wide range of thermodynamic conditions (a
temperature range of 250−350 K and a pressure range of 1−
30 MPa), while PR-EOS, SRK-EOS, and the empirical formula
can only deliver good results in a limited range of temperature
and pressure. Overall, the calculation accuracy of PR-EOS is
still acceptable in most practical engineering problems.
Although the performance of the empirical formula is not so
16729
good, it is much simpler for engineering applications and can
save appreciable computation resources. To ensure the
completeness of our investigation and reveal the influences
of hydrogen blending on the J−T coefficient of the natural gas
mixture by different EOSs, all of the above four methods are
adopted in the following study.
3.3. Further Validation by the Methane−Hydrogen
Mixture at Low Temperature. In Section 3.2, the
calculation accuracy of the empirical formula, SRK-EOS, PR-
EOS, and BWRS-EOS is validated by the experimentally
measured J−T coefficients of three different samples in the
work of Ernst et al.16 It should be noted that in the above
https://doi.org/10.1021/acsomega.1c00248
ACS Omega 2021, 6, 16722−16735
ACS Omega http://pubs.acs.org/journal/acsodf Article

Table 6. Composition of the Investigated Natural Gas

substance CH4 C2H6 C3H8 i-C4 n-C4 i-C5 n-C5 n-C6 n-C7 n-C8 N2 CO2
mole fraction (%) 92.45 3.64 1.37 0.16 0.13 0.20 0.05 0.05 0.09 0.02 1.30 0.54

comparisons, there is no hydrogen in the three samples. To natural gas pipelines will not be influenced appreciably as
further verify the applied methods for a hydrogen-enriched well.32,33 Therefore, the upper limit of the hydrogen blending
system, the experimental data of the J−T coefficient of the ratio is set as 30% in this study.
CH4 + H2 mixture from Randelman and Wenzel30 are used for 4.1.1. Analysis of the Calculated Joule−Thomson
comparison with our numerical results. In the experiment of ref Coefficient. Figures 4−7 display the variation of the J−T
30, the purity of hydrogen is 99.97%, with the impurity being
predominantly nitrogen. The mole fraction of hydrogen and
methane in the mixture is 56.57 and 43.43%, respectively.
Interested readers can refer to ref 30 for more experimental
details. However, it is worth mentioning that the experimental
temperature in ref 30 is very low (around 200 K), and BWRS-
EOS is inapplicable at this condition. Thus, in Table 5, only
the calculated J−T coefficients of the CH4 + H2 mixture by the
empirical formula, SRK-EOS, and PR-EOS are compared with
the experimentally measured J−T coefficients in ref 30.
It can be clearly seen from Table 5 that at the same
experimental pressure and temperature, PR-EOS can give a
much better prediction of the J−T coefficient than the
empirical formula and SRK-EOS. The average relative error of
PR-EOS is only −3.79%, which is much smaller than −10.03%
of SRK-EOS and −20.76% of the empirical formula.
Compared with Tables 2−4, it can also be found in Table 5
that the relative errors of the empirical formula, SRK-EOS, and Figure 4. J−T coefficient of the natural gas−hydrogen mixture at
PR-EOS are all larger than those at a relatively high- different hydrogen blending ratios and thermodynamic conditions
temperature range of 250−350 K. Thus, the thermodynamic calculated using the empirical formula.
condition has a significant influence on the calculation
accuracy of the applied EOSs and the empirical formula.
Overall, the comparisons of the experimental measurement
data with the calculated results as shown in Tables 2−5
indicate that PR-EOS and BWRS-EOS are capable of
accurately predicting the J−T coefficient, and BWRS-EOS
can perform much better if the temperature is not very low
(≥250 K in this study).

