i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 8 2 3 6 e8 2 4 5

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Thermal effects on breakthrough curves of

pressure swing adsorption for hydrogen
purification

Jinsheng Xiao a,b,*, Yuzhi Peng a, Pierre Benard b, Richard Chahine b

a
Hubei Key Laboratory of Advanced Technology for Automotive Components and Hubei Collaborative Innovation
Center for Automotive Components Technology, School of Automotive Engineering, Wuhan University of Technology,
Hubei 430070, China
b
Hydrogen Research Institute, Universite du Quebec a
 Trois-Rivieres, QC G9A 5H7, Canada

article info abstract

Article history: Applying pressure swing adsorption (PSA) to recover hydrogen from industrial exhaust gas
Received 31 July 2015 is an effective way to recycle by-product industrial exhaust gas. In this paper, the PSA
Received in revised form process for hydrogen purification is studied using a one-dimensional multicomponent
21 November 2015 adsorption, heat and mass transfer model which is implemented in Comsol Multiphysics
Accepted 23 November 2015 version 3.5a. This model is validated by experimental data on activated carbon (AC) and
Available online 21 December 2015 zeolite 5A bed. Both the breakthrough curve and the bed temperature distribution show
good agreement with experiments. This paper considers two hydrogen ternary mixtures
Keywords: (H2/CH4/CO ¼ 60.4/28.1/11.5 vol% in activated carbon bed; H2/CH4/CO ¼ 60/30/10 vol% in
Hydrogen purification zeolite 5A bed) and one hydrogen quaternary mixture (H2/CO2/CH4/CO ¼ 69/26/3/2 vol% in
Pressure swing adsorption activated carbon bed). The purpose of two ternary mixtures (H2/CH4/CO) that are fed into
Breakthrough curve an activated carbon PCB bed and a zeolite 5A bed respectively is to study the influence of
Thermal effect adsorbent on the breakthrough characteristics of the mixture. The quaternary mixture (H2/
Heat and mass transfer CO2/CH4/CO) is fed into an activated carbon bed aimed at investigating the effect of mixture
composition on adsorption performance. The thermal effects associated with the
adsorption process are examined by comparing various thermal boundary conditions:
adiabatic, isothermal and general heat transfer boundary conditions. The results suggest
that good control of bed temperature is an effective way to restrain thermal effects on
breakthrough curves. The operating parameters of feed flow rate and axial mass dispersion
coefficient are also examined.
© 2015 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

oven gases and ethylene plant effluent gases [1,2]. Depending

Introduction
Adsorption separation technology is an state-of-the-art way
to recover hydrogen from industrial hydrogen-rich exhaust
gases including steam and catalytic reforming off-gases, coke
on the industrial process and separating objectives, frequently
adopted adsorption technologies include pressure swing
adsorption (PSA), temperature swing adsorption (TSA) and
thermal pressure swing adsorption (TPSA), etc. Current

* Corresponding author. Hydrogen Research Institute, Universite  du Quebec a Trois-Rivie

