Separation and Purification Technology 188 (2017) 238–249

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Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

Numerical simulation of CO2 condensation process from CH4-CO2 binary

gas mixture in supersonic nozzles
Wenjuan Sun a, Xuewen Cao a,⇑, Wen Yang b, Xuetang Jin a
a
College of Pipeline and Civil Engineering, China University of Petroleum, No.66, Changjiang West Road, Qingdao 266580, China
b
South China Branch, SINOPEC Sales Co., Ltd., No.191, Tiyu West Road, Guangzhou 510620, China

a r t i c l e i n f o a b s t r a c t

Article history: Supersonic separation technology is a technique potentially applicable in separating CO2 from natural
Received 19 January 2017 gas. An Euler-Euler two-fluid model is developed to predict the spontaneous condensation process of
Received in revised form 20 June 2017 CO2 in CH4-CO2 binary gas system during supersonic expansion using the nucleation theory and droplet
Accepted 11 July 2017
growth model. The proposed model is validated by the experimental data obtained from literature and
Available online 14 July 2017
the effects of inlet temperature, pressure and gas composition on the condensation process are analyzed.
The simulation results show that the homogeneous nucleation of CO2 occurs intensively within a short
Keywords:
period in the diverging part of the nozzle and the mass fraction of condensed phase increases continu-
CO2 separation
Condensation
ously until the nozzle outlet. The onset of the condensation occurs earlier and more CO2 can be condensed
Supersonic nozzle out of the gas mixture at lower inlet temperature, higher inlet pressure and bigger CO2 feed
Numerical simulation concentration.
Ó 2017 Elsevier B.V. All rights reserved.

1. Introduction
As one of the safest and cleanest energy sources, natural gas
plays a more and more important role in the energy supply. Exxon-
Mobil has projected that the demand for natural gas globally will
rise 45% and surpass coal by the year 2040 [1]. Natural gas is a
multi-component mixture with methane (CH4) as its primary con-
stituent and water vapor, inert gases, carbon dioxide (CO2), hydro-
gen sulphide (H2S) as impurities. The presence of CO2 will decrease
the heating value of the natural gas and cause corrosion of the
pipeline and process equipment with the presence of water.
Therefore, CO2 must be removed from natural gas to meet pipeline
quality requirements and sales gas specifications.
Many techniques can be employed to separate CO2 from natural
gas, such as absorption [2,3], adsorption [4,5], cryogenic separation
[6], and membrane [7]. Chemical absorption is the most well-
established industrial method being used for CO2 separation. This
method can effectively remove CO2 to an acceptable level, but it
is energy intensive and requires relatively large facilities. In addi-
tion, using alkylamine solutions as absorption liquid has several
limitations such as high energy consumption for regeneration, high
equipment corrosion rate and the possibility of having negative
effects on the environment. Supersonic separation technology
⇑ Corresponding author.
E-mail address: caoxw@upc.edu.cn (X. Cao).
provides a new and promising choice for CO2 separation with high
efficiency and small footprint. This technology combines expansion
cooling and centrifugal separation in a single compact device with
no chemicals requirement [8]. It has been widely studied for natu-
ral gas dehydration and hydrocarbon recovery [9–11] and is also
being proposed for natural gas liquefaction [12]. The potential
application in separating CO2 from natural gas has been investi-
gated using a flow loop based on the prototype of the supersonic
separator [13].
Supersonic separation technology is based on expansion cooling
inside the Laval nozzle which will lead to the condensation of tar-
get components. A key precondition of the separation is related to
the possibility of predicting and, therefore controlling the conden-
sation process of CO2 in the natural gas. Despite its importance,
limited studies on the condensation process of CO2 have been
reported. Tests involving the condensation of CO2 in supersonic
nozzles have been conducted, but the study was restricted to the
report of pressure profiles and conditions at the onset of condensa-
tion [14]. The nucleation behavior of CO2 from CH4-CO2 binary gas
mixture has been investigated in a pulse expansion chamber (PEC)
[15]. The droplets formation process of CO2 in CH4 or N2 atmo-
sphere has been studied and the size of condensed droplets has
been measured using the optical reflectance method, but the
expansion cooling was performed in a Joule-Thomson (J-T) valve
and the droplet measurements were carried out in an induction
pipe connected to the low pressure side of J-T valve [16]. The

http://dx.doi.org/10.1016/j.seppur.2017.07.023
1383-5866/Ó 2017 Elsevier B.V. All rights reserved.
 W. Sun et al. / Separation and Purification Technology 188 (2017) 238–249 239

