International Conference on Chemical, Biological and Environment Sciences (ICCEBS'2011) Bangkok Dec.
, 2011
Simulation of a Single Bed Pressure Swing
Adsorption for Producing Nitrogen
Ashkan. Mostamand, Masoud. Mofarahi
Abstract— A troublesome aspect of nitrogen is that a single atom
released to the environment can cause a cascading sequence of
events, resulting ultimately in harm to the natural balance of our
ecosystems and to our very health. Reusing and recovering nitrogen
from available sources is one of the approaches to overcome the
disrupted natural nitrogen cycle. The adsorption dynamics of N 2 -
PSA process over carbon molecular sieve based on modified LDF
mass transfer rate are determined using a mathematical model
incorporated mass, energy and momentum balances. A VISUAL
BASIC code using finite difference method was developed to solve
the set of coupled differential-algebraic equations. Simulation studies
are performed to investigate the effect of changing various process
variables such as feed flow rate, bed length, purge to feed ratio and
cycle time are studied. The simulation results are agreed well with
some literature experimental results.
Keywords— Pressure swing adsorption, Reusing and recovering
nitrogen, Simulation.
I. INTRODUCTION
T HE public does not yet know much about nitrogen, but in
many ways it is as big an issue as carbon, and due to the
interactions of nitrogen and carbon, makes the challenge of
providing food and energy to the world's peoples without
harming the global environment a tremendous challenge. A
nitrogen atom that starts out as part of a smog-forming
compound may be deposited in lakes and forests as nitric acid,
which can kill fish and insects. Carried out to the coast, the
same nitrogen atom may contribute to red tides and dead
zones. Finally, the nitrogen will be put back into the
atmosphere as part of the greenhouse gas nitrous oxide, which
destroys atmospheric ozone. Ideally, it would be most
economically and environmentally beneficial to keep all the
nitrogen in this tight cycle. In reality, however, some leakage
occurs. Where there is too much nitrogen leakage, there can
be environmental harm. One of the approaches to reduce this
problem is to minimizing nitrogen use, such as optimizing its
uptake by plants and animals, recovering and reusing nitrogen
from available sources, and decreasing nitrogen emissions
from fossil fuel combustion. Recovering and reusing nitrogen
from available sources can be implemented by PSA. Also the
Ashkan. Mostamand is with the Department of Chemical Engineering,
Persian Gulf University, Bushehr, IRAN
Masoud. Mofarahi, is with the Department of Chemical Engineering,
Persian Gulf University, Bushehr, IRAN (corresponding author to provide
phone:+987714222192; fax:+987714540376; e-mail: mofarahi@pgu.ac.ir ).
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produced nitrogen by PSA is so economical.
Fuel gas and nitrogen are choices for blanket, purge or seal
gas but Fuel gas, it often is to be chosen in production areas
such as the oil patch where it is usually the only gas available
and producing nitrogen by other custom methods such as
cryogenic distillation is not economical. Although natural gas
(& other light hydrocarbons) is not an inert, it is used and
finally will be burned in flare and lead to environmental harm.
But producing nitrogen by PSA is economical and not harmful
for environment. Pressure swing adsorption (PSA) processes
for separation and purification of gaseous mixtures have
become important unit operations in the chemical process
industry. A large variety of binary and multi component gas
mixtures are commercially separated using this technology.
The applications range from bulk gas separations and drying
to trace contaminant removal [1]. There has been a growing
demand for economical and energy efficient gas separation
processes. The new generation of more selective adsorbents
developed in recent years has enabled adsorption-based
technologies to compete successfully with traditional gas
separation techniques, such as cryogenic distillation and
absorption [2]. Oxygen and nitrogen are produced from
atmospheric air by either of two methods depending upon the
volume of production. For high volume production, cryogenic
distillation of liquefied air is employed, whereas, for low to
medium volume production, air separations by methods such
as pressure swing adsorption are found to be more economical
[3].With extensive industrial applications, there is a
significant interest for an efficient modeling, simulation, and
optimization strategy. However, the design and optimization
of PSA processes have largely remained an experimental
effort because of the complex nature of the mathematical
models describing practical PSA processes. The mathematical
models are described by coupled nonlinear partial differential
equations (PDEs) distributed in space and time, with different
initial and boundary conditions defining the steps of the
process and high nonlinearities arising from nonisothermal
effects[2].
In 1985, Suzuki [4] has proposed a strategy in order to
estimate the cyclic steady state (CSS), assuming equivalency
of the PSA system operated on a Skarstrom cycle and the
continuous countercurrent flow (CCF) system. The model is
then largely simplified, and computation times are strongly
decreased. Raghavan et al. [5] modeled the N 2 –PSA system
by using a linear driving force (LDF) approximation for
 International Conference on Chemical, Biological and Environment Sciences (ICCEBS'2011) Bangkok Dec., 2011