4. RESULTS AND DISCUSSION

In this section, the effects of hydrogen blending on the Joule−
Thomson coefficient of the natural gas−hydrogen mixture are
discussed in detail.
4.1. Natural Gas−Hydrogen Mixture. Table 6 depicts
the components of the natural gas for the study below.7 The
J−T coefficients of the natural gas at six different
thermodynamic conditions and six different hydrogen blending
ratios are calculated and analyzed. According to the trans-
portation condition using natural gas pipelines or pipe
networks, the six thermodynamic conditions are, respectively,
set as (1) p = 0.1 MPa and T = 283.15 K; (2) p = 1.0 MPa and
T = 283.15 K; (3) p = 1.0 MPa and T = 293.15 K; (4) p = 5.0
MPa and T = 293.15 K; (5) p = 5.0 MPa and T = 308.15 K;
and (6) p = 10.0 MPa and T = 323.15 K. The six hydrogen
blending ratios (mole fraction) are, respectively, set as 5, 10,
15, 20, 25, and 30%.
It should be mentioned that the reason why the maximum
hydrogen blending ratio is set as 30% is that the present
reports in the literature show that when the hydrogen blending
ratio is not higher than 30%, the mixed hydrogen does not
significantly affect the combustion characteristics of natural
gas, and there is no need to reform the domestic gas appliances
of end users.31 The hydraulic and thermal characteristics of
16730
Figure 5. J−T coefficient of the natural gas−hydrogen mixture at
different hydrogen blending ratios and thermodynamic conditions
calculated using SRK-EOS.
coefficient of the natural gas−hydrogen mixture at different
hydrogen blending ratios and thermodynamic conditions by
the empirical formula, SRK-EOS, PR-EOS, and BWRS-EOS,
respectively. It can be obviously seen that under the same
thermodynamic conditions, the J−T coefficient of the natural
gas−hydrogen mixture approximately linearly decreases with
the increase of the hydrogen blending ratio. For instance,
Figures 4−7 show that the slope of the μJT−H2% curve (the J−
T coefficient versus the hydrogen blending ratio) obtained by
the empirical formula, SRK-EOS, PR-EOS, and BWRS-EOS is,
respectively, −0.066, −0.085, −0.073, and −0.077 (K/MPa)/
https://doi.org/10.1021/acsomega.1c00248
ACS Omega 2021, 6, 16722−16735
ACS Omega http://pubs.acs.org/journal/acsodf Article

by PR-EOS at 0.1 MPa/283.15 K and 1.0 MPa/283.15 K is

Figure 6. J−T coefficient of the natural gas−hydrogen mixture at
different hydrogen blending ratios and thermodynamic conditions
calculated using PR-EOS.
Figure 7. J−T coefficient of the natural gas−hydrogen mixture at
different hydrogen blending ratios and thermodynamic conditions
calculated using BWRS-EOS.
% at 0.1 MPa and 283.15 K. Moreover, for the same EOS at
the thermodynamic conditions of 0.1−5.0 MPa and 283.15−
308.15 K, the decrease range of the J−T coefficient against the
increase of the hydrogen blending ratio is approximately the
same. That is, the slope of the J−T coefficient curve changing
with the hydrogen blending ratio is nearly the same, and the
curves under different thermodynamic conditions (except for
10 MPa and 323.15 K) are approximately parallel to each
other. For example, the slope of the μJT−H2% curve obtained
−0.073 and −0.074 (K/MPa)/%, respectively. It indicates that
the impact of the hydrogen blending ratio on the J−T
coefficient is almost the same under different thermodynamic
conditions, except for the high-pressure and -temperature
conditions, such as 10 MPa and 323.15 K.
In addition, Figures 4−7 also demonstrate that at the same
temperature and hydrogen blending ratio, the J−T coefficient
of the natural gas−hydrogen mixture decreases with increasing
pressure, such as the two curves corresponding to 1.0 and 5.0
MPa at 293.15 K. Similarly, at the same pressure and hydrogen
blending ratio, the J−T coefficient of the natural gas−hydrogen
mixture decreases with the increase of temperature, such as the
two curves corresponding to 293.15 and 308.15 K at 5.0 MPa.
Thus, either higher pressure or temperature leads to a smaller
J−T coefficient of the natural gas−hydrogen mixture. The
hydrogen-mixed natural gas and natural gas without hydrogen
(the hydrogen blending ratio is 0% in Figures 4−7) show the
same variation trend, implying that hydrogen blending does
not affect the variation trend of the J−T coefficient with
pressure and temperature. The underlying reason for this
phenomenon can be attributed to the influences of temper-
ature and pressure on the physical and thermal properties of
the natural gas−hydrogen mixture, such as the density and the
specific heat capacity.
To sum up, hydrogen blending has great influences on the
J−T coefficient of the natural gas−hydrogen mixture. With the
increase of the hydrogen blending ratio, the J−T coefficient of
the natural gas−hydrogen mixture decreases approximately
linearly. In addition, the decreasing trend of the J−T
coefficient with the increasing hydrogen blending ratio is
similar under different thermodynamic conditions. In engineer-
ing practice, the effect of hydrogen blending on the J−T
coefficient is actually a double-edged sword. For example, in
pipeline transportation of the natural gas−hydrogen mixture,
the influence of hydrogen blending on the J−T coefficient is
favorable. Due to this, the J−T coefficient of the natural gas−
hydrogen mixture becomes smaller than that of natural gas, the
cooling effect is weakened, and thus the risk of gas hydrate
blockage at the pipeline valve can be reduced. However, in the
liquefaction of hydrogen-enriched natural gas, it is disadvanta-
geous that the J−T cooling of the natural gas−hydrogen
mixture is weakened compared with that without hydrogen.
Under the same pressure drop, the temperature drop of the
natural gas−hydrogen mixture produced by the J−T cooling is
lower than that of natural gas without hydrogen. To obtain the
same cooling effect, it is necessary to increase the pressure
drop, which consumes much more energy. For the
convenience of quantitative comparison, Tables 7−10 present
detailed data of the J−T coefficient of the natural gas−
hydrogen mixture calculated using the empirical formula, SRK-