Nomenclature

a sound speed [m/s] x arbitrary length along the axis of the nozzle [m]
a0 molecular surface area [m2] Xm relative coordinate of the junction point [–]
Aij combination factor of i and j components for thermal y mole fraction [–]
conductivity [–] Y mass fraction of condensed liquid [–]
cp specific heat at constant pressure [J/(mol K)] Z compressibility factor [–]
cv specific heat at constant volume [J/(mol K)]
d collision diameter [1010 m] Greek symbols
dr/dt droplet growth rate [m/s] c ratio of specific heats [–]
D nozzle diameter [m] C thermal conductivity parameter [(W/(m K))1]
Dev deviation between experimental data and calculated dij Kronecker delta [–]
values [–] e correction factor for nucleation rate [–]
E total energy [J/kg] DG⁄ energy barrier [J]
h vapor total enthalpy [J/kg] DT supercooling degree [K]
hlv latent heat of condensation [J/kg] h dimensionless surface tension [–]
J nucleation rate per unit volume per unit time [m3 s1] k thermal conductivity [W/(m K)]
K kinetic prefactor [m3 s1] l viscosity [N s/m2]
kB Boltzmann constant [1.3807  1023 J/K] n viscosity parameter [(lP)1]
keff effective thermal conductivity [W/(m K)] q density [kg/m3]
Kn Knudsen number [–] qC CO2 density [kg/m3]
kr heat transfer coefficient [W/(m K)] r surface tension [N/m]
L1 convergent section length [m] seff effective viscous stress [–]
m condensation mass per unit vapor volume per unit time Uij combination factor of i and j components for viscosity
[kg/(m3 s)] [–]
mv mass of single vapor molecule [kg] x acentric factor [–]
M molecular weight [kg/mol]
Ma mach number [–]
Subscripts
N droplets number density [kg1] 0 nozzle inlet
NA Avogadro’s number [6.02  1023 mol1] c critical property
p pressure [Pa]
cal calculated value
Prv Prandtl number [–] CNT classical nucleation theory
r droplet radius [m] cr nozzle throat
rc critical radius [m] exp experimental value
R universal gas constant [8.314 J/(mol K)]
i, j components in the mixture
Rv gas constant [J/(kg K)] ICCT internally consistent classical theory
S supersaturation [–] ij property characteristic of interactions between species i
Sh source term of vapor energy equation [J/(m3 s)] and j
Sm source term of vapor continuity equation [kg/(m3 s)]
l liquid phase
Su source term of vapor momentum equation [kg/(m2 s2)] m mixture
SY source term of liquid continuity equation [kg/(m3 s)] r reduced property
t time [s] s saturation
T temperature [K]
v vapor phase
Tb normal boiling point [K]
Td temperature of droplet [K]
u velocity [m/s] Superscript
u0 velocity fluctuation [m/s] 0 property at atmospheric pressure
V molar volume [m3/mol]


condensation process of CO2 in a CH4 atmosphere during the rapid DG
J ¼ K exp  ð1Þ
expansion cooling inside supersonic nozzles has not been kB T
addressed previously, which makes it become the objective of
the current work. In this study, a numerical model is developed where J is the nucleation rate per unit volume per unit time, K is the
to predict the condensation process of CO2 in the CH4-CO2 binary kinetic prefactor, kB is the Boltzmann constant, T is the temperature,
gas system within a supersonic nozzle and the effects of inlet DG⁄ is the energy barrier.
parameters on the condensation characteristics are discussed. The evolution of nucleation theory starts with the development
of the classical nucleation theory (CNT) [17], which can be
expressed by Eq. (2).
2. Mathematical model
sffiffiffiffiffiffiffiffiffiffi !
2.1. Condensation model q2 2r 16p r3
J CNT ¼ v exp  ð2Þ
ql pm3v 3 kB q2 R2v T 3 ðln SÞ2
l
The homogeneous nucleation of supersaturated vapor is the
first stage of the condensation process when no foreign particles where subscripts v and l respectively stand for vapor phase and liq-
are present. In general terms, the rate at which nuclei are formed uid phase. JCNT is the nucleation rate calculated by CNT, q is the den-
per unit volume per unit time can be described by Eq. (1). sity, r is the surface tension, mv is the molecular mass, Rv is the gas
240 W. Sun et al. / Separation and Purification Technology 188 (2017) 238–249