res, QC G9A 5H7, Canada. Tel.: þ1 819 376
50114478; fax: þ1 819 376 5164.
nard), Richard.Chahine@uqtr.ca (R. Chahine).
E-mail addresses: Jinsheng.Xiao@uqtr.ca (J. Xiao), Pierre.Benard@uqtr.ca (P. Be
http://dx.doi.org/10.1016/j.ijhydene.2015.11.126
0360-3199/© 2015 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 8 2 3 6 e8 2 4 5
studies on adsorption separation technologies are mostly
concentrated on pressure swing adsorption. Gas separation
using PSA was studied experimentally and theoretically by
Cen and Yang [3]. Schell and Mazzotti carried out PSA exper-
iments for pre-combustion CO2 capture from CO2/H2 mixture
[4]. Lopes and Grande conducted multicomponent break-
through experiments and VPSA cycle experiments in a ten-
steps one-column system [5]. Chahhani and Tondeur stud-
ied the pressure equalization step of PSA and results indicated
that equilibrium pressure is important so as to assess accu-
rately system performances [6]. Temperature swing adsorp-
tions (TSA) are based on adsorption thermodynamics, TSA
process is energy intensive because it requires additional heat
for the regeneration process of bed. Little information in
literature on the studies of TSA seems to be available. Rezaei
et al. studied rapid temperature swing adsorption (RTSA)
using hollow fiber sorbents [7]. The thermal pressure swing
adsorption (TPSA) can achieve high performance because it
takes full advantage of PSA and TSA. TPSA process operates at
high pressure and the bed regeneration is achieved by using
the waste heat of system. Vinay and Handan studied TPSA
process for CO2 recovery from flue gas using Ceca 13X and
concluded that good regeneration conditions used in a TPSA
cycle is essential over PSA cycle for regaining maximum
adsorption capacity [8].
Current researches on PSA are mostly related to adsor-
bents, the structure of adsorption bed and PSA cycles. Some
new adsorbents are being developed upon the activated
carbons and the zeolites which have already been widely
applied in PSA sorbent beds. For example, Rezaei et al applied
a novel polymeric hollow fiber reactor for CO2 capture
because polymeric hollow fiber beds have the advantages of
efficient heat transfer, faster heat and mass equilibration
and low pressure drops [7]. Banu et al made multi-scale study
of MOFs (UiO-66(Zr), UiO-66(Zr)eBr, UiO-67(Zr) and
ZreCl2AzoBDC) for H2 PSA purification and found that UiO-
66(Zr)eBr was the most promising among the four recom-
mended MOFs due to its longest dimensionless breakthrough
time [9]. In order to improve the separation efficiency of PSA
systems, adsorption beds frequently contain two or more
adsorbent layers, each of which is designed to target specific
chemical species. In addition, more than one adsorbent col-
umn can be used in a single PSA system. Lee and co-workers
investigated the adsorption dynamics and characteristics of
a layered bed packed with activated carbon and zeolite 5A
[10e13].
However, little researches seem to have been devoted to
the thermal effects generated during the adsorption pro-
cess of PSA for hydrogen purification. As a pioneer work in
this area, Ahn et al studied thermal effects on the con-
centration curves of ternary hydrogen system at a fixed bed
[14]. Lee et al proposed a novel heat-exchange PSA (HE-PSA)
to alleviate the thermal effects during adsorption process
[15]. They found that the separation performance (purity
and recovery rate) of the new HE-PSA was higher than
conventional PSA systems. The authors of this paper
have already contributed some fundamental studies on
adsorption-based hydrogen storage [16,17]. In such sys-
tems, management of thermal effect during adsorption
8237
process is a key factor in improving the performance of
hydrogen storage system.
The overall objective of this paper is to study the adsorp-
tion properties of hydrogen gas mixtures in the adsorption
beds of activated carbon and zeolite and to explore the influ-
ence of the thermal effects generated during the adsorption
step on the breakthrough curves of a gas mixture. A one-
dimensional model for adsorption, heat and mass transfer is
implemented in Comsol Multiphysics version 3.5a. The PSA
processes in the adsorption beds using an activated carbon
PCB and zeolite 5A are simulated using a one dimensional
model implemented in Comsol. The adsorption process on the
activated carbon bed is studied using a ternary and a quater-
nary gas mixture containing hydrogen, whereas the bed con-
taining the zeolite is studied using a ternary mixture
containing hydrogen. The effect of three different thermal
boundary conditions on the breakthrough curves and bed
temperature profiles are examined (adiabatic, isothermal and
general heat transfer). The axial mass transfer coefficient DL is
calculated using the Wakao equation, and axial heat con-
duction is expressed by the effective axial thermal conduc-
tivity KL. In addition, we use equivalent heat capacities and
thermal conductivities averaged by the molar fractions of the
species in the mixture. Furthermore, we examine the effects
of the feed rate, the adsorbent materials, the mixture
composition, and the axial mass dispersion coefficient on
hydrogen purification performance.
Models of adsorption, heat and mass transfer
Adsorption isotherms and kinetics
The extended Langmuir adsorption isotherm as parametrized
in reference [11] is used to predict equilibrium behaviours of
multicomponent adsorption on activated carbon PCB (Calgon
Co.) and zeolite 5A (Grace Co.):
,0 1
X
N
n*i ¼ nsi bi pi @1 þ bj pj A; i ¼ 1; …; N (1)
j¼1
where n*i andnsi are the equilibrium and saturated adsorption
amounts of ith component, respectively. bi is the Langmuir
isotherm parameter of species i and pi is the partial pressure of
species i. And the saturated adsorption amount is
nsi ¼ ai1 þ ai2 =T; bi ¼ bi0 expðbi1 =TÞ; i ¼ 1; …; N (2)
The adsorption kinetics is expressed by linear driving force
(LDF) model:
vni  
¼ ki n*i  ni ; i ¼ 1; …; N (3)
vt
where ni and ki are the dynamic adsorption amount and mass
transfer coefficient of species i.
Mass balance equations
The mass balance equations for each component and for the
total mass of the mixture are [14,18]:
8238 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 8 2 3 6 e8 2 4 5