Table 7. J−T Coefficient of the Natural Gas−Hydrogen Mixture Using the Empirical Formula; Unit, K/MPa

p/T 0% 5% 10% 15% 20% 25% 30%

0.1 MPa/283.15 K 5.85 5.60 5.17 4.84 4.51 4.18 3.87
1.0 MPa/283.15 K 5.59 5.34 4.94 4.62 4.30 3.98 3.66
1.0 MPa/293.15 K 5.18 4.95 4.59 4.29 3.99 3.69 3.40
5.0 MPa/293.15 K 4.19 4.01 3.74 3.48 3.21 2.93 2.63
5.0 MPa/308.15 K 3.84 3.66 3.39 3.15 2.89 2.63 2.34
10 MPa/323.15 K 2.77 2.63 2.40 2.18 1.94 1.66 1.36

16731 https://doi.org/10.1021/acsomega.1c00248
ACS Omega 2021, 6, 16722−16735
ACS Omega http://pubs.acs.org/journal/acsodf Article

Table 8. J−T Coefficient of the Natural Gas−Hydrogen Mixture Using SRK-EOS; Unit, K/MPa
p/T 0% 5% 10% 15% 20% 25% 30%
0.1 MPa/283.15 K 6.43 5.99 5.56 5.13 4.71 4.29 3.87
1.0 MPa/283.15 K 6.28 5.84 5.41 4.99 4.57 4.16 3.76
1.0 MPa/293.15 K 5.87 5.46 5.06 4.67 4.28 3.89 3.51
5.0 MPa/293.15 K 5.01 4.67 4.33 3.99 3.67 3.35 3.03
5.0 MPa/308.15 K 4.52 4.21 3.91 3.61 3.32 3.03 2.74
10 MPa/323.15 K 3.09 2.93 2.76 2.58 2.40 2.22 2.03

Table 9. J−T Coefficient of the Natural Gas−Hydrogen Mixture Using PR-EOS; Unit, K/MPa
p/T 0% 5% 10% 15% 20% 25% 30%
0.1 MPa/283.15 K 5.99 5.60 5.22 4.85 4.48 4.13 3.79
1.0 MPa/283.15 K 5.91 5.51 5.13 4.75 4.39 4.03 3.69
1.0 MPa/293.15 K 5.53 5.16 4.80 4.45 4.11 3.78 3.46
5.0 MPa/293.15 K 4.92 4.56 4.22 3.89 3.58 3.28 2.98
5.0 MPa/308.15 K 4.43 4.12 3.82 3.53 3.25 2.97 2.71
10 MPa/323.15 K 3.13 2.93 2.73 2.53 2.34 2.15 1.96