constant, S is the supersaturation ratio. The calculation of the gas

and liquid properties is specified in Appendix A.
Since the introduction of the CNT, various modifications have
been proposed to improve its accuracy. One of these in active use
is the internally consistent classical theory (ICCT) [18,19], and fur-
ther researches have shown that the ICCT is more accurate than the
CNT [20,21]. Therefore, the ICCT model improved by Lamanna [22]
is adopted to predict the nucleation rate in this study, which can be
expressed as Eq. (3).
expðhÞ
J ICCT ¼ eJ CNT ð3Þ
S
where JICCT is the nucleation rate calculated by ICCT, e is the correc-
tion factor proposed by Lamanna, h is the dimensionless surface
tension, defined as Eq. (3).
ra0
h¼ ð4Þ
kB T
where a0 is the molecular surface area.
Due to the release of latent heat in the phase change process,
Fig. 2. Simulation results for liquid phase mass fraction with different cell numbers.
the produced cluster becomes hotter than its surrounding vapor.
The droplet temperature can be determined by capillarity effect
[23], which is presented in Eq. (5).
rc
T d ¼ T s  DT ð5Þ
r
where Td is the temperature of droplet, Ts is the saturation temper-
ature at local pressure, r is the droplet radius, rc is the critical dro-
plet radius, which can be calculated by Eq. (6). DT is the level of
supercooling, which is defined as the difference between the satu-
ration temperature and the local vapor temperature, presented by
Eq. (7).
2r
rc ¼ ð6Þ
ql Rv T ln S
DT ¼ T s  T ð7Þ
The subsequent growth of the condensed droplet is highly
affected by the heat transfer rate, which is based on modeling
the released latent heat, convective heat transfer into the vapor
phase, and the temperature change of the droplet. Due to the small
size of the produced clusters, the droplet heating term can be
neglected comparing with the droplet-vapor convective heat trans-
fer. Therefore, the energy equation can be described by Eq. (8).
dr
4pr 2 ql hlv ¼ 4pr 2 kr ðT d  TÞ ð8Þ Fig. 3. Comparison of experimental and calculation viscosity values.
dt
where hlv is the latent heat of condensation, dr/dt is the droplet
growth rate, kr is the heat transfer coefficient between the droplet
and its surrounding gas, which can be calculated by Eq. (9) [24].
kv 1
kr ¼ pffiffiffiffi ð9Þ Table 1
r 1 þ 2 8p c Comparison of experimental and calculation thermal conductivity values.
1:5Prv cþ1 Kn
T/K p/atm q/(mol/L) kexp  103/ kcal  103/ Dev/%
[W/(m K)] [W/(m K)]
228.13 14.69 0.885 20.54 19.67 4.24
238.14 15.52 0.886 21.47 20.66 3.77
246.84 16.18 0.883 22.23 21.53 3.15
254.39 16.93 0.891 22.61 22.3 1.37
267.12 17.68 0.876 24.45 23.55 3.68
238.22 10.54 0.579 20.6 20.07 2.57
246.77 10.97 0.578 21.77 20.92 3.90
266.93 11.98 0.577 23.39 22.94 1.92
228.32 2.61 0.142 19.14 18.24 4.70
238.51 2.74 0.142 19.8 19.25 2.78
246.75 2.82 0.142 20.65 20.07 2.81
253.94 2.91 0.142 21.68 20.79 4.11
266.92 3.06 0.142 23.02 22.1 4.00
272.07 3.12 0.142 23.28 22.62 2.84
Fig. 1. Structural schematic of designed nozzle.
 W. Sun et al. / Separation and Purification Technology 188 (2017) 238–249 241

equation, presented as Eqs. (11)–(14). As the size of the liquid dro-

plets is very small, the inter-phase slippage can be ignored. The liq-
uid flow characteristics can be depicted by the continuity equation
and droplet number density conservation equation, described as
Eqs. (15), (16).
@ qv @
þ ðq uj Þ ¼ Sm ð11Þ
@t @xj v