  temperature Tw in isotherm adsorption model because the

v2 ci vðUz ci Þ vci 1  εb vni
DL þ þ þ rp ¼ 0; i ¼ 1; …; N (4) temperature of bed and wall are invariable. In the adiabatic
vz 2 vz vt εb vt
model, Eq. (10) is not used for solution of wall temperature Tw
because of no heat exchange between bed and wall.
vc vðUz cÞ 1  εb X
N
vnj
þ þ rp ¼0 (5)
vt vz εb j¼1 vt
Ergun equation for momentum balance
where Uz is the physical (interstitial) velocity in z direction.
The parameters rp , t and z represent the pellet density, the The Ergun equation is used as a simplified momentum bal-
time and the axial coordinates of the bed, respectively. The ance equation to calculate the pressure drop along the
gas phase concentration is ci , where the index i refers to the adsorption bed [10]:
ith species. The mixture concentration is c. The mass balance
dp 150mVz ð1  εb Þ2 rg Vz2 ð1  εb Þ
equation is used to estimate the physical velocity Uz. The  ¼ þ 1:75 (11)
dz 4R2p ε3b 2Rp εeb
axial mass dispersion coefficient DL is calculated from Ref.
[10]: where m is the viscosity of the gas phase and Darcy velocity is
V z ¼ Uz ε b .
DL 20
¼ þ 0:5 (6)
2Uz Rp ReSc
Molar concentrations and partial pressure
where Rp is the average radius of particles, Re and Sc are the
Reynolds number and Schmidt number, respectively.
The molar fraction yi is calculated from the ideal gas equation.
The partial pressures pi are obtained from the molar fraction
Energy balance equation and the total pressure p of the mixture [18]:

Assuming that the gas phase and the solid phase reach instant ci RT
yi ¼ ; pi ¼ yi p; i ¼ 1; …; N (12)
thermal equilibrium, the energy balance equation for the bed p
(including the contribution of heat transfer from the wall) can where ci is the molar concentration of species i. The equivalent
be expressed as [14,18]: heat capacity and the equivalent thermal conductivities are
defined by a molar fraction weighted average:
v2 T   vT vT
KL þ εb cCpg þ ð1  εb Þrp cps þ εb cCpg Uz
vz 2 vt vz X
n X
n
XN
vnj 2hin Cpg ¼ yi Cpi ; kg ¼ yi kgi ; i ¼ 1; …; N (13)
¼ ð1  εb Þrp DHj þ ðTw  TÞ (7) i¼1 i¼1
j¼1
vt Rin
where Cpi, kgi are the heat capacity and thermal conductivity of
where εb is porosity of the porous material, Cpg (J/mol/K) and ith component evaluated at a temperature of 300 K and a
cps (J/kg/K) are the specific heats of the gas and solid phases, pressure of 980 KPa.
Tw , hin and Rin are wall temperature, inner column wall heat
transfer coefficient and the column inner radius, respectively;
and DHj is heat of adsorption of species i. The effective axial
Model implementation and parameters
thermal conductivity KL is estimated with the empirical cor-
relation [10]:
Model implementation
KL 1  εb
¼ εb þ    þ dPrRe (8)
kg 4  ð2=3Þ kg ks The model is implemented in the Comsol Multiphysics 3.5a.
The following modules are used: diffusion (CHDI), convection
 
