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Comparative study of zeolite 5A and zeolite 13X in air separation by pressure

swing adsorption

Article  in  Korean Journal of Chemical Engineering · January 2016

DOI: 10.1007/s11814-015-0232-6

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Korean J. Chem. Eng., 33(4), 1391-1401 (2016) pISSN: 0256-1115
DOI: 10.1007/s11814-015-0232-6 eISSN: 1975-7220
INVITED REVIEW PAPER

Comparative study of zeolite 5A and zeolite 13X in air separation

by pressure swing adsorption
Ehsan Javadi Shokroo*,†, Danial Jafari Farsani**, Hadiseh Khalilpour Meymandi*, and Nadia Yadollahi*

*PART-SHIMI Knowledge Based Company, Shiraz, Iran

**Bidboland Refining Co., NIGC, Bidboland, Iran
(Received 23 June 2015 • accepted 6 November 2015)

Abstract−The performance of zeolites 5A and 13X is numerically investigated in oxygen separation from air by a
two-bed PSA system. The effect of operating variables such as adsorption step time, PH/PL ratio and cycle time was
investigated on product purity and recovery. The simulation results showed that nitrogen adsorption capacity on zeo-
lite 13X was slightly more than the one on zeolite 5A. In the completely same operating conditions, zeolite 5A had a
larger mass transfer zone than zeolite 13X. Therefore, the adsorption and desorption rate of nitrogen on zeolite 5A is
less than zeolite 13X. Moreover, for the equal volume of adsorbed nitrogen on both adsorbents, zeolite 5A is more
capable rather than zeolite 13X to desorb much more volume of nitrogen at certain time. Furthermore, for achieving
oxygen with purity of 96%, utilizing zeolite 5A is more economical than zeolite 13X, when 5.5<PH/PL<7 and 75<cycle
time≤90.
Keywords: Pressure Swing Adsorption, Zeolite 5A, Zeolite 13X, Separation, Numerical Simulation

INTRODUCTION equilibrium conditions and oxygen is a process product. The sec-

ond one contains processes which utilize carbon molecular sieves
Air separation is one of the most important gas separation pro- (CMSs) as oxygen adsorbent. Based on kinetic separation in this
cesses in the chemical industry. The two most commonly meth- kind of category, oxygen is adsorbed owing to its faster perme-
ods used for the separation of oxygen and nitrogen from air are as ation and higher selectivity. Moreover, nitrogen is produced as a
follows: 1. Cryogenic distillation (by use of the relative volatility product in such these processes. The operating conditions, prod-
difference between two components). 2. Adsorption processes such uct purity and type of cycles are completely different in these two
as pressure swing adsorption (PSA), which works based on the categories. As a matter of fact, producing oxygen from air depends
selective adsorption capability of a component on a suitable adsor- on its applications in different industries.
bent. PSA technology is used to separate some gas species from a Oxygen is one of the most important products in the chemical
gas mixture under pressure according to the molecular characteris- industry. This chemical element is used in various processes, such
tics of the species and affinity for an adsorbent material. This pro- as refineries, manufacturing metal and other industrial operations.
cess operates at near-ambient temperatures. Specific adsorptive For instance, oxygen with high purity is used in different chemical
materials such as zeolites, activated carbon, molecular sieves are processes like steel construction, paper industries, wastewater treat-
used as adsorbents to adsorb the target gas species at high pres- ment and glass production. In 1907, oxygen was produced for the
sure. The process then swings to low pressure for the purpose of first time, when Linde built a first cryogenic distillation bed for air
desorbing the adsorbed material [1]. separation [3].
In addition to PSA, there is also temperature swing adsorption A widely used unit operation for gas separation or purification
(TSA), which is based on adsorption at operating conditions and is pressure swing adsorption used in most of the commercial ad-
regeneration at an elevated temperature. Similar to other adsorp- sorption applications [4-8]. Before 1980, PSA systems were used
tion processes, there are at least two stages in TSA processes: adsorp- with adsorption pressure greater than atmospheric pressure and
tion and desorption. Desorption in the cycle of this process includes desorption pressure near atmospheric conditions. In comparison
two stages of heating and cooling. After ending the heating stage, with cryogenic distillation process, these systems are low-cost in
the bed cooling operation starts in order that the first adsorption terms of initial investment (because of their simplicity), whereas
condition is obtained [1,2]. they are costly in terms of energy consumption. Vacuum swing
Generally, the common adsorption processes of air separation adsorption (VSA) systems (a kind of operations which work with
are divided into two categories. The first category consists of pro- adsorption pressure of slightly more than atmospheric pressure and
cesses which make use of zeolites as nitrogen adsorbent under the desorption pressure of about 0.2 atm) have been developed due to
availability of modified adsorbents and the less cost of vacuum equip-
†
To whom correspondence should be addressed. ment, rather than feed compression.
E-mail: [email protected] Over the past 40 years, several processes of PSA and VSA sys-
Copyright by The Korean Institute of Chemical Engineers. tems have been designed in order that pure oxygen from air mix-

1391
1392 E. J. Shokroo et al.