intraparticle mass transfer and the linear equilibrium and (v) the pressure drop along the bed is considered by using
relationship for both oxygen and nitrogen. They also assumed the Ergun’s equation. The assumption of neglecting radial
isothermal behavior, negligible pressure drop, axial dispersed gradient was widely accepted by numerous studies, and the
plug flow model, linear pressurization and blow down, as well others are also common assumptions in simulating the
as frozen loading for all pressure changes steps. Hassan et al. adsorption processes.
[6] modeled the N 2 –PSA system by using the Langmuir
equilibrium relationships for both oxygen and nitrogen. This
is the main difference between two previously mentioned
models. Farooq et al. [7] and Shin et al. [8], [9] have
considered the pore diffusion for intraparticle mass transfer
instead of LDF, which is the most important difference from
the Raghavan model [5]. Sundaram [10] solved analytically
the CCF model for a single adsorbing component, under
Fig. 1 A four-step PSA cycle for single bed
isothermal conditions. Farooq and Ruthven [11] extended the
CCF model for a bulk separation process, and Farooq et al.
III. MATHEMATICAL MODEL
[12] applied the CCF model to a bulk PSA process operated
on a Skarstrom cycle in which the durations of the individual
steps are different. The simulations results obtained by Farooq The component and overall mass balances for the bulk
NOTATION
and Ruthven [11] and Carta [13] give only qualitative trends:
AW cross sectional area of q, adsorbed concentration,
the purities of the products are over-estimated by the CCF the wall, cm2 q*, q equilibrium adsorbed and
model. This deviation can be related to the accumulated average concentration,
products present in the interstitial volume at the end of each respectively, mol/g
B Extended Langmuir qm equilibrium parameter for
constant pressure step. equation parameter, extended Langmuir
In this study, the adsorption dynamics of process are kPa−1 equation, mol/g
determined using a mathematical model incorporated mass, C diffusion time R gas constant, J/molK
constant, s−1
energy and momentum balances. Simulation studies by Ci i component Rp pellet radius, cm
VISUAL BASIC code are performed to investigate the effect concentration in bulk
of changing various process variables, such as feed flow rate, phase, mol/cm3
C pg ,C ps ,C pw gas, pellet, and wall R Bi inside and outside radius
bed length, purge to feed ratio and cycle time. For Simulator heat capacity, ,R Bo of the bed, respectively,
validity, experimental and simulation results is compared. respectively, J/gK cm
Dc intracrystalline t time, s
II. PROCESS DESCRIPTION diffusivity, cm2/s
De effective diffusivity T atm temperature of atmosphere,
The original Skarstrom cycle was developed for a two-bed defined by solid K
process in which the pressurization and blowdown steps and diffusion model, cm2/s
DL axial dispersion T,T w Bed temperature and wall
adsorption and purge steps have equal durations. In this study coefficient, cm2/s temperature,respectively,K
a single fixed-bed of adsorbent with a four-step PSA cycle is hi internal heat transfer u interstitial velocity, cm/s
used to simplify investigation of each variable while the other coefficient, J/cm2 K s
ho external heat transfer yi mole fraction of species i
variables is kept as constant as possible [8], [9], [14]. The coefficient, J/cm2 K s in gas phase,
cycle is composed of four steps: (1) a high-pressure feed step dimensionless
−∆ H i
during which the mixture to be separated is fed to the bed; (2) average heat of z axial distance in bed from
adsorption, J/mol the inlet, cm
a blowdown step during which the pressure in the bed is
k parameter for extended α particle porosity,
decreased to a low value with gas flowing out of the feed end Langmuir equation dimensionless
of the bed; (3) the bed undergoes countercurrent purge with
product from the product tank to remove the heavy KL axial thermal ε, ε t voidage of adsorbent bed
conductivity, J/cm sK and total void
component, and finally (4) a pressurization step during which fraction, respectively,
the pressure is increased to high-pressure using feed. The bed dimensionless
is then subjected to the four-step PSA cycle, which is run L Bed length, cm µ viscosity, Pa s
P total pressure, kPa ρg, ρp, gas density, pellet density,
continuously until the cyclic steady state is reached [15]. ρ B ,ρ w bulk density
To understand the dynamic behaviors of a CMS PSA and bedw all density,
process, the mathematical models were developed on the basis respectively, g/cm3
Pr reduced ω LDF coefficient, s−1
of the following main assumptions: (i) the gas phase behaves
pressure,dimensionless
as an ideal gas mixture, (ii) radial concentration and Phase in the adsorption column are given by (1) and (2):
temperature gradients are negligible, (iii) thermal equilibrium
∂ 2 Ci 1 − ε ∂qi ∂ (C iU ) ∂C i
between adsorbents and bulk flow is assumed, (iv) the flow − DL +( ) + + = 0 (1)
pattern is described by the axially dispersed plug flow model, ∂Z 2
ε ∂t ∂z ∂t