εb  0:26 and conduction (CHCC), and convection and diffusion (CHCD).
4 ¼ 42 þ ð41  42 Þ 0:260  εb  0:476 (9)
0:216 The CHDI module is used to model the adsorption dynamics
(based on the LDF model). The CHCC module is used in the
where Pr is the Prandtl number and where kg and ks are the
implementation of the two energy conservation equations for
thermal conductivity of the gas and solid phases. The values
the adsorption bed and the column wall domain. The CHCD
of the parameters d, 41 , and 42 are 0.75, 0.2, and 0.1,
module is used to implement the mass conservation
respectively.
equations.
The energy balance equation per unit length of column
wall can be written as [14,18]:
Model parameters
vTw  
rw cpw Aw ¼ 2pRin hin ðT  Tw Þ  2pRout hout Tw  Tf (10)
vt The model parameters of adsorbent and adsorption bed are
where rw , cpw and Aw are the density, specific heat and the wall shown in Table 1. The equilibrium isothermal parameters, the
cross-section area of the wall, respectively. Tf is the ambient LDF coefficients and the heat of adsorption for hydrogen,
temperature, hout and Rout are the heat transfer coefficient with carbon monoxide, carbon dioxide and methane adsorbed in
outer column wall and outer radius of column wall. the activated carbon PCB (Calgon Co.) and Zeolite 5A are given
Note that Eq. (7) and Eq. (10) are not necessary for the in Table 2. The adsorption bed is initially saturated with pure
solution of the adsorption bed temperature T and wall H2 under adsorption pressure 980 kPa before the breakthrough
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 8 2 3 6 e8 2 4 5 8239

Table 1 e Characteristics of adsorbents and adsorption bed and transport parameters [14].
Activated carbon Zeolite 5A Adsorption bed
Average pellet size, Rp (cm) 0.115 0.157 Length, L (cm) 100
Pellet density, rp (g/cm3) 0.85 1.16 Inside radius, Rin (cm) 3.71
Bulk density, rb (g/cm3) 0.482 0.746 Outside radius, Rou (cm)t 4.52
Bed porosity, εb 0.433 0.357 Heat capacity of column, cpw (J/kg/K) 523
Total void porosity, εt 0.78 0.77 Density of column, rw (g/cm3) 7.830
Heat capacity, cps (J/kg/K) 1046 920 Internal heat transfer coefficient, hin (cal/cm2/K/s) 2.1e-3
Thermal conductivity, ks (W/m/K) 0.406 0.462 External heat transfer coefficient, hout (cal/cm2/K/s) 5.4e-3

Table 2 e Langmuir parameters, LDF coefficient and isosteric heats of adsorption of activated carbon [11].
Component ai1 (mol/kg) ai2  102 (mol/K/kg) bi0  104 (1/bar) bi1 (K) ki (1/s) DHi (cal/mol)
Activated carbon
H2 16.943 2.100 0.6248 1229 0.700 2880
CO 33.850 9.072 2.311 1751 0.150 4300
CH4 23.860 5.621 34.780 1159 0.195 4290
CO2 28.7973 7.000 100 1030 0.0355 5240
Zeolite 5A
H2 4.314 1.06 25.15 458 0.700 2800
CO 11.8454 3.13 202 763 0.063 5000
CH4 5.833 1.192 6.0504 1731 0.147 5300
CO2 10.03 1.858 15781 207 0.0135 9330