@ qC @
þ ðq uj Þ ¼ Sm ð12Þ
@t @xj C


@ @ @p @ @u @u 2 @u
ðqv ui Þ þ ðqv ui uj Þ ¼  þ l i þ j  dij j
@t @xj @xi @xj @xj @xi 3 @xj
@
þ ðqu0i u0j Þ þ Su ð13Þ
@xj


@ @ @ @T
ðqv EÞ þ ðqv uj E þ uj pÞ ¼ keff þ ui seff þ Sh ð14Þ
@t @xj @xj @xj

Fig. 4. Comparison of experimental and simulation results in Wyslouzil’s nozzle. @ @

ðqYÞ þ ðquj YÞ ¼ SY ð15Þ
@t @xj
where kv is the thermal conductivity, Prv is the Prandtl number, c is
the specific heat ratio, and Kn is the Knudsen number. @ @
Substituting Eq. (9) into Eq. (8), the droplet growth rate can be ðqNÞ þ ðquj NÞ ¼ J ð16Þ
@t @xj
calculated by Eq. (10).
where Sm, Su, Sh and SY are the source terms, which can be written as
dr k ðT s  TÞð1  r c =rÞ
¼  pffiffiffiffi  ð10Þ Sm ¼ m ð17Þ
dt ql hlv r 1 þ 2 8p c Kn
1:5Prv cþ1

Su ¼ mui ð18Þ
2.2. Governing equations
Sh ¼ mðhlv  hÞ ð19Þ
The gas flow characteristics in the Laval nozzle can be described
SY ¼ m ð20Þ
by the continuity equation, momentum equation, and energy

Fig. 5. Flow and condensation parameters distribution in Laval nozzle. (a) Mach number (b) Supercooling degree (c) Nucleation rate (d) Mass fraction of liquid phase and (e)
CO2 mole fraction in gas phase.
242 W. Sun et al. / Separation and Purification Technology 188 (2017) 238–249

The symbol m denotes the condensation mass per unit volume inlet, D is the diameter at x, L1 is the length of the convergent sec-
per unit time, which can be calculated by Eq. (21). tion, and Xm is the relative coordinate of the junction point between
the front section and the back section.
4pr 3c dr
m¼ ql J þ 4pr2 qv ql N ð21Þ The size of the throat cross section is a key geometric parameter
3 dt for the supersonic nozzle, as it determines the flow rate through
the nozzle [28]. For supersonic nozzles, the flow should be chocked
2.3. Nozzle structure at the throat, fixing the flow through the nozzle as shown in
Eq. (23).
Laval nozzle is a convergent-divergent nozzle which can be _ ¼ Acr qcr acr
m ð23Þ
divided into three zones – subsonic section, critical section, and
supersonic section. The convergent profile is calculated by the where m _ is the mass flow rate, A is the cross sectional area, and a is
cubic polynomial equation shown in Eq. (22) [25,26], while the the speed of sound.
divergent contour is designed via Foelsch’s analytical method [27]. In order to calculate the cross sectional area of throat, it is nec-
8  3 essary to find the critical flow parameters. An approach similar to
>
< 1  12 Lx x
6 Xm that of Castier [29] is used to obtain the flow parameters at the
D  Dcr Xm 1 L1
¼  3 ð22Þ nozzle throat for sonic condition. The equations for energy balance
D0  Dcr >: 1 1 x 2
ð1X m Þ L1
x
L1
> Xm and isentropic condition are presented in Eqs. (24), (25).

where subscripts 0 and cr stand for inlet and throat section, respec- Mu20 Ma2cr
h0 þ ¼ hcr þ ð24Þ
tively. x is the distance between an arbitrary cross section and the 2 2