ture is produced. In O2-PSA industrial units the ratio of high pres- technology development can be associated with reducing the cost
sure, in the adsorption step, to low pressure, in the desorption step, of oxygen production via this process which is illustrated in Fig. 1.
(PH/PL), is considered to be one of the most important factors Several investigations and experimental researches have been
owing to determine required energy [9]. Typically, the pressure separately done in order to separate oxygen from air by PSA pro-
ratio of 4 and higher than 4 is utilized in the industries. Further- cess using zeolites 5A and 13X [9]. However, there are not any
more, many units with low capacity make use of two-bed systems investigations in accordance with the range of operating condi-
based on Skarstrom cycle, which are sometimes associated with an tions of these two adsorbents in order to compare their effects on
equalization step in order to improve the recovery. the process performance. Despite there being many investigations
Selecting a suitable adsorbent is a critical parameter to design a which were performed on the dynamics of a zeolite adsorption
PSA process. Generally, finding a suitable adsorbent is the first and desorption, there are not any investigations on the PSA pro-
step in developing adsorption separation process. As the separa- cess performance according to the type of adsorbent. For instance,
tion factor usually varies with temperature and considerably with the adsorption and desorption experiments for N2/O2 system on
composition, choosing appropriate conditions for maximizing the zeolite 5A, 10X, and 13X beds were performed by Jee et al. [27] to
separation factor is considered to be a major issue in the process study the dynamic characteristics of air separation adsorption pro-
design. Sometimes an initial selection of suitable adsorbents can cesses. Although zeolites 5A and 13X are both commonly used for
be directly achieved according to available Henry’s law constants. oxygen separation from air in the PSA process, there are still unan-
Most of the time, selecting the adsorbents can be easily achieved swered questions. For example, whether to use 5A or 13X at dif-
with measurement of chromatographic retention times (MCRT). ferent operating conditions when the product purity is more im-
Moreover, to achieve a quick and actual estimation of separation portant than recovery. Is zeolite 5A better than zeolite 13X when a
factors, chromatographic methods are better than the other meth- product recovery with an acceptable level of purity is considered?
ods because of their prediction in adsorption kinetic. Or which type of zeolite should be used when both purity and
Zeolites 5A and 13X are the most commonly used adsorbents recovery of oxygen are expected to be in the acceptable range?
in air separation for oxygen production. The unique properties of Answering these important questions requires strong and effec-
zeolites are originated from this fact that their surfaces are formed tive studies which have been investigated in the current study.
with negatively charged oxides. Moreover, the presence of isolated Two processes of oxygen separation from air by means of PSA
cations above their surface structure is another reason for their technique, using zeolites 5A and 13X as adsorbents, are simulated
uniqueness. Despite knowing the selectivity of O2/N2 by zeolite, at the same operating conditions in this study. The influence of
there was no progress in the case of air separation by adsorption adsorbent type on O2-PSA process performance is examined. Fur-
process until 1960 [9], even after the innovation of synthetic zeo- thermore, the importance of zeolite type in the quality and quantity
lites 5A and 13X and PSA cycles. The innovation of zeolites 5A of oxygen has been interpreted according to different operational
and 13X by Milton (1959) created conditions which were always variables. The simulated PSA process is a six-step process with the
available [3]. Zeolites are aluminosilicate crystallines of alkaline or following sequence: (I) co-current feed pressurization (PR); (II)
earth alkaline elements such as sodium, potassium and calcium. high-pressure adsorption (AD) step; (III) counter-current depres-
More detailed description of the zeolite structures is accessible in surizing pressure equalization (ED) step; (IV) counter-current blow
the literature [11]. There are many studies which have been done down (BD) step; (V) counter-current purge with a light product (PG)
on the separation of oxygen from air [12-26]. By these innova- step; (VI) co-current pressurizing pressure equalization (EP) step.
tions, the industrial ideologists were e ncouraged to examine the
feasibility of air separation at ambient temperature by applying ad- MATHEMATICAL MODEL
sorption processes, while the temperature for cryogenic processes
was 77 K. From an economical point of view, the history of PSA To develop a mathematical model for a PSA system, the follow-
ing assumptions were made:
1. Gas behaves as an ideal gas;
2. Total pressure versus time remains constant during adsorp-
tion and purge steps;
3. Total pressure changes nonlinearly with time during pressur-
ization, pressure equalization and blow down steps;
4. The flow pattern is axially assumed as plug-flow model;
5. Equilibrium equations for air are expressed as triple Langmuir-
Freundlich isotherm (oxygen, nitrogen and argon);
6. Rate of mass transfer is presented by linear driving force (LDF)
relations;
7. Bed is clean at initial state and there is no gas flow in it;
8. Air is considered a mixture of oxygen and argon (21%) and
Fig. 1. Cost of oxygen production by applying PSA process (in con- nitrogen (79%) as feed.
stant dollars). Zeolites 5A and 13X were used before 1990 According to these assumptions, dynamic behavior of system in
and zeolite LiLSX was used afterwards [10]. terms of mass, energy and momentum balances can be expressed