Table 10. J−T Coefficient of the Natural Gas−Hydrogen Mixture Using BWRS-EOS; Unit, K/MPa
p/T 0% 5% 10% 15% 20% 25% 30%
0.1 MPa/283.15 K 5.41 5.01 4.62 4.23 3.85 3.47 3.10
1.0 MPa/283.15 K 5.38 4.97 4.57 4.18 3.79 3.41 3.04
1.0 MPa/293.15 K 4.98 4.60 4.23 3.86 3.50 3.15 2.80
5.0 MPa/293.15 K 4.66 4.27 3.89 3.53 3.19 2.86 2.54
5.0 MPa/308.15 K 4.16 3.81 3.48 3.16 2.85 2.55 2.26
10 MPa/323.15 K 3.03 2.82 2.61 2.39 2.17 1.96 1.74

EOS, PR-EOS, and BWRS-EOS at six thermodynamic

conditions and six hydrogen blending ratios for reference.
4.1.2. Relative Deviation of the Calculated Joule−
Thomson Coefficient. To quantitatively reveal the influences
of hydrogen blending on the J−T effect of natural gas, the
relative deviation between the J−T coefficient of hydrogen-
enriched natural gas and that of natural gas without hydrogen
is displayed and analyzed in this section. Figures 8−11 show
the relative deviation of the J−T coefficient at six
thermodynamic conditions and six hydrogen blending ratios
calculated using the empirical formula (eEF), SRK-EOS (eSRK),
PR-EOS (ePR), and BWRS-EOS (eBWRS), respectively.

Figure 9. Relative deviation of the J−T coefficient between the

hydrogen-enriched natural gas and natural gas without hydrogen
under different conditions using SRK-EOS.

It can be clearly observed from Figures 8−11 that with the

Figure 8. Relative deviation of the J−T coefficient between the
hydrogen-blended natural gas and natural gas without hydrogen under
different conditions using the empirical formula.
16732
increase of the hydrogen blending ratio, the relative deviation
of the J−T coefficient between the natural gas−hydrogen
mixture and natural gas without hydrogen increases gradually.
When the hydrogen blending ratio is up to 30%, the relative
deviations of the J−T coefficient calculated using the empirical
formula, SRK-EOS, PR-EOS, and BWRS-EOS are as high as
50.9, 40.2, 39.4, and 45.7%, respectively, compared with those
of natural gas without hydrogen. This indicates that the
hydrogen blending ratio has important impacts on the J−T
effect of natural gas. That is to say, when the hydrogen
blending ratio reaches 30%, the temperature drop caused by
https://doi.org/10.1021/acsomega.1c00248
ACS Omega 2021, 6, 16722−16735
ACS Omega http://pubs.acs.org/journal/acsodf Article

reference and benchmark. Since the prediction result of

BWRS-EOS is most accurate, only the J−T coefficient
calculated using BWRS-EOS is presented here. Table 11

Table 11. J−T Coefficient of the Methane−Hydrogen

Mixture at 275 K; Unit, K/MPa
p (MPa) 5% 10% 15% 20% 25% 30%
0.5 4.76 4.38 4.00 3.64 3.28 2.95
1.0 4.74 4.35 3.97 3.60 3.25 2.91
2.0 4.69 4.28 3.89 3.52 3.16 2.82
3.0 4.61 4.20 3.80 3.42 3.06 2.72
5.0 4.39 3.96 3.57 3.19 2.84 2.50
7.5 3.96 3.56 3.19 2.84 2.51 2.20
10.0 3.39 3.06 2.75 2.45 2.16 1.89
12.5 2.78 2.54 2.30 2.06 1.82 1.59
15.0 2.23 2.07 1.89 1.71 1.52 1.33
17.5 1.78 1.68 1.55 1.41 1.25 1.10
Figure 10. Relative deviation of the J−T coefficient between the 20.0 1.43 1.36 1.27 1.16 1.03 0.91
hydrogen-enriched natural gas and natural gas without hydrogen
under different conditions using PR-EOS. shows the J−T coefficient of the methane−hydrogen mixture
at the hydrogen blending ratios (mole fraction) of 5, 10, 15,
20, 25, and 30%; pressure of 0.5−20 MPa; and a temperature
of 275 K. Similarly, the J−T coefficients of the methane−
hydrogen mixture at the same hydrogen blending ratios and
pressure and temperatures of 300 and 350 K are presented in
Tables 12 and 13, respectively.