experiment. The feed rate is 6.8 L/min. The ambient and initial adsorption pressure is kept at 980 kPa and the feed rate is
temperatures are set to 289.1 K. maintained at 6.8 L/min. The comparison of the simulation
results with the experimental data is shown in Fig. 1 to Fig. 3.
Fig. 1 shows the breakthrough curves of the gas mixtures.
Boundary and initial conditions
The results show good agreement with the experimental data.
The first impurity gas to break through from the bed is CO and
The boundary conditions for the mass, energy, and mo-
followed by CH4. The maximum that can be observed in the
mentum balance equations are respectively given by the
CO breakthrough curve is due to the onset of adsorption of
following relations:
CH4 on the activated carbon bed. As shown in Fig. 1, a plateau

vci
    þ  vci of the molar fraction of the CO appears between 500 s and
DL ¼ u c 0 ; t  c 0 ; t ; D ¼ 0; i ¼ 1; …; N
vz z¼0 vz z¼L
i i L
800 s, during this period the CH4 replaces CO and CO desorbing
(14) to gas phase. The breakthrough curve of hydrogen is strongly
influenced by the two other gases and shows a two-step drop.

vp vUz About 900 s later, the molar fractions of the mixture at the
pjz¼0 ¼ p0 ; ¼ 0; Uz jz¼0 ¼ Uzo ; ¼0 (15)
vz z¼L vz z¼L outlet are almost equivalent to the feed end that indicating the
mixture adsorption reaches equilibrium. The breakthrough

vT
    vT
KL ¼ εb cCpg Uz T 0 ; t  T 0þ ; t ; KL ¼0 (16)
vt z¼0 vt z¼L

Eq. (16) is a general boundary condition for non-adiabatic

and non-isothermal systems. For the adiabatic case, the heat
flux at z ¼ 0 is set to zero. The energy balance equation is not
required for the isothermal case, since the temperature of the
bed is kept constant. The initial conditions are thus:

cH2 ðz; 0Þ ¼ c0 ; cCO ðz; 0Þ ¼ 0; cCH4 ðz; 0Þ ¼ 0; cCO2 ðz; 0Þ ¼ 0

Tðz; 0Þ ¼ T0 ; Tw ðz; 0Þ ¼ T0 (17)
pðz; 0Þ ¼ p0 ; ni ðz; 0Þ ¼ n*i ðzÞ

Model validation

We used experimental data from reference [14] to validate the

model. A hydrogen ternary mixture (H2/CH4/CO ¼ 60.4/28.1/
11.5 vol%) is feed to an adsorption bed containing a Calgon Fig. 1 e Concentration breakthrough curves validated by
activated carbon. The bed was initially filled with pure experimental [14] and compared with adiabatic and
hydrogen and injection of gas mixture starts at t ¼ 0. The isothermal boundary conditions.
8240 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 8 2 3 6 e8 2 4 5

Fig. 2 e Temperature evolution validated by experimental [14] and shown with simulated concentrations (Solid: H2, Dot: CO,
Dash: CH4).

Fig. 3 e Temperature distributions validated by experimental [14] and associated with simulated concentrations at (a) 100 s,
(b) 300 s and (c) 500 s (Solid: H2, Dot: CO, Dash: CH4).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 8 2 3 6 e8 2 4 5 8241