Fig. 6. Flow and condensation parameters distribution in inlet-temperature-effect study. (a) Temperature (b) Pressure ratio (c) Supercooling degree (d) Nucleation rate (e)
Droplet number density (f) Droplet radius (g) Mass fraction of liquid phase and (h) CO2 mole fraction in gas phase.
 W. Sun et al. / Separation and Purification Technology 188 (2017) 238–249
Fig. 6 (continued)
s0 ¼ scr
where h is the molar enthalpy, s is the molar entropy, and M is the
molar mass.
The need for computation of sound velocity occurs in this calcu-
lation. Different approaches have been proposed for the sound
speed calculation in single and multi-phase systems in the recent
years [30–32]. For the nozzle design, the calculation is limited to
finding the critical flow parameters at the throat. As the condensa-
tion process occurs downstream the throat for the set of inlet con-
ditions (which can be seen from the simulation results), the flow at
the throat is in single phase condition. The sound speed at the
throat can be derived by Eq. (26) [33].
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Z cr ccr RT cr
acr ¼
M flow. In order to close the flow governing equations, a turbulence
In order to simplify the calculation while maintaining the prac-
ticality, contaminated natural gas is modeled as a binary mixture
of CH4 (90% in mole fraction) and CO2 (10% in mole fraction). The
inlet conditions for the nozzle design are 293.15 K, 4 MPa, and
5000 Nm3/h. According to the method mentioned above, a Laval
nozzle with outlet Mach number of 2.5 is designed. The diameters
243
ð25Þ of the throat and the outlet are 13.33 mm and 25.29 mm, respec-
tively. The nozzle inlet diameter is about 7.5 times of the throat
diameter. The structural schematic of the designed nozzle is shown
in Fig. 1. The throat section locates at x = 161.82 mm.
2.4. Numerical schemes
The computational fluid dynamics (CFD) modeling software
Fluent is used to solve the governing equations in this study.
User-Defined Scalar (UDS) flux functions are needed to establish
the governing equations of liquid phase. The source terms caused
by condensation are added to the governing equations using
User-Defined Function (UDF) written by C language.
The density based solver is chosen to solve the flow governing
ð26Þ equations as it can give more accurate results for compressible
model is necessary to derive the Reynolds stresses. The k-x turbu-
lence model is used in this study due to its applicability to com-
pressible flow and wall-bonded flow. The second order upwind
scheme is employed for the flow, turbulent kinetic energy and
specific dissipation rate equations. Peng-Robinson (PR) equation
of state (EOS) [34] is adopted to calculate the gas stream
244 W. Sun et al. / Separation and Purification Technology 188 (2017) 238–249

density as it is widely used in the oil and gas industry (presented in
Appendix A).
According to the supersonic flow characteristics, pressure inlet
and pressure outlet conditions are specified for the entrance and
the exit of the nozzle, respectively. No-slip and adiabatic boundary
conditions are posted to the wall. The total pressure, static pres-
sure, turbulence parameters, total temperature, and species are
preassigned for the inlet. The intensity and hydraulic diameter
are assigned as the turbulence parameters. As the flow is super-
sonic at the outlet, no parameters are specified for the outlet.
The solution is considered as converged when the residuals drop
below 106 for the energy and 103 for the others, while the mass
flow rate relative error between the inlet and outlet is less than
0.05%.
In order to minimize the computation time using CFD, the sym-
metry in the geometry is used to reduce the computational
domain. Unstructured meshes are generated and gird indepen-
dence is investigated for the designed nozzle. The inlet pressure,
temperature and CO2 concentration for the gird independence
study are 4 MPa, 293.15 K and 10% (mole fraction), respectively.
The simulation results of condensed liquid mass fraction with four
different cell numbers are shown in Fig. 2. As shown in
Fig. 2, 10,742 cells can provide sufficient gird independence in con-
sideration of the computing efficiency and accuracy.
3. Results and discussion
3.1. Model validation
Before the model is used, results should be checked against the
experimental data to verify reliability. The available experimental
data associated with viscosity, thermal conductivity and condensa-
tion process are obtained from previously published literature to
verify the accuracy of the proposed models.
3.1.1. Viscosity validation
The experimental viscosity data for CH4-CO2 binary gas mixture
reported by Kestin and Ro [35] are used to assess the accuracy of
the viscosity model. The measurement is conducted at 298.15 K
and 0.1 MPa. Fig. 3 presents the comparison between the experi-
mentally measured data and the predicted values for different
concentrations of CH4, showing maximum disagreement of 1.2%.