Table 12. J−T Coefficient of the Methane−Hydrogen

Mixture at 300 K; Unit, K/MPa
p (MPa) 5% 10% 15% 20% 25% 30%
0.5 3.97 3.64 3.33 3.02 2.73 2.44
1.0 3.95 3.62 3.30 2.99 2.69 2.40
2.0 3.89 3.55 3.23 2.91 2.61 2.33
3.0 3.82 3.48 3.15 2.83 2.53 2.24
5.0 3.63 3.28 2.95 2.64 2.34 2.06
7.5 3.31 2.98 2.66 2.37 2.09 1.82
10.0 2.92 2.62 2.34 2.07 1.82 1.58
12.5 2.50 2.25 2.01 1.78 1.56 1.34
Figure 11. Relative deviation of the J−T coefficient between the 15.0 2.09 1.90 1.70 1.51 1.32 1.13
hydrogen-enriched natural gas and natural gas without hydrogen 17.5 1.74 1.59 1.43 1.27 1.11 0.95
under different conditions using BWRS-EOS.
20.0 1.44 1.32 1.19 1.06 0.93 0.80

the J−T effect is decreased by 40−50% under the same

pressure drop. This phenomenon exerts negative effects on the
process of liquefaction of natural gas; the same pressure drop
of the hydrogen-blended natural gas can only yield a 50−60%
cooling effect compared with that of natural gas without
hydrogen. It is suggested that if the end user of the hydrogen- Table 13. J−T Coefficient of the Methane−Hydrogen
enriched natural gas is a natural gas liquefaction plant, the Mixture at 350 K; Unit, K/MPa
throttling process that induces the cooling effect should be
p (MPa) 5% 10% 15% 20% 25% 30%
improved accordingly. For pipeline transportation of the
natural gas−hydrogen mixture, it is also essential to carefully 0.5 2.84 2.60 2.37 2.14 1.92 1.71
consider the impact of hydrogen blending on downstream end 1.0 2.81 2.57 2.34 2.11 1.89 1.68
users. 2.0 2.76 2.52 2.28 2.05 1.83 1.62
4.2. Methane−Hydrogen Mixture. It is worth pointing 3.0 2.70 2.45 2.22 1.99 1.77 1.55
out that due to the difference in the composition of natural gas 5.0 2.56 2.31 2.07 1.85 1.63 1.42
produced from different natural gas fields, the J−T coefficient 7.5 2.35 2.11 1.88 1.66 1.50 1.25
of different natural gas components at different hydrogen 10.0 2.11 1.89 1.67 1.46 1.27 1.08
blending ratios varies substantially, which is inconvenient for 12.5 1.87 1.66 1.47 1.28 1.10 0.93
readers to compare and benchmark. Therefore, the J−T 15.0 1.63 1.45 1.27 1.10 0.94 0.78
coefficient of the methane−hydrogen mixture at different 17.5 1.41 1.25 1.09 0.95 0.80 0.66
hydrogen blending ratios is presented in this study for readers’ 20.0 1.21 1.07 0.94 0.81 0.68 0.55