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 International Conference on Chemical, Biological and Environment Sciences (ICCEBS'2011) Bangkok Dec., 2011

∂ 2C  1 − ε  n ∂ qi  ∂ (C U ) ∂C ∂Ci
− DL + ρ p  ∑ + + = 0 (2) DL = u feed (Ci − Ci ) (9)
 ε  i =1 ∂t 
Z =0 Z =0 −
∂Z 2 ∂z ∂t ∂Z Z =0

∂Ci
Another characteristic of the adsorption process is the =0 (10)
temperature variation caused by the heat of adsorption and ∂Z Z =L
desorption. Thermal effect on the total cyclic performance was u Z =0 = u feed (11)
considered to minimize the deviation in the prediction of
product purity. The energy balance for the gas phase also ∂u
Z =L =0 (12)
includes the heat transfer to the column wall. ∂Z
∂ 2T ∂T ∂u ∂T ∂T
− KL + ερ g C Pg (u +T ) + (ε t ρ g C Pg + ρ B C Ps ) KL = u feed ρ g C pg (T −T )
∂Z 2
∂Z ∂Z ∂t Z =0 Z =0 − (13)
∂Z Z =0
n
∂ qi 2hi
− ρ B (−∆ H i ) × ∑ + (T − Tw ) = 0 (3) ∂T
∂t RBi Z =L =0 (14)
i =1
∂Z
∂Tw Boundary conditions for purge (PU) step:
ρ wC pw Aw = 2πRBi hi (T − Tw ) − 2πRBo ho (Tw − Tatm ) (4)
∂t ∂Ci
DL = u purge (Ci − Ci ) (15)
Where, Ɛ t is the total void fraction (= ε + (1−ε) α), and ρ B is ∂Z Z =L Z =L Z = L−
the bed density, (= (1 − ε) ρ p ).
Ppurge
In order to consider the heat loss through a wall and the Ci − purge Z =L =( )Ci − AD Z =L
) (16)
heat accumulation in the wall, the corresponding energy PAD
balance is used.
u = u purge (17)
∂T Z =L
ρ wC pw Aw w = 2πRBi hi (T − Tw ) − 2πRBo ho (Tw − Tatm ) (5) ∂u
∂t Z =0 = 0 (18)
Where, Aw = π ( R Bo − R Bi ) .
2 2 ∂Z
∂T
In this study, the extended Langmuir was used to KL = u purge ρ g C pg (T Z =L −T Z = L−
) (19)
predict the adsorption isotherm while the modified LDF ∂Z Z = L
model was applied for the sorption rate by using
∂T
concentration-dependent diffusivity combined with Langmuir Z =0 =0 (20)
isotherm [16]. ∂Z
Bi qmi Pi Boundary conditions for Blow down (BL) step:
qi∗ = n
(6)
1 + ∑ B j Pj ∂Ci ∂u ∂T
j =1
= Z =0 = Z =0 =0
∂Z Z =0
∂Z ∂Z (21)
K ∂Ci ∂u ∂T
Where, qmi = K1 + K 2 × T , Bi = K 3 exp( 4 ) = Z =L = Z =L =0
T ∂Z Z =L
∂Z ∂Z
∂ qi 15D Initial conditions for fluid flow and heat flow:
= ωi (qi* − qi ) , ωi = 2 ei (7)
∂t rc Ci ( z ,0) = qi ( z ,0) = 0, T ( z ,0) = Tatm (22)
15Dei A finite difference method (FDM) was used to solve a
Where, 2
= CPr.5 (1 + Bi Pi ) 2 . mathematical model that considered of coupled partial
rc differential equations. The spatial dimension was discretized
The adsorption isotherm of N 2 and O 2 on CMS are by using a second order central difference and a second order
presented in Table 1, which came from the published data by backward difference for the second order and the first order
Bae et al. [16]. space derivatives. A VISUAL BASIC code is developed to
To consider the pressure drop effect across the bed, solve the set of these equations. The developed program is