time of a component is the time when this component breaks carbon bed to investigate the effects of gas filling velocity on
through the column and can be detected at the outlet of the the breakthrough curves and the bed temperature. As shown
column. It provides a criterion for a direct comparison of the in Fig. 4(a), the breakthrough curves of H2 indicates that the
breakthrough behaviours under different operating larger feed rate results in earlier breakthrough time and the
conditions. concentration wave front of H2 becomes steeper, which are
The effects of three thermal boundary conditions (adia- mainly contributed by the contact between adsorbates and
batic, isothermal and general) have been examined and the adsorbent decrease as feed rate increases. Fig. 4(b) shows the
results are shown in Fig. 1. For isothermal conditions, the temperature evolutions at 75 cm for discussion the effect of
breakthrough times of CO and CH4 are increased by 150 s feed rate. Larger feed rate induces higher peak temperature
compared to the general thermal boundary conditions (non and earlier temperature rising point. The higher peak tem-
isothermal non adiabatic). In the adiabatic case, the break- perature is due to the intensive adsorption heat generated by
through times of CO and CH4 are lowered by 80 s compared to faster feed flow. The earlier temperature rising point is due to
the general conditions. In addition, the adsorbed amounts of the faster mass transfer under larger velocity in the bed. The
CO and CH4 at the isothermal situation are larger than non- simulation results and experimental data [14] show good
adiabatic non-thermal and adiabatic situation. Those results agreements in both breakthrough curves and temperature
suggest that keeping the bed under isothermal or lower tem- evolutions.
perature conditions would improve adsorption ability and
that controlling the thermal effects during the adsorption Effect of axial mass dispersion coefficient
process may optimize PSA processes for improved efficiency.
Fig. 2 shows the evolution of temperature over time at the Under constant adsorption pressure 980 kPa and feed rate
following positions: 10 cm, 30 cm, 50 cm and 75 cm from the 6.8 L/min, a ternary hydrogen mixture is charged into acti-
feed end. As the mixture is charged into the bed, the tem- vated carbon bed under different axial mass dispersion coef-
peratures at the four positions keep rising until they reach a ficient aimed to study the influence of the axial mass
peak due to the heat generated by the adsorption process. The dispersion coefficient on the breakthrough curves and the bed
bed is eventually cooled by heat exchange with the environ- temperature. Figs. 5 and 6 show breakthrough curves and bed
ment. As shown in Fig. 2, when the bed height increasing from temperature profiles, respectively, which implies that as the
10 cm to 70 cm, temperatures profiles intend to appear two
peaks correlated to the maximum adsorption times of the CO
and CH4 respectively. The concentration wave fronts of CO
and CH4 become more and more separated due to the differ-
ence of their breakthrough times and their competitive
adsorption affinities.
Fig. 3 shows the simulated distributions of concentrations
and temperatures at 100 s, 300 s and 500 s, from which a more
intuitive understanding of the relationship between thermal
effect and breakthrough curve can be obtained. As shown in
Fig. 3, the concentrations of CO and CH4 increase slowly to
reach equilibrium, conversely, the concentration of H2 de-
creases gradually. Concentration curves can be divided into
three zones, namely, saturated zone, mass transfer zone
(MTZ), and clean zone. In saturated zone, all components reach
adsorption equilibrium. The impurity gases CO and CH4 have
not yet transferred to the clean zone where the H2 was adsor-
bed initially. In the mass transfer zone, component of H2 hap-
pens to desorption and CO and CH4 occur adsorption. The
pressure drop and the velocity variation in the bed predicted by
the simulations were found to be very small: the pressure dif-
ferenceDp between the inlet and outlet of bed was only around
70Pa. For practical simulations of adsorption process, we
conclude that the system pressure and the gas velocity can be
assumed to be constant to further simplify the adsorption
model.