16733 https://doi.org/10.1021/acsomega.1c00248
ACS Omega 2021, 6, 16722−16735
ACS Omega
http://pubs.acs.org/journal/acsodf
5. CONCLUSIONS
Hydrogen blending has significant influences on the J−T effect
of natural gas. In this study, the equation of state of real gas
and a widely used empirical formula are applied to numerically
investigate the effects of hydrogen blending on the J−T
coefficient of a natural gas−hydrogen mixture in detail. The
main work and findings of this study can be summarized as
follows.
(1) Theoretical formulas for calculating the J−T coefficient
of the natural gas−hydrogen mixture using the empirical
formula, SRK-EOS, PR-EOS, and BWRS-EOS are
mathematically derived. The experimental measurement
data of the J−T coefficient of CH4, CH4 + C2H6, natural
gas, and CH4 + H2 are used to validate the calculated J−
T coefficient using the empirical formula, SRK-EOS, PR-
EOS, and BWRS-EOS. Relative errors of the J−T
coefficient between the experimentally measured data
and these four methods indicate that both PR-EOS and
BWRS-EOS are accurate in predicting the J−T
coefficient, and BWRS-EOS can perform much better
if the temperature is not very low (≥250 K).
(2) The J−T coefficient of natural gas at six different
thermodynamic conditions and hydrogen blending ratios
is calculated using the empirical formula, SRK-EOS, PR-
EOS, and BWRS-EOS, respectively. Results indicate that
under different thermodynamic conditions and hydro-
gen mixing ratios, the J−T coefficient of the natural gas−
hydrogen mixture decreases approximately linearly with
the increasing hydrogen blending ratio. When the
hydrogen blending ratio reaches 30%, the J−T
coefficient of the natural gas−hydrogen mixture is 40−
50% lower than that of natural gas without hydrogen. In
addition, the influence of the hydrogen blending ratio on
the J−T coefficient is nearly the same under different
thermodynamic conditions.
(3) The database for the J−T coefficient of the methane−
hydrogen mixture at 275, 300, and 350 K is presented in
this work to provide a reference and a benchmark for
interested readers, where the pressure is set as 0.5−20
MPa and the hydrogen blending ratio of 5−30% is taken
into account.
This study also demonstrates that the impact of hydrogen
blending on the J−T coefficient of natural gas is a double-
edged sword. For long-distance pipeline transportation of the
natural gas−hydrogen mixture, hydrogen blending can reduce
the risk of gas hydrate blockage at the pipeline valves. For
natural gas liquefaction, however, the temperature drop of the
hydrogen-mixed natural gas is smaller than that of natural gas
without hydrogen under the same pressure drop. To produce
the same cooling effect, a larger pressure drop is required for
the natural gas−hydrogen mixture.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsomega.1c00248.
Derivation of eq 3 (PDF)
16734
■
Article
AUTHOR INFORMATION
Corresponding Author
Bo Yu − School of Mechanical Engineering, Beijing Key