Ergun’s equation was introduced as a momentum balance. user friendly and a user is capable of considering feed,
dP 150(1 − ε ) 2 1.75(1 − ε ) Langmuir parameters, diffusion rate constants, various steps
− = uaµ + bρu u , a = ,b = (8) such as equalization steps and bed conditions. In this work, a
dZ 4 R pε
2 2
2 R pε
four step PSA cycle (adsorption, blowdown, purge, and
Where u is the interstitial velocity. pressurization) is just applied to study process variables.
Boundary conditions for feed pressurization (PR) and
adsorption (AD) steps: IV. RESULTS AND DISCUSSION
The comparison of experimental data [8], [9], [14] for a

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 International Conference on Chemical, Biological and Environment Sciences (ICCEBS'2011) Bangkok Dec., 2011

single bed N 2 -PSA and results from simulation studies can be

TABLE II
seen in Fig. 3. The nitrogen fraction in the product was EQUILIBRIUM AND KINETIC DATA AND OTHER COMMON PARAMETERS
measured at a constant product flow for different adsorption USED IN THE PSA SIMULATIONS
step times. According to Fig. 2, A good agreement is observed Union Carbide
between experimental and simulation results. Adsorbent molecular sieve
RS-10
Equilibrium and kinetic data and other common Dry Air (79% N 2 , 21%
parameters used in the PSA simulations are given in table 2. Feed
O2)
In order to better understanding of the N 2 -PSA process, the Bed length (cm) 101.6
effect of process variables on the nitrogen purity and recovery Bed diameter (cm) 2.08
Bed voidage (cm) 0.34
obtained by a series of simulation runs. Adsorbent particle diameter (cm) 0.08
Adsorbent particle density (g/cm3) 1.1
Effect of Feed flow rate Saturation constant for O 2 (g mol/cm3) 2.1x 10-3
The effect of feed flow rate on N 2 -PSA was Saturation constant for N 2 (g mol/cm3) 2.1x 10-3
Equilibrium constant for O2 2.95
investigated at a constant cycle time for different adsorption Equilibrium constant for N2 5.92
flow rates. The results are shown in Fig. 3.It can be seen that Limiting diffusional time constant for O 2 (S-1) 2.75x 10-2
by increasing adsorption flow rate, Nitrogen purity and Limiting diffusional time constant for N 2 (S-1) 7.5x 10-4
recovery are decreasing and increasing, respectively.
For better understanding, O 2 purity in product as impurity is
plotted as a function of adsorption step time and flow rate in
Fig. 4. This figure is resulted from 1000 simulation runs. The
area which is O 2 purity is close to zero is situated at low flow
rates and low adsorption times. Also it can be seen that
increasing adsorption step time up to specific value cause to
decrease nitrogen purity but more than this value, has no
Fig. 2 Comparison of simulation and experimental product purity effect on nitrogen purity due to saturation condition in the
results at adsorption step as a function of adsorption time. column.