April, 2016
 Comparative study of zeolite 5A and zeolite 13X in air separation by pressure swing adsorption 1393

as follows: Adsorption isotherm parameters and diffusion rate constants of

Dimensionless partial mass balance for gas phase in the adsorp- oxygen, nitrogen and argon over zeolites 5A and 13X are presented
tion bed is [9,20,25,26]: in Table 1.
2 Overall dimensionless mass balance for gas phase in the adsorp-
1 ∂y ∂û ∂y 1 ∂P̂ 1 ∂T̂
− ⎛⎝ -----m-⎞⎠ ⋅ --------2-i + yi ⋅ ------ + û ⋅ ⎛ -------i + yi ⋅ ⎛ --- ⋅ ------ − --- ⋅ ------⎞ ⎞ tion bed is [12,19,23,28]:
Pe ∂ẑ ∂ẑ ⎝ ∂ẑ ⎝ P̂ ∂ẑ T̂ ∂ẑ ⎠ ⎠
∂y 1 ∂P̂ 1 ∂T̂ ∂P̂- ∂û û ∂P̂ ⎛ 1 ⎞ ⎛ ∂T̂ ∂T̂⎞
⎛ --1-⎞ ⋅ ----- ------ --- ------ --- ------ ------
+ -------i + yi ⋅ ⎛⎝ --- ⋅ ------ − --- ⋅ ------⎞⎠ (1) ⎝ P̂⎠ ∂τ + ∂ẑ + P̂ ⋅ ∂ẑ − ⎝ T̂⎠ ⋅ ⎝ ∂τ + û ∂ẑ ⎠
∂τ P̂ ∂τ T̂ ∂τ (8)
ρp ⋅ R ⋅ T0 ⋅ T̂⎞ ⎛ 1− ε⎞ 3 ⎛ ∂q̂ ∂qm, i⎞
ρp ⋅ R ⋅ T0 ⋅ T̂⎞ ⎛ 1− ε⎞ ⎛ ∂q̂ ∂qm, i⎞ + ⎛⎝ -------------------------
- ⋅ --------- ⋅ ∑ qm, i ⋅ -------i + q̂i ⋅ -----------
- =0
+ ⎛ -------------------------
- --------- q ⋅ -------i ⋅ -----------
- P0 ⋅ P̂ ⎠ ⎝ ε i=1⎠ ⎝ ∂τ ∂τ ⎠
⎝ P ⋅ Pˆ ⎠ ⋅ ⎝ ε ⎠ ⋅ ⎝ m, i ∂τ + q̂i ∂τ ⎠ = 0
0

Dimensionless equilibrium loading of ith component for solid phase Dimensionless energy balance for gas phase in the adsorption bed
in the adsorption bed is: is [13-15,18,24]:
1 ∂ T̂
2
∂T ∂û ρB ⋅ cp, s⎞ ∂T̂
∂qm, i ∂qm, i ∂T̂
- = ------------ × ------ = k2, iT0 × ∂T̂
----------- ------ − ⎛⎝ ----h-⎞⎠ ⋅ -------2- + ε ⋅ ⎛⎝û------ + T̂ ------⎞⎠ + ⎛⎝εt + ---------------
- ⋅ ------
∂τ ∂T̂ ∂τ ∂τ
(2) Pe ∂ẑ ∂z ∂ẑ ρg ⋅ cp, g⎠ ∂τ

Dimensionless loading of ith component for solid phase in the ad- ρB 3 ∂q̂ ∂qm, i⎞
− ⎛ -----------------------
-⎞ ⋅ ∑ ⎛qm, i ⋅ -------i + q̂i ⋅ -----------
- ⋅ (− ΔHi) (9)
sorption bed is (LDF relation): ⎝ T0 ⋅ ρg ⋅ cp, g⎠ i=1 ⎝ ∂τ ∂τ ⎠

⎛ ⎞ 2hi ⋅ L
⎜ β ⋅ yni ⎟ + ⎛⎝ ------------------------------------
-⎞ ⋅ (T̂ − T̂w) = 0
∂q̂i q̂i ∂qm, i⎞ RB, i ⋅ U0 ⋅ ρg ⋅ cp, g⎠
i i
- − q̂i⎟ − ⎛ --------
------- = αi ⋅ ⎜ ------------------------- - ⋅ ------------ (3)
∂τ ⎜ N
nj ⎟ ⎝ qm, i ∂τ ⎠
⎜ ∑ j j
1+ β ⋅ y ⎟ Dimensionless energy balance for the wall of adsorption bed is:
⎝ j=1 ⎠
∂T̂w 2π ⋅ RB, i ⋅ hi ⋅ L
According to Eq. (3), the LDF relation depends on various param- --------- = ------------------------------------ ⋅ (T̂ − T̂w )
∂τ ρw ⋅ cp, w ⋅ Aw ⋅ U0
eters, such as equilibrium parameter for the Langmuir model, mole (10)
2π ⋅ RB, o ⋅ ho ⋅ L ⎛ Tatm⎞
fraction of species i in the gas phase, average amount adsorbed − ------------------------------------ ⋅ T̂w − ---------
-
ρw ⋅ cp, w ⋅ Aw ⋅ U0 ⎝ T0 ⎠
and equilibrium parameter for the Langmuir model.
The equilibrium of triple Langmuir-Freundlich isotherm is as Cross-sectional area of adsorption bed wall is:
follows:
2 2
ni Aw = π ⋅ (RB, o − RB, i) (11)
βi yi
q̂*i = -------------------------
- (4)
N
nj Dimensionless boundary conditions for mass and energy balances
1+ ∑ βj ⋅ yj
j=1 are as follows:
Pressurization and adsorption steps:
where β, n and qm are as follows:
qm, i = k1+ k2T0T̂ (5) ⎛ ∂y
-------i⎞ m
= − Pe ⋅ û ⋅ (yi − yi
∂y
); -------i = 0 (12)
⎝ ∂ẑ ⎠ ẑ=0
−
ẑ=0
+
∂ẑ ẑ=1
ẑ=0
k4 ⎞
βi = k3 exp ⎛⎝ --------
- (6) ⎛ ∂T̂ ∂T̂
T0T̂⎠ ------⎞ h
= − Pe ⋅ û ⋅ (T̂ − T̂ ); ------ = 0 (13)
⎝ ∂ẑ ⎠ ẑ=0
−
ẑ=0
+
∂ẑ ẑ=1
ẑ=0
k6
n = k5 + --------
- (7) yi andT z=0 are composition of ith component in the inlet feed
T0T̂ z=0
− −