Parametric study

Effect of feed rate

Under constant adsorption pressure 980 kPa, we charge Fig. 4 e Effect of feed rate on (a) concentration
different feed rates (4.5, 6.8, 9.1 L/min) into the activated breakthrough curves and (b) temperatures at 75 cm.
8242 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 8 2 3 6 e8 2 4 5
Fig. 5 e Effect of axial mass dispersion coefficient on
concentration breakthrough curves.
axial mass dispersion coefficient increases, the breakthrough
time of components decrease and the adsorbed amounts of
CO and CH4 reduce, and the roll-up extent of CO breakthrough
curve becomes moderate. which are mainly caused by large
axial mass dispersion coefficient increases the capacities of
mass transfer. Fig. 6 shows that the effect of the axial mass
dispersion decrease the bed temperature peaks and uni-
formize the bed temperature distributions in different loca-
tions. In this work, axial mass dispersion coefficient used in
mass conservation equation is calculated by Eq. (6), which is
the function of adsorbent size and fluid velocity, etc. Actually,
the effective particles radius of activated carbon (about
0.115 cm) and Darcy velocity (about 2.62 cm/s) in the adsorp-
tion bed are small, we calculated the practical axial mass
dispersion coefficient from Eq. (6) is around 1  105 m2/s.
According to the above simulation results, we can neglect the
axial mass coefficient to simplify the model referred from Figs.
5 and 6.
Fig. 6 e Effect of axial mass dispersion coefficient on temperatures at 10 cm, 30 cm, 50 cm and 70 cm.
Fig. 7 e Concentration breakthrough curves of quaternary
system (shown with experimental data [15]).
Effect of component composition
Figs. 7 and 8 show the breakthrough curves and bed temper-
ature profiles as a hydrogen quaternary mixture (H2/CO2/CH4/
CO ¼ 69/26/3/2 vol%) were feed into the activated carbon bed.
The adsorption pressure is 912 kPa and feed rate is 7 L/min. As
Fig. 7 shows, we can see that the simulation results of CO2 are
well consistent with experimental values [15]. The theoretical
predictions of CH4 and CO are a little higher than experi-
mental values and H2 is slightly lower than experimental
values. Compared with that of ternary mixture, a roll-up ap-
pears in CH4 breakthrough curve of quaternary mixture duo to
the more strongly adsorbed component of CO2. In quaternary
mixture, CO2 is the most strongly adsorbed component in
activated carbon and followed by CH4, CO and H2. The results
make us tentatively put forward that reducing the mixture of
CO and CH4 concentration and increasing the mixture of CO2
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 8 2 3 6 e8 2 4 5 8243

Fig. 8 e Temperature evolutions curves of quaternary system (shown with experimental data [15]).

concentration is benefit for obtaining higher purity of product

gas and getting a better rational adsorption time. The simu-
lation results show great agreement with experimental values
in the bed temperature profiles, as Fig. 8 shows. With respect
to that of ternary mixture, three temperature peaks can be
seen in temperature profiles at 75 cm of quaternary system,
the first is caused by CO adsorption, the second contributed by
CH4 adsorption and the last by CO2 adsorption. The appear-
ance of temperature roll-ups are mainly caused by the dif-
ference of adsorption abilities of CO, CH4 and CO2 in activated
carbon bed.

Effect of adsorbent

In order to study the influence of the adsorbent on the

breakthrough characteristics of the mixture, we also exam-
ined the use of zeolite 5A as adsorbent of PSA. A ternary
hydrogen mixture (H2/CH4/CO ¼ 60/30/10 vol%) was feed to
zeolite 5A bed at a rate of 6.8 L/min. The operating pressure
was 980 kPa. Fig. 9 shows the evolution of the breakthrough
curves over time. Unlike what was observed for activated
carbon, the breakthrough curve of H2 shows a one-step drop
due to the similar adsorption affinity of CO and CH4 in the
zeolite 5A bed. The breakthrough time of CO increases
approaching CH4. This is because that CO has stronger
adsorption affinity on zeolite 5A than that on activated car-
bon. Compared with the activated carbon, the zeolite 5A is a
more favourable adsorbent to remove CO. However, it is worth
noting that the breakthrough time of the mixture in zeolite 5A
bed is shorter by nearly 100 s compared to activated carbon,
which will decrease the operation time of adsorption process
of PSA cycle. Fig. 10 represents the evolution of the bed tem-
perature over time. Unlike what was observed for activated
carbon, the temperature at four sensor positions kept rising
and no roll-up appeared in the temperature profiles at 50 cm
and 70 cm, which is mainly contributed by the higher heat of
adsorption and the similar breakthrough time of CO and CH4
Fig. 9 e Breakthrough curves of ternary mixture (H2/CO/
CH4) in zeolite 5A bed.
in zeolite 5A bed. Figs. 9 and 10 show that the simulations and
the experiments [14] are in good agreement.
Conclusions
The heat and mass transfer properties during the adsorption
process in a PSA for hydrogen purification have been studied.
A one-dimensional multicomponent adsorption model has
been implemented to simulate the breakthrough curves for
several gas mixtures in Comsol. The Comsol modules: CHID,
CHCC and CHCD were used to implant the mass, energy and
momentum conservation equations in the Comsol model.
Good agreement between the simulation results and the
available experimental data was achieved for both break-
through curves and bed temperature profiles.
8244 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 8 2 3 6 e8 2 4 5