Laboratory of Pipeline Critical Technology and Equipment
for Deepwater Oil and Gas Development, Beijing Institute of
Petrochemical Technology, Beijing 102617, China;
orcid.org/0000-0002-4231-6914; Email: yubobox@
vip.163.com
Authors
Jingfa Li − School of Mechanical Engineering, Beijing Key
Laboratory of Pipeline Critical Technology and Equipment
for Deepwater Oil and Gas Development, Beijing Institute of
Petrochemical Technology, Beijing 102617, China
Yue Su − Beijing Key Laboratory of Process Fluid Filtration
and Separation, College of Mechanical and Transportation
Engineering, China University of Petroleum (Beijing), Beijing
102249, China
Peng Wang − School of Mechanical Engineering, Beijing Key
Laboratory of Pipeline Critical Technology and Equipment
for Deepwater Oil and Gas Development, Beijing Institute of
Petrochemical Technology, Beijing 102617, China
Dongliang Sun − School of Mechanical Engineering, Beijing
Key Laboratory of Pipeline Critical Technology and
Equipment for Deepwater Oil and Gas Development, Beijing
Institute of Petrochemical Technology, Beijing 102617, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsomega.1c00248
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This study is supported by the National Natural Science
Foundation of China (Nos. 51904031 and 51936001) and the
Beijing Municipal Natural Science Foundation (No. 3204038).
■ REFERENCES
(1) Dincer, I.; Midilli, A.; Hepbasli, A.; Karakoc, T. H. Global
Warming: Engineering Solutions; Academic Press: Springer, 2010; pp
71−80.
(2) Zhou, S. Y.; Sun, K. Y.; Wu, Z.; Gu, W.; Wu, G. X.; Li, Z.; Li, J. J.
Optimized operation method of small and medium-sized integrated
energy system for P2G equipment under strong uncertainty. Energy
2020, 199, No. 117269.
(3) Belderbos, A.; Valkaert, T.; Bruninx, K.; Delarue, E.; D’haeseleer,
W. Facilitating renewables and power-to-gas via integrated electrical
power-gas system scheduling. Appl. Energy 2020, 275, No. 115082.
(4) Guandalini, G.; Campanari, S.; Romano, M. C. Power-to-gas
plants and gas turbines for improved wind energy dispatchability:
Energy and economic assessment. Appl. Energy 2015, 147, 117−130.
(5) Schnuelle, C.; Wassermann, T.; Fuhrlaender, D.; Zondervan, E.
Dynamic hydrogen production from PV & wind direct electricity
supply − Modeling and techno-economic assessment. Int. J. Hydrogen
Energy 2020, 45, 29938−29952.
(6) Messaoudani, Z. L.; Rigas, F.; Hamid, M. D. B.; Hassan, C. R. C.
Hazards, Safety and knowledge gaps on hydrogen transmission via
natural gas grid: A critical review. Int. J. Hydrogen Energy 2016, 41,
17511−17525.
(7) Li, Y. X.; Yao, G. Z. Design and Management of Natural Gas
Pipeline, 2nd ed.; Academic Press: Dongying, China, 2009; pp 22−42.
(8) Liu, W.; Hu, J.; Li, X.; Sun, Z.; Sun, F.; Chu, H. Assessment of
hydrate blockage risk in long-distance natural gas transmission
pipelines. J. Nat. Gas Sci. Eng. 2018, 60, 256−270.
https://doi.org/10.1021/acsomega.1c00248
ACS Omega 2021, 6, 16722−16735
ACS Omega http://pubs.acs.org/journal/acsodf Article