and the feed temperature in Eqs. (12) and (13), respectively.

Blow down and equalization to depressurization steps:
Table 1. Equilibrium parameters and adsorption heat of oxygen,
nitrogen and argon on zeolites 5A and 13X ∂yi ∂y ∂T̂ ∂T̂
------- = -------i = 0; ------ = ------ = 0 (14)
Zeolite 5A Zeolite 13X ∂ẑ ẑ=0 ∂ẑ ẑ=1 ∂ẑ ẑ=0 ∂ẑ ẑ=1
Parameters [21,22] [20]
Purge step:
N2 O2 N2 O2
⎛ ∂y
-------i⎞
∂y
= 0; ⎛ -------i⎞ = − Pe ⋅ û ⋅ (yi
m
− yi )
k1 ×103 (mol/g) 6.21 7.252 12.52 6.705 ⎝ ∂ẑ ⎠ ⎝ ∂ẑ ⎠ ẑ=1 ẑ=1
+ −
(15)
5
k2 ×10 (mol/g·K) −1.27 −1.820 −1.785 −1.435 ẑ=0 ẑ=1

k3 ×104 (1/atm) 1.986 54.19 2.154 3.253 ⎛ ∂T̂

------⎞
∂T̂
= 0; ⎛ ------⎞
h
= − Pe ⋅ û ⋅ (T̂ − T̂ ) (16)
k4 (K) 1970 662.6 2333 1428 ⎝ ∂ẑ ⎠ ⎝ ∂ẑ ⎠ ẑ=1
+
ẑ=1
−

ẑ=0 ẑ=1
k5 2.266 −1.101 1.666 −0.3169 where, yi andT z=L are concentration of the ith component in
+ +
k6 (K) −396.5 656.4 −245.2 387.8 z=L
the product of AD step and the output flow temperature of AD
Heat of adsorption (cal/mol) 5470 3160 4390 3060 step, respectively.
LDF constant (s−1) 0.05 0.15 0.197 0.62 Equalization to pressurization step:

Korean J. Chem. Eng.(Vol. 33, No. 4)

1394 E. J. Shokroo et al.

∂yi⎞
⎛ ------ ∂y The effects of production pressure, purge and product flow rates,
- m
= − Pe ⋅ û ⋅ (yi − yi ); -------i = 0 (17)
⎝ ∂ẑ ⎠ ẑ=0
−
ẑ=0
+
∂ẑ ẑ=1 and production step duration on the product purity and recovery
ẑ=0
are investigated for both cycles and compared. Furthermore, a lin-
⎛ ∂T̂
------⎞ h
= − Pe ⋅ û ⋅ (T̂ − T̂
∂T̂
); ------ = 0 (18)
⎝ ∂ẑ ⎠ ẑ=0
−
ẑ=0
+
∂ẑ ẑ=1
ẑ=0

yi andT
−
are concentration of ith component in the outlet
−
z=0 z=0
flow of ED step and the outlet flow temperature of ED step in Eqs.
(17) and (18), respectively.
Ergun equation is utilized to investigate the pressure drop across
the adsorption bed [16,17].

− ------ = [a ⋅ μ ⋅ U0 ⋅ û + b ⋅ ρ ⋅ U0 ⋅ û ⋅ û ] ⋅ ⎛⎝ -----⎞⎠
dP̂ 2 L
(19)
dẑ P0
2
150 (1− ε)- (1− ε)
a = --------2 ⋅ --------------- ; b =1.75-------------- (20)
4Rp ε
2 2Rpε

Moreover, a non-linear equation for variable pressure step is used

to study the pressure changes versus dimensionless time [16,17]:
2
P̂(τ) = A ⋅ τ + B ⋅ τ + C (21)

Physical properties of adsorbents and characteristics of adsorption

bed are depicted in Tables 2 and 3, respectively.

RESULTS AND DISCUSSION

The fourth-order Runge-Kutta Gill scheme was used to solve a

mathematical model considered as coupled partial differential equa-
tions. The experimental data obtained from the literature has been
simulated to validate the simulation results in this study [17,20,21].
An experimental and simulation study of a PSA unit which is
running a traditional Skarstrom cycle and a Skarstrom cycle with
co-current equalization owing to separate oxygen from air using a
5A zeolite has been proposed by Mendes et al. in 2001.