Fig. 7. Flow and condensation parameters distribution in inlet-pressure-effect study. (a) Temperature (b) Pressure ratio (c) Supercooling degree (d) Nucleation rate (e)
Droplet number density (f) Droplet radius (g) Mass fraction of liquid phase and (h) CO2 mole fraction in gas phase.
 W. Sun et al. / Separation and Purification Technology 188 (2017) 238–249
Fig. 7 (continued)
It clearly demonstrates that the present approach provides an
excellent approximation to the viscosity of CH4-CO2 binary
mixture.
3.1.2. Thermal conductivity validation
The experimental thermal conductivity data for CH4-CO2 binary
gas mixture reported by Christensen and Fredenslund [36] are used
to validate the thermal conductivity model. The measurement is
conducted at temperature ranging from 228.13 K to 272.07 K and
pressure ranging from 2.61 atm to 17.68 atm. The mole fraction
of CH4 is 0.5061. Table 1 displays the comparison of the experi-
mental data and the calculated values. The model is found to rep-
resent the experimental data within a maximum deviation of 4.7%,
which illustrates that the model can provide reliable estimation of
the thermal conductivity value.
3.1.3. Condensation model validation
The experimental data of Wyslouzil et al. [37] are used to test
the condensation model and numerical method discussed above.
The converging and diverging section of the nozzle used in the
experiment are 38 mm and 95 mm long, respectively. The throat
245
size is 12.7 mm  5.0 mm, and the ratio of outlet area to the throat
area is 1.58. The working fluid is water vapor and nitrogen. The
inlet pressure and temperature are 60 kPa and 286.7 K, and the
water partial pressure is 1 kPa. The pressure distribution along
the nozzle axis is measured. The comparison of experimental data
and simulation results is presented in Fig. 4. As shown in Fig. 4, the
simulation results are in good agreement with the experimental
data, which demonstrates that the mathematical model discussed
above is capable of predicting the homogeneous condensation pro-
cess in a supersonic nozzle.
3.2. CO2 condensation process
The condensation process of CO2 in CH4-CO2 binary gas mixture
inside the supersonic nozzle is numerically simulated using the
above model. The inlet pressure, temperature and CO2 mole frac-
tion are 4 MPa, 293.15 K and 10%, respectively. The simulation
results of flow and condensation parameters distribution in the
nozzle are shown in Fig. 5.
As shown in Fig. 5(a), the gas flow is accelerated uniformly in
the convergent part and becomes sonic at the throat. Then the flow
246 W. Sun et al. / Separation and Purification Technology 188 (2017) 238–249

is accelerated further to supersonic in the divergent part. The
superheated vapor will enter into supercooling state along with
the rapid expansion, as illustrated in Fig. 5(b). In absence of foreign
particles, the phase transition is preceded by homogeneous nucle-
ation and adequate level of supercooling is required for homoge-
neous nucleation to proceed. The maximum supercooling degree
can reach about 11K in this case, which indicates a metastable
non-equilibrium state of the vapor phase.
As can be seen from Fig. 5(c), the nucleation process occurs fier-
cely within a short distance. Then the nucleation process is inter-
rupted as a result of the latent heat release, which will lead to
the decline of the supercooling degree. After nucleation, the pro-
cess of droplet growth sets in, resulting in a rising mass fraction
of liquid phase as shown in Fig. 5(d). Corresponding decrease of
CO2 mole fraction in the gas stream can be seen from Fig. 5(e).
The mole fraction of CO2 in vapor phase can be reduced to 2.4%
at the nozzle exit and the product gas stream will become rich in
CH4 after the separation of the condensed phase. This clearly
illustrates the powerful capability of the supersonic separator on
effective separating CO2 from natural gas.
3.3. Effect of inlet temperature
The working fluid with different temperature and fixed pressure
(4 MPa) and CO2 mole fraction (10%) is introduced to the nozzle to
study the effect of inlet temperature on the condensation process.
Fig. 6 shows the distribution of flow and condensation parameters
along the axis of the nozzle for various inlet temperatures.
The distributions of temperature and dimensionless pressure,
defined as the ratio of local static pressure to the inlet one, along
the nozzle axis are shown in Fig. 6(a) and (b). As depicted in
Fig. 6(a) and (b), the temperature and pressure reduce rapidly
along the nozzle axis and experience a sudden jump due to the
release of latent heat during the phase transition process.
When the inlet temperature is lower, the supercooling degree at
the nozzle inlet is bigger and the supercooling requirement can be
achieved sooner, as illustrated in Fig. 6(c). Therefore, the nucleation
process occurs earlier at lower inlet temperature, as can be seen from
Fig. 6(d). The nucleation occurs at x = 0.187 m when the inlet tem-
perature is 298.15 K, while the nucleation occurs at x = 0.179 m
when the inlet temperature is 283.15 K. It also appears that the