TABLE I
EQUILIBRIUM/RATE PARAMETERS AND HEATS OF ADSORPTION OF O 2 AND N 2
FOR CMS
Heat of
Diffusion rate
Langmuir Model adsorption
constants, C (s−1)
-∆(H) (kJ/mol)
Equilibrium
O2 N2 O2 N2 O2 N2
constants
5.817 × 1.13 ×
13.81 13.39 0.0275 0.00075
k1 (mol/g) 10−3 10−2
−7.512 −2.800 ×
k2 (mol/g K) × 10−6 10−5
7.94 × 30.89 ×
k3 (1/kPa) 10−6 10−5 Fig. 4 Combined effect of adsorption flow rate and time on O 2 purity
k4 (K) 1381 359.7
t2 =2 s, t3 =3 s, t4 =15 s, purge velocity = 4.54 cm/s

Effect of purge/feed ratio

The effect of varying the purge/feed ratio is shown in
Fig. 5.It is apparent that product purity increases with
purge/feed ratio but, on the other hand, an increase in
purge/feed ratio implies a lower recovery of nitrogen.

Effect of cycle time

As we can see in Fig. 6, in short cycle time, higher purity will
be achieved. Because there is not enough time for nitrogen
adsorption instead of oxygen. On the other hand, recovery is
Fig. 3 Effect of feed flow rate on (a) product purity and (b) recovery increasing slowly with cycle time. As a result, purity is
under constant cycle time decreased while high purity is not achieved.
t1 =35 s, t2 =2 s, t3 =3 s, t4 =15 s,
Purge velocity = 4.54 cm/s