Table 2. Physical properties of beds and adsorbents

Zeolite 5A Zeolite 13X
Characteristic
[21,22] [20]
Type Sphere Sphere
Average pellet size, RP (cm) 0.157 0.070
Pellet density, ρp (g/cm3) 1.160 1.170
Heat capacity, Cps (cal/g·K) 0.320 0.320
Bed porosity, ε 0.314 0.391
Bed density, ρB (g/cm3) 0.795 0.713

Table 3. Adsorption bed properties [29]

Length, L (cm) 76
Inside radius, RBi (cm) 2.138
Outside radius, RBo (cm) 2.415
Heat capacity of the column, Cpw (cal/g·K) 0.12
Density of column, ρw (g/cm3) 7.83
Internal heat-transfer coefficient, hi (cal/cm2 ·K·s) 9.2×10−4
External heat-transfer coefficient, ho (cal/cm2 ·K·s) 3.4×10−4 Fig. 2. (a) Numerical simulation of experimental data in this work
[17]. (b) Numerical simulation of experimental data in this
Axial thermal conductivity, KL (cal/cm·s·K) 6.2×10−5 work [20]. (c) Numerical simulation of experimental data in
Axial dispersion coefficient, DL (cm2/s) 1×10−5 this work [21].

April, 2016
 Comparative study of zeolite 5A and zeolite 13X in air separation by pressure swing adsorption 1395

ear driving force representation of the dusty gas intra particle mass adsorption dynamics in their studies [21].
transport is considered in their model [17]. Moreover, a small- Figs. 2(a) and (b) indicate the effect of product flow rate and P/F
scale two-bed six-step PSA process using zeolite 13X was per- on the purity and recovery of oxygen during PSA process, respec-
formed by Jee et al. to provide oxygen-enriched air. The effects of tively. The impact of temperature variations in gas phase during
different operating parameters such as the P/F ratio, adsorption adsorption as a function of time is illustrated in Fig. 2(c). It is obvi-
pressure, feed flow rate, and adsorption step time were investigated ously seen that there is a relatively high accuracy in the simulation
experimentally under the nonisothermal condition. They showed of experimental data [29]. Breakthrough curves for nitrogen and
that there is a strong effect of feed flow rate on O2 purity [20]. The oxygen on both zeolites 13X and 5A are shown in Figs. 3(a) and
effects of adsorption and desorption on zeolite 5A and CMS beds (b), respectively. The term “break-through time” is originated from
were investigated in a mixture of N2/O2/Ar by Jee et al. in 2004. A the response of initially cleaned bed per a flow with a constant
non-isothermal mathematical model was applied to simulate the composition. As an initial condition, it is assumed that the adsorp-
tion bed is pressurized with a non-adsorptive gas. As shown in
Fig. 3(a), oxygen exits from the top of zeolite 13X earlier than
nitrogen at a time of approximately 230 seconds [29].
As time is passing, high roll-up phenomenon is observed in the
case of oxygen. Owing to high roll-up phenomenon effect, oxy-
gen concentration is approximately 4.5 times more than feed con-
centration during the time of 400-500 seconds. Occurring high roll-
up phenomenon in the case of oxygen is because there is a com-
petitive adsorption between oxygen and nitrogen molecules to be
adsorbed on the adsorbent.
This competitive adsorption can be developed according to
nitrogen and oxygen properties like polarizability, dipole moment
and quadruple moment. The isotropic polarizability is defined as
the average of the diagonal terms of the polarizability tensor. Nitro-
gen and oxygen molecules are symmetrical and thus they are not
dipole. Both of these molecules are diatomic molecules. The polar-
izability of oxygen and nitrogen is 1.562 and 1.710 (Å3), respectively.
Furthermore, the bond description of oxygen molecule is double
bond (O=O); however, the nitrogen bond description is triple
bond (N#N). Moreover, the electric quadruple moment of nitro-
gen is (xx, yy, zz)=(0.697, 0.697, −1.394). Besides, the molecular
diameters of oxygen and nitrogen are 3.8 Å and 4.2 Å, correspond-
ingly [30].
The adsorption kinetics and equilibrium have been investigated
in this study. In fact, the adsorption capacity will be greater for
more polarity molecules which is consistent with adsorption equi-
librium. On the other hand, the rate of adsorption will be greater
for molecules with smaller sizes, which is based on the adsorption
kinetics.
The superiority of adsorption equilibrium mechanism than ad-
sorption kinetic mechanism in zeolite adsorbents for separation of
oxygen and nitrogen has been depicted in the literature [1].
Oxygen is affected by the high roll-up phenomenon because
nitrogen adsorption on the adsorbent sites is much more than
oxygen adsorption. Therefore, oxygen concentration is relatively in-
creased rather than feed concentration. While time reaches nitro-
gen breakthrough at the time of 550 seconds, oxygen concentra-
tion is starting to be reduced. As clearly shown in Fig. 3(a), the high
Fig. 3. (a) The simulated breakthrough curves of zeolite 13X for roll-up phenomenon does not occur in the case of nitrogen due to
oxygen and nitrogen at adsorption pressure of 6 bar and its strong adsorption on zeolite 13X adsorbent. Fig. 3(b) presents
feed flow rate of 5 LSTP/min. The adsorption bed was ini- the breakthrough curves in zeolite 5A. According to this figure,
tially saturated with a non-adsorptive gas. (b) The simulated
breakthrough curves of zeolite 5A for oxygen and nitrogen
although oxygen penetration on zeolite 5A is similar to the one on
at adsorption pressure of 6 bar and feed flow rate of 5 LSTP/ zeolite 13X, nitrogen penetration occurs at the time of 450 sec-
min. The adsorption bed was initially saturated with a non- onds. By comparing Figs. 3(a) and 3(b), the breakthrough curves
adsorptive gas. for zeolite 5A is slightly broader than zeolite 13X. In addition, the