(9) Li, X.; Liu, Y.; Liu, Z.; Chu, J.; Song, Y.; Yu, T.; Zhao, J. A (28) Peng, D. Y.; Robinson, D. B. A new two-constant equation of
hydrate blockage detection apparatus for gas pipeline using ultrasonic state. Ind. Eng. Chem. Fundam. 1976, 15, 59−64.
focused transducer and its application on a flow loop. Energy Sci. Eng. (29) Starling, K. E.; Powers, J. E. Enthalpy of mixtures by modified
2020, 8, 1770−1780. BWR equation. Ind. Eng. Chem. Fundam. 1970, 9, 531−537.
(10) Liu, Z.; Yang, M.; Liu, Y.; Song, Y.; Li, Q. Analyzing the Joule- (30) Randelman, R. E.; Wenzel, L. A. Joule-Thomson coefficients of
Thomson effect on wellbore in methane hydrate depressurization with hydrogen and methane mixtures. J. Chem. Eng. Data 1988, 33, 293−
different back pressure. Energy Procedia 2019, 158, 5390−5395. 299.
(11) Qing, D. S.; Xu, J.; Chi, S. G.; Zhou, B.; Jian, Z. Y.; Yang, F.; (31) Wang, W.; Wang, Q.; Deng, H.; Cheng, G.; Li, Y. Feasibility
Gao, T. Optimization of the high-pressure ejection process in small- analysis on the transportation of hydrogen−natural gas mixtures in
scale natural gas liquefaction plants. Nat. Gas Ind. 2020, 40, 118−125. natural gas pipelines. Nat. Gas Ind. 2020, 40, 130−136.
(12) Francis, P. G.; Mcglashan, M. L.; Wormaldsa, C. J. A vapour- (32) Tabkhi, F.; Azzaro-Pantel, C.; Pibouleau, L.; Domenech, S. A
flow calorimeter fitted with an adjustable throttle. The isothermal mathematical framework for modelling and evaluating natural gas
Joule-Thomson coefficient of benzene. The temperature-dependence pipeline networks under hydrogen injection. Int. J. Hydrogen Energy
of the second virial coefficient of benzene. J. Chem. Thermodyn 1969, 2008, 33, 6222−6231.
1, 441−458. (33) Huang, M.; Wu, Y.; Wen, X.; Liu, W.; Guan, Y. Feasibility
(13) Clarke, P. H.; Francis, P. G.; George, M.; Phutela, R. C.; analysis of hydrogen transport in natural gas pipeline. Gas Heat Ind.
Roberts, G. K. S. C. Flow calorimeters for the measurement of the 2013, 033, 39−42.
isothermal Joule-Thomson coefficient of benzene and of cyclohexane
vapour. J. Chem. Thermodyn. 1979, 11, 125−139.
(14) Francis, P. G. A flow calorimeter for the measurement of the
heat capacities and Joule-Thomson coefficients of condensable
vapours. J. Chem. Thermodyn. 1990, 22, 545−556.
(15) Cuscó, L.; McBain, S. E.; Saville, G. A flow calorimeter for the
measurement of the isothermal Joule-Thomson coefficient of gases at
elevated temperatures and pressures. Results for nitrogen at
temperatures up to 473 K and pressures up to 10 MPa and for
carbon dioxide at temperatures up to 500 K and pressures up to 5
MPa. J. Chem. Thermodyn. 1995, 27, 721−733.
(16) Ernst, G.; Keil, B.; Wirbser, H.; et al. Flow-calorimetric results
for the massic heat capacity cp and the Joule−Thomson coefficient of
CH4, of (0.85 CH4 + 0.15 C2H6), and of a mixture similar to natural
gas. J. Chem. Thermodyn. 2001, 33, 601−613.
(17) Vrabec, J.; Kumar, A.; Hasse, H. Joule−Thomson inversion
curves of mixtures by molecular simulation in comparison to
advanced equations of state: Natural gas as an example. Fluid Phase
Equilib. 2007, 258, 34−40.
(18) Figueroa-Gerstenmaier, S.; Lísal, M.; Nezbeda, I.; Smith, W. R.;
Trejos, V. M. Prediction of isoenthalps, Joule−Thomson coefficients
and Joule−Thomson inversion curves of refrigerants by molecular
simulation. Fluid Phase Equilib. 2014, 375, 143−151.
(19) Zhang, D. T.; Teng, L.; Li, Y. X. A calculation method for
Joule-Thomson coefficient of pipeline CO2. Oil Gas Storage Transp.
2018, 37, 35−39.
(20) Tay, W. H.; Lau, K. K.; Shariff, A. M. Numerical simulation for
dehydration of natural gas using Joule Thompson cooling effect.
Procedia Eng. 2016, 148, 1096−1103.
(21) Haghighi, B.; Hussaindokht, M. R.; Reza, B. M.; Matin, N. S.
Joule−Thomson inversion curve prediction by using equation of state.
Chin. Chem. Lett. 2007, 18, 1154−1158.
(22) Abbas, R.; Ihmels, C.; Enders, S.; Gmehling, J. Joule−Thomson
coefficients and Joule−Thomson inversion curves for pure com-
pounds and binary systems predicted with the group contribution
equation of state VTPR. Fluid Phase Equilib. 2011, 306, 181−189.
(23) Ghanbari, M.; Check, G. R. New super-critical cohesion
parameters for Soave−Redlich−Kwong equation of state by fitting to
the Joule−Thomson Inversion Curve. J. Supercrit. Fluids 2012, 62,
65−72.
(24) Regueira, T.; Varzandeh, F.; Stenby, E. H.; Yan, W. Heat
capacity and Joule-Thomson coefficient of selected n-alkanes at 0.1
and 10 MPa in broad temperature ranges. J. Chem. Thermodyn. 2017,
111, 250−264.
(25) Soave, G. Equilibrium constants from a modified Redkh-Kwong
equation of state. Chem. Eng. Sci. 1972, 27, 1197−1203.
(26) Redlich, O.; Kwong, J. N. S. On the thermodynamics of
solutions. V. An equation of state. Fugacities of gaseous solutions.
Chem. Rev. 1949, 44, 233−244.
(27) Li, C.; Huang, Z. Pipeline Transport of Natural Gas, 3rd ed.;
Academic Press: Beijing, 2016; pp 30−45.

16735 https://doi.org/10.1021/acsomega.1c00248
ACS Omega 2021, 6, 16722−16735