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 International Conference on Chemical, Biological and Environment Sciences (ICCEBS'2011) Bangkok Dec., 2011
Fig. 5 Effect of purge to feed ratio on (a) product purity and (b)
recovery under constant cycle time
t1 =35 s, t2 =2 s, t3 =3 s, t4 =15 s
Fig. 6 Effect of cycle time on (a) product purity and (b) recovery
under Constant flow rate
t1 = t3 =.4 x cycle time sec t2 = t4 =.1 x cycle time sec
purge/feed = 0.5
Effect of Bed length
The effect of bed length is illustrated in Fig. 7. It may
be seen that purity will be increased by length of bed but this
will happen up to specific bed length. After this limit,
increasing length of bed has no effect on purity while
recovery is decreasing. So, the optimum bed length should be
chosen. Results of simulation show that temperature variation
during a cycle is less than 5 °C and pressure drop during
constant pressure steps is less than 5% .
Fig. 7 Combined effect of adsorption step time and Bed length on O 2
purity
t2 =2 s, t3 =3 s, t4 =15 s, Feed velocity = 1.93 cm/s
purge velocity = 4.52 cm/s
V. CONCLUSIONS
Excess nitrogen can be harmful to environment and
Reusing and recovering nitrogen from available sources is one
of the approaches to overcome the disrupted natural nitrogen
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cycle and can be done by PSA. Due to a significant interest
for an efficient modeling, simulation, and optimization
strategy, a non-isothermal dynamic model incorporating mass,
energy and momentum balances with concentration-dependent
rate model was used to predict kinetically controlled PSA
cycles. The developed model was applied to the N 2 –PSA
systems and a good agreement between the experimental and
simulation results are observed. The effects of feed flow rate,
purge to feed ratio, cycle time and bed length on product
purity and recovery are studied. The results show that the N 2
purity decreases when the duration of the cycle time and feed
flow rate increases. However, with increase of purge to feed
and bed length, product purity will be increased. All above
conclusions are reverse for recovery. It is observed that for a
specified cycle time, the effects of feed and purge flow on
purity and recovery are more than other process variables. The
effects of pressure drop and non-isothermal condition are not
shown significant change.
REFERENCES
[1] R. Rajasree, A.S. Moharir, Simulation based synthesis, design and
optimization of pressure swing adsorption (PSA) processes, J.
Computers and Chemical Engineering. 24 (2000) 2493–2505.
[2] A. Agarwal, T. Biegler, E. Zitney, Simulation and Optimization of
Pressure Swing Adsorption Systems Using Reduced-Order Modeling, J.
Ind. Eng. Chem. Res. 48 (2009) 2327–2343.
[3] M.Mofarahi, J. Towfighi, Oxygen Separation from Air by Four-Bed
Pressure Swing Adsorption, J. Ind. Eng. Chem. Res. 48 (2009) 5439–
5444.
[4] M.Suzuki, Continuous counter-current flow approximation for dynamic
steady state profile of pressure swing adsorption, J.
A.I.Ch.E.Symposium Series. 81 (1985) 67–73.
[5] N. S. Raghavan, D. M. Ruthven, Pressure swing adsorption part II:
numerical simulation of a kinetically controlled bulk gas separation, J.
AIChE J. 31 (1985) 2017-2025.
[6] M. M. Hassan, D. M. Ruthven, N. S. Raghavan, Air separation by
pressure swing Adsorption a carbon molecular sieve, J. Chem. Eng. Sci.
41 (1986) 1333-1343.
[7] S. Farooq, D. M. Ruthven, A comparison of linear driving force and
pore diffusion models for a pressure swing adsorption bulk separation
process, J. Chem. Eng. Sci. 45 (1990) 107-115.
[8] H. S. Shin, K. S. Knaeble, Pressure swing adsorption: A theoretical
study of diffusion induced Separation, J. AIChE J. 33 (1987) 654-662.
[9] H. S. Shin, K. S. Knaeble, Pressure swing adsorption: An experimental
study of diffusion induced Separation, J. AIChE J. 34 (1988) 1409-
1416.
[10] N. Sundaram, A noniterative solution for periodic steady states in gas
purification pressure swing adsorption, J. Industrial Engineering
andChemical Research. 32 (1993) 1686–1691.
[11] S. Farooq, D.M. Ruthven, Continuous countercurrent flow model for a
bulk PSA separation process, J. A.I.Ch.E. Journal. 36 (1990) 310–314.
[12] S.Farooq, M.N. Rathor, K. Hidajat, A modified continuous
countercurrent flow model for a PSA separation process, J. Transactions
of the Institution of Chemical Engineers. 72 (1994) 114–118.
[13] G. Carta, Adsorption calculations using the film model approximation
for intraparticle mass transfer, J. Adsorption. 9 (2003) 55–65.
[14] S. Farooq, M. N. Rathor, K. Hidajat, A predictive model for kinetically
controlled pressure swing adsorption separation process, J. Chem. Eng.
Sci. 48 (1993) 4129-4141.
[15] D.M.Ruthven, S. Farooq, K. S. Knaeble, Pressure Awing Adsorption,
VCH, New York, 1993.
[16] Y. Bae, J.H. Moon, H. Ahn, C.H. Lee, Effects of adsorbate properties
on adsorption mechanism in a carbon molecular sieve, J. K.Chem. Eng.
21 (2004) 712-720.