Korean J. Chem. Eng.(Vol. 33, No. 4)

1396 E. J. Shokroo et al.

capacity of nitrogen adsorption on zeolite 13X is slightly more than expected, nitrogen adsorption capacity on zeolites 13X and 5A en-
the one on zeolite 5A. Moreover, the high roll-up phenomenon hances with pressure increasing. Although nitrogen adsorption
occurs in both zeolites 5A and 13X in the case of oxygen. The ad- capacity is approximately the same on both adsorbents, nitrogen
sorption capacity in the adsorption bed depends on the factors such breakthrough on zeolite 13X occurs with a steeper slope rather than
as pressure, temperature, flow rate [9,20]. Actually, the adsorption zeolite 5A in different adsorption pressures. Furthermore, the effect
and desorption cycle of a PSA system operates by pressure increas- of increasing the adsorption pressure on zeolite 13X is more effec-
ing and decreasing. Adsorption and desorption phenomenon are tive than the other zeolite and the adsorption capacity increases
inherently exothermic and endothermic, respectively. Therefore, gradually. Therefore, the rate of nitrogen adsorption on zeolite 13X
the optimal setting of temperature is very important owing to bet- is more than the one on zeolite 5A due to different kinetic param-
ter performance of adsorption and desorption phenomenon. On eters of these two zeolites. It is depicted in Table 1 that the nitro-
the other hand, the adsorption of impurities on the adsorbent bed gen LDF coefficient for zeolite 13X is almost four-times more than
is a function of retention time on the adsorbent. Consequently, the the one on zeolite 5A. On the other hand, the rate of nitrogen
flow rate factor is necessary for better performance of system. adsorption on zeolite 13X is approximately four-times more than
The concentration of nitrogen on zeolites 13X and 5A in terms the one on zeolite 5A in the completely same conditions. The dif-
of different adsorption pressures and time are presented in Figs. ference in the rate of adsorption can be investigated in the differ-
4(a) and (b), respectively. As pressure increases, the adsorption rate ent mass transfer zones (MTZs) of these two zeolite beds.
of more strongly adsorbed component increases [9,20]. As it is Oxygen concentration along the bed length for zeolites 13X and
5A in different times have been depicted in Figs. 5(a) and (b), re-
spectively. Obviously, the slope of oxygen concentration curves in
the case of zeolite 13X is faster than zeolite 5A. On the other hand,
there is a larger MTZ for zeolite 5A rather than zeolite 13X in the

Fig. 4. (a) The outlet mole fraction of nitrogen form zeolite 13X at Fig. 5. (a) Distribution of oxygen concentration along the length of
different adsorption pressures and feed flow rate of 4 LSTP/ zeolite 13X during adsorption process in different times.
min. The adsorption bed was initially saturated with a non- The feed flow rate is 5 LSTP/min and the adsorption pres-
adsorptive gas. (b) The outlet mole fraction of nitrogen form sure is 6 bar. (b) Distribution of oxygen concentration along
zeolite 5A at different adsorption pressures and feed flow the length of zeolite 5A during adsorption process in differ-
rate of 4 LSTP/min. The adsorption bed was initially satu- ent times. The feed flow rate is 5 LSTP/min and the adsorp-
rated with a non-adsorptive gas. tion pressure is 6 bar.

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 Comparative study of zeolite 5A and zeolite 13X in air separation by pressure swing adsorption 1397

Fig. 6. (a) The outlet simulated concentration of gas phase from Fig. 7. (a) The outlet concentration of nitrogen from zeolite 13X in
zeolite 13X during desorption at pressure of 0.1 bar. The de- the gas phase as a function of desorption pressure and time.
sorption bed was completely clean in the initial state. (b) The Desorption process is applied with a non-adsorptive gas. (b)
outlet simulated concentration of gas phase from zeolite 5A The outlet concentration of nitrogen from zeolite 5A in the
during desorption at pressure of 0.1 bar. The desorption bed gas phase as a function of desorption pressure and time. De-
was completely clean in the initial state. sorption process is applied with a non-adsorptive gas.