Fig. 8. Flow and condensation parameters distribution in inlet-composition-effect study. (a) Temperature (b) Pressure ratio (c) Supercooling degree (d) Nucleation rate (e)
Droplet number density (f) Droplet radius (g) Mass fraction of liquid phase and (h) CO2 mole fraction in gas phase.
 W. Sun et al. / Separation and Purification Technology 188 (2017) 238–249
Fig. 8 (continued)
nucleation process happens less fiercely at lower inlet temperature,
resulting in the decrease of the droplet number density showing in
Fig. 6(e). The maximum nucleation rate and droplet number density
drop from 2.58  1025 m3 s1 and 9.20  1018 kg1 to 8.23  1024 -
m3 s1 and 2.73  1018 kg1 respectively when the inlet tempera-
ture decreases from 298.15 K to 283.15 K.
Fig. 6(f)–(h) shows that bigger droplets are formed with the
decrease of the inlet temperature, leading to larger liquid phase
mass fraction even with less droplet number. It is also very appar-
ent that the remaining volume of CO2 in the gas stream becomes
less when the inlet temperature is lower, as more CO2 has con-
densed into liquid phase. The liquid phase mass fraction increases
from 17.09% to 19.77% when the inlet temperature decreases from
298.15 K to 283.15 K and the mole fraction of CO2 remaining in the
gas stream at the nozzle exit is less than 3%.
3.4. Effect of inlet pressure
The working fluid with different pressure and fixed temperature
(293.15 K) and CO2 mole fraction (10%) is introduced to the nozzle
247
to study the effect of inlet pressure on the condensation process.
The simulation results are shown in Fig. 7.
As can be found from Fig. 7, the temperature and pressure
reduce rapidly along the nozzle axis and experience a sudden rise
due to the release of latent heat. The nucleation process occurs ear-
lier with decreasing maximum nucleation rate and droplet number
density when the inlet pressure increases. The reason for these
phenomena is comparable to that presented in Section 3.3. The
supercooling requirement for nucleation is achieved sooner as
the supercooling degree at the inlet is bigger under a higher pres-
sure. The nucleation process moves from x = 0.185 m to
x = 0.181 m, and the maximum nucleation rate and droplet number
density decrease from 1.88  1025 m3 s1 and 6.16  1018 kg1 to
4.91  1024 m3 s1 and 1.01  1018 kg1 respectively when the
inlet pressure increases from 4 MPa to 5.5 MPa.
As can be seen from Fig. 7(f)–(h), the mass fraction of condensed
liquid phase increases as a result of bigger droplet radius, leading
to less amount of CO2 remaining in the gas stream. The liquid mass
fraction increases from 18.10% to 19.43% when the inlet pressure
increases from 4 MPa to 5.5 MPa and the mole fraction of CO2 in
the gas stream can be reduced to less than 3% at the nozzle outlet.
248 W. Sun et al. / Separation and Purification Technology 188 (2017) 238–249

3.5. Effect of inlet gas composition ð1 þ xÞð1  T br Þ ln 10

D¼ ðA:3Þ
lnðpc =101325Þ
The working fluid with different CO2 concentration and fixed
temperature (293.15 K) and pressure (6 MPa) is introduced to the T c ð0:7D  0:3T br Þ
C¼ ðA:4Þ
nozzle to study the impact of inlet gas composition on the conden- 0:3  D
sation characteristics. The simulation results are shown in Fig. 8.
As can be seen from Fig. 8, the CO2 vapor enters into supercool- T c ð1 þ C=T c ÞðT br þ C=T c Þ lnðpc =101325Þ
B¼ ðA:5Þ
ing state along with the drop of temperature and pressure. When 1  T br
the gas mixture has more CO2 component, the supercooling
requirement for nucleation is achieved sooner as the supercooling B=T c
A ¼ ln 101325 þ ðA:6Þ
degree at the entrance is bigger. The nucleation process shifts T br þ C=T c
towards the throat with decreasing maximum nucleation rate
and droplet number density. Bigger droplets are formed and more Tb
T br ¼ ðA:7Þ
CO2 is condensed into liquid phase. When the inlet CO2 mole frac- Tc
tion increases from 10% to 40%, the onset of the condensation
Surface tension [40]:
moves forwards by 9 mm (from x = 0.179 m to x = 0.170 m), and