Fig. 10 e Temperature evolution of ternary mixture (H2/CO/CH4) in zeolite 5A bed.

The temperature in the adsorption bed was observed to DL axial mass dispersion coefficient, cm2/s
rise quickly up to the peak temperature during adsorption Dm molecular diffusion coefficient, cm2/s
process and then decreases slowly due to the heat exchange h heat transfer coefficient, W/m2/K
with the environment. The temperature of the bed close to the DH heat of adsorption, cal/mol
inlet was observed to rise faster than in the vicinity of the k LDF coefficient, s1
outlet. The order of adsorption affinity was CO2>CH4>CO > H2 kg thermal conductivity of gas, W/m/K
for the activated carbon PCB (Calgon Co.) and CO > CH4 > H2 for ks thermal conductivity of solid, W/m/K
zeolite 5A. KL effective axial thermal conductivity, W/m/K
The thermal effects during the adsorption process L column length, m
influenced strongly the behavior of the breakthrough M molecular weight, g/mol
curves. The thermal effect of the adsorption causes smaller N number of species
adsorption amounts and earlier breakthrough times of im- p adsorption bed pressure or partial pressure of
purity gases. Lowering the bed temperature or maintaining component, atm or Pa
the bed in isothermal conditions could lead to higher Pr Prandtl number, cpg m=kg
hydrogen purification performance (purity and recovery n* equilibrium adsorption amount, mol/kg
rate). n dynamic adsorption amount, mol/kg
The parametric study shows that faster feed rates lead to ns saturated adsorption amount, mol/kg
earlier breakthrough times, smaller uptakes of impurity gases R radius of column and particles, m, or universal gas
and higher temperature peaks. We also noted that the axial constant, 8.314 J/mol/K
mass dispersion coefficient can be neglected to simplify the Re Reynolds number, rg Vz ð2Rp Þ=m
model. Sc Schmidt number, m=rg =Dm
t time, s
T temperature of adsorption bed, K
Acknowledgments Tf ambient temperature, K
Tw wall temperature, K
We wish to thank the National Natural Science Foundation of Uz physical velocity in axial direction, m/s
China (NSFC Project No.51476120) and the Natural Sciences Vz superficial (Darcy) velocity, m/s
and Engineering Research Council of Canada (NSERC) for their y molar fraction of ith component
financial supports. z axial position in the bed, m

Nomenclature Greek symbols

εb bed porosity
Aw cross-section area of column wall, m2 rb bulk density, kg/m3
b Langmuir isotherm parameter, 1/bar rg gas density, kg/m3
c molar concentration of mixture, mol/m3 rp particle density, kg/m3
ci molar concentration of component i, mol/m3 rw wall density, kg/m3
cp specific heat, J/kg/K m viscosity, Pa$s
Cp specific heat, J/mol/K d, 4 parameters used in Eqs. (8) and (9)
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 8 2 3 6 e8 2 4 5 8245

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