completely equal conditions. The bed with smaller MTZ has larger centration drop in the outlet of zeolite 5A occurs at the time of
adsorption rate in the completely same conditions [9,20,22]. More- about 155 seconds;
over, it is considerable to mention that the transfer rate of MTZ is 2. However nitrogen concentration in the outlet of zeolite 13X
almost equal for both adsorbents. approaches zero after about 180 seconds, nitrogen concentration
In the dynamic study of adsorption beds it is considerable to in the outlet of zeolite 5A does not approach zero after approxi-
investigate desorption curves. The desorption curves of zeolites 13X mately 300 seconds and its value is almost 10%.
and 5A are illustrated in Figs. 6(a) and (b), respectively. To simu- Besides, according to these figures, nitrogen desorption capac-
late desorption over the beds, it is assumed that a pure inert gas is ity from zeolite 5A is more than zeolite 13X. On one hand, for the
utilized for cleaning the beds. By passing the inert gas through the equal volume of adsorbed nitrogen on adsorbents, zeolite 5A is
bed in a pressure of 0.1 bar, nitrogen with high concentration is more capable than zeolite 13X owing to desorb much more vol-
first desorbed from top of the bed. As nitrogen is desorbed, a little ume of nitrogen in a certain time. This can be justified in the ad-
adsorbed oxygen is removed from the bed with nitrogen. As time sorption and desorption hysteresis loops of zeolites 13X and 5A.
passes and the desorbed volume of nitrogen and oxygen gases On the other hand, in the completely same conditions, the rate of
decreases, the concentration of inert gas in the outlet of bed begins nitrogen desorption from zeolite 13X is more than the one on zeo-
to increase. By comparing Figs. 6(a) and (b), it is considerable to lite 5A owing to smaller MTZ in zeolite 13X rather than zeolite
point out: 5A. Similarly to adsorption capacity, the desorption capacity in ad-
1. The main drop of nitrogen concentration in the outlet of zeo- sorbent beds depends on some parameters such as pressure, tem-
lite 13X occurs at the time of about 125 seconds, while this con- perature, time, flow rate [9,20], which have been described in details

Korean J. Chem. Eng.(Vol. 33, No. 4)

1398 E. J. Shokroo et al.

Fig. 8. The simulated purity and recovery of oxygen as a function Fig. 9. The simulated purity and recovery of oxygen versus the ratio
of adsorption time. The feed flow rate is 20 LSTP/min, ad- of operational pressures. The feed flow rate is 2 LSTP/min
sorption pressure is 6 bar, desorption pressure is 1 bar and and the ratio of P/F is 0.1. ED and BD time steps are 5 and
the ratio of P/F is 0.1. ED and BD time steps are 5 and 15 15 seconds, respectively.
seconds, respectively.
decreased zone. It is depicted that the performance of a PSA sys-
above. tem for oxygen separation from air can work better, where zeolite
Figs. 7(a) and (b) propose nitrogen concentration in the bed out- 13X is utilized under simulated operational conditions. Fig. 9
lets for different desorption pressures as a function of time. The shows the effect of O2-PSA system performance versus PH/PL for a
desorption amount of more strongly adsorbed component reduces 60-second cycle. Where 8>PH/PL, the performance of PSA pro-
by increasing the pressure [9,20]. As expected, nitrogen desorp- cess in terms of oxygen purity and recovery on zeolite 13X is bet-
tion capacity from both zeolites 13X and 5A increases by reducing ter than zeolite 5A. This result can also validate the curve behavior
the pressure. Despite the rate of nitrogen desorption from zeolite in Fig. 8. Where 8≤PH/PL≤28.5, the rate of product recovery using
13X is more than zeolite 5A, the capacity of nitrogen desorption zeolite 5A is more than zeolite 13X. Moreover, it is better to apply
from zeolite 5A is more than the one on zeolite 13X. As men- 25≤PH/PL≤28.5 (VSA system), for both adsorbents, in order to
tioned above, the adsorption capacity and the rate of adsorption achieve oxygen with high purity and recovery. It occurs because
are based on molecules with more polarity and molecules with purity and recovery are at their maximum values in Fig. 9. The
small sizes, respectively. Therefore, there is smaller pore size on high value of PH/PL ratio for N2/O2 system gives the meaning of
zeolite 13X rather than zeolite 5A. In addition the polarity of zeo- VSA system. Because pressure higher than 6 bar is not required
lite 5A is more than zeolite 13X [11]. The importance of this issue for oxygen production in a PSA system, which is considered as a
can be followed in product recovery and productivity curves. zeolite adsorbent system [9]. Due to this fact, when the value of
Fig. 8 shows oxygen purity and recovery as a function of ad- PH/PL is high, the desorption pressure is approximately zero which is
sorption time for both zeolites. As obvious, there is a light effect VSA system. When a VSA system is utilized, the desorption phe-
on oxygen purity for both adsorbents with increasing the adsorp- nomenon is done in vacuum conditions due that the adsorbents
tion time at first. Afterwards, the product purity begins to decline are well decontaminated in the desorption step. Therefore, the purity
with a sharp slope by increasing the time more than 15 and 20 in the adsorption step and recovery will reach their maximum values.
seconds for zeolites 5A and 13X, respectively. The reason for oxygen Consequently, the overall results obtained from Fig. 9 are as follows:
purity behavior versus the adsorption time is due to breakthrough 1. It is better to apply zeolite 13X in O2-PSA system to achieve an
time. In the PSA process, the adsorption time is determined ac- optimal process performance in terms of product purity and recov-
cording to the study on breakthrough curves. In fact, the adsorp- ery in the range of 5≤PH/PL≤8 in comparison with zeolite 5A.
tion time is a required time for occurring breakthrough time. After 2. Applying a PSA system in the range of 8≤PH/PL≤28.5 with
this time, the product purity decreases while the entire capacity of zeolite 5A operates better than zeolite 13X, when much more oxy-
the bed has not been utilized before this time. gen recovery is considered. Note that the performance of men-
Therefore, the adsorption time must be close to the breakthrough tioned unit will improve by increasing the ratio of PH/PL (in Fig. 9,
time in order that the best process performance in terms of the optimal ratio of PH/PL is 22.5).
adsorption time is achieved [31]. The rate of oxygen recovery for 3. The performance of oxygen separation unit using a VSA system
both adsorbents increases at first and then it reduces. It is consid- (25≤PH/PL≤28.5) is almost the same for both zeolites 13X and 5A.
erable to note that the slope of recovery curve for zeolite 13X is Cycle time is another variable which is effective for the perfor-
gradually greater than zeolite 5A in incremental zone, while the mance of the PSA unit in oxygen separation from air. Figs. 10(a)
slope of recovery curve is approximately equal for both zeolites in and (b) show that oxygen purity depends on cycle time in differ-