2=3
the maximum nucleation rate and droplet number density NA
decrease from 3.32  1024 m3 s1 and 6.44  1017 kg1 to
r ¼ kB T c ð4:35 þ 4:14xÞs1:26 ð1 þ 0:19s0:5  0:25sÞ ðA:8Þ
Vc
1.78  1023 m3 s1 and 2.68  1016 kg1 respectively.
As can be seen from Fig. 8(h), although more CO2 has condensed T
into liquid phase, there is still more CO2 remaining in the gas
s¼1 ðA:9Þ
Tc
stream when the inlet mole fraction of CO2 increases. Only part
Latent heat [39,41]:
of the CO2 can be condensed out of the gas mixture by the nozzle

n
used in this study. The use of nozzle with deep expansion and two- 0 1  Tr
stage supersonic separation may be considered to enhance the hlv ¼ hlv ðA:10Þ
1  T br
condensation process further.
8
>
< 0:3 T br < 0:57
4. Conclusions n ¼ 0:74T br  0:116 0:57 < T br < 0:71 ðA:11Þ
>
:
0:41 T br > 0:71
The condensation behavior of CO2 in CH4-CO2 binary gas mix-
ture during the rapid expansion within the supersonic nozzle is Liquid density [42]:
numerically simulated. The simulation results show that the

1
homogeneous nucleation of CO2 vapor occurs at adequate levels RT c ½1þð1T r Þ2=7 
of supercooling. The nuclei are generated intensively in a short per- ql ¼ Z RA ðA:12Þ
pc
iod and the mass fraction of condensed phase increases continu-
ously until the nozzle exit as a result of droplet growth. Z RA ¼ 0:29056  0:08775x ðA:13Þ
The condensation process occurs much earlier with decreasing
droplet number density at lower inlet temperature, higher inlet Viscosity [39,43,44]:
pressure and bigger CO2 feed concentration. Meanwhile, larger liq- pffiffiffiffiffiffiffiffiffi
26:69 M i T
uid phase mass fraction can be achieved at the exit of the nozzle as l0i ¼ 2
ðA:14Þ
bigger droplets are formed. Although more CO2 can be condensed d XV
out of the gas mixture with the increase of CO2 feed concentration,
there is still more CO2 remaining in the gas mixture. X
n
y l0
l0m ¼ Pn i i ðA:15Þ
The mole fraction of CO2 in the outlet gas stream significantly i¼1 j¼1 yi /ij
decreases for various inlet conditions. The residual CO2 in the out-
let gas phase can be reduced to less than 3% when the mole fraction
12
Mj
of CO2 in the feed gas is 10%. It clearly shows the capability of /ij ¼ ¼ /1
ji ðA:16Þ
Mi
supersonic separation technology in separating CO2 from CH4 rich
natural gas.
ðlm  l0m Þnm ¼ 1:08½expð1:439qrm Þ  expð1:111q1:858
rm Þ ðA:17Þ
Acknowledgements !1=6
T cm
nm ¼ ðA:18Þ
This work is supported by the National Natural Science Founda- M 3m p4cm
tion of China (Grant number 51274232) and the Fundamental
Research Funds for the Central Universities (Grant number Thermal conductivity [39,45–49]:
16CX06004A).
k0i Mi 1:77
¼ 1:32 þ ðA:19Þ
Appendix A. Physical properties li cv i ðcpi =RÞ  1

Saturated vapor pressure/temperature [38,39]: X

n
y ki
k0m ¼ Pn i ðA:20Þ
B i¼1 j¼1 yi Aij
ln ps ¼ A  ðA:1Þ
T þC h i2
1 3
1 þ ðli =lj Þ2 ðM j =Mi Þ4
B Aij ¼ ðA:21Þ
Ts ¼ C ðA:2Þ 1
A  ln ps ½8ð1 þ M i =Mj Þ2
 W. Sun et al. / Separation and Purification Technology 188 (2017) 238–249 249

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