April, 2016
 Comparative study of zeolite 5A and zeolite 13X in air separation by pressure swing adsorption 1399

economical than zeolite 13X when a higher cycle time is applied,

because the cycle time can be increased at a low ratio of PH/PL.
Accordingly, applying zeolite 5A is more economical than zeolite
13X while 5.5<PH/PL<7 and 75<cycle time≤90, in order that oxy-
gen purity of 96% is achieved.

CONCLUSIONS

Two types of zeolites, zeolite 5A and zeolite 13X, were simulated

in a laboratory scale of PSA unit in the same operational condi-
tions. Desorption and adsorption dynamics of zeolites 5A and
13X were investigated to study the behavior of these zeolites. Fur-
thermore, the dependency of PSA process performance in terms
of product purity and recovery over operational variables such as
adsorption time, PH/PL and cycle time was compared in this study.
The results obtained from dynamic simulation of beds showed
that:
The breakthrough curves for zeolite 5A are broader than zeo-
lite 13X. Moreover, nitrogen adsorption capacity on zeolite 13X is
relatively more than the one on zeolite 5A. In addition, the high
roll-up phenomenon occurs for both zeolites in the case of oxygen.
There is a larger mass transfer zone (MTZ) for zeolite 5A rather
than zeolite 13X in the completely same conditions. Therefore, the
adsorption rate of zeolite 13X is much more than the one on zeo-
lite 5A. The rate of nitrogen desorption from zeolite 13X is more
than zeolite 5A owing to its smaller MTZ. On the other hand, for
equal volume of adsorbed nitrogen on the both adsorbents, zeo-
lite 5A is more capable to desorb much more volume of nitrogen
rather than zeolite 13X at certain time.
The effect of PH/PL on PSA process performance was modeled.
The results obtained from this simulation are as follows:
1. Zeolite 13X is more effective than zeolite 5A in the O2-PSA
system. Furthermore, an optimal process performance in terms of
Fig. 10. (a) The distribution of oxygen concentration versus the ratio
product purity and recovery in the range of 5≤PH/PL≤8 is achieved
of operational pressures in different cycle times for zeolite by applying zeolite 13X rather than zeolite 5A.
13X. The product flow rate is 2 LSTP/min and the ratio of 2. The performance of zeolite 5A in the range of 8≤PH/PL≤28.5
P/F is 0.1. (b) The distribution of oxygen concentration ver- in a PSA system is more effective than zeolite 13X. Note that the
sus the ratio of operational pressures in different cycle times performance of a PSA system will improve via increasing the ratio
for zeolite 5A. The product flow rate is 2 LSTP/min and of PH/PL.
the ratio of P/F is 0.1. 3. It is shown that in a VSA system (25≤PH/PL≤28.5), the perfor-
mance of oxygen separation unit is approximately identical by apply-
ent ratios of PH/PL for both zeolites 13X and 5A, respectively. The ing both zeolites 5A and 13X.
difference in PSA process performance in oxygen separation uti- Furthermore, simulation results of the cycle time effects showed
lizing zeolites 5A and 13X can be seen by white dashed line in the that:
surrounded area in Figs. 10(a) and (b). Applying higher cycle time Applying zeolite 5A is more economical than zeolite 13X in
and adjusting the ratio of 15>PH/PL leads to high purity product. order to achieve oxygen with purity of 0.96, when 5.5<PH/PL<7
According to the definition, the productivity of the PSA unit over and 75<cycle time≤90.
the utilized adsorbent is the ratio of received product rate to the
used cycle time [20]. ACKNOWLEDGEMENT
On one hand, applying a higher cycle time will increase the
unit productivity. On the other hand, increasing the ratio of PH/PL The authors gratefully acknowledge BIDBOLAND refinery plant
will increase the operating costs. is in agreement with this research.
It is suggested that at a low ratio of PH/PL and with respect to
maintaining high product purity, it is possible to increase the cycle NOMENCLATURE
time. According to the white dashed line in the surrounded area
in Figs. 10(a) and (b), it is understandable that zeolite 5A is more Aw : cross-sectional area of the wall [cm2]

Korean J. Chem. Eng.(Vol. 33, No. 4)

1400 E. J. Shokroo et al.

AD : adsorption step H : higher operating pressure

BD : blow down step i : component i
Cpg, Cps, Cpw : gas, pellet, and wall heat capacities, respectively [cal/ L : lower operating pressure
g·K] p : pellet
DL : axial dispersion coefficient [cm2/s] g : gas phase
G : purge to feed ratio [kgfeed/kgpurge] s : solid
hi : internal heat-transfer coefficient [cal/cm2·K·s] w : wall
ho : external heat-transfer coefficient [cal/cm2·K·s]
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