Chemical Engineering Journal 226 (2013) 444–459

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Chemical Engineering Journal

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

The enhancement of hydrogen recovery in PSA unit of domestic petro-

chemical plant
M.R. Rahimpour a,b,⇑, M. Ghaemi a, S.M. Jokar a, O. Dehghani a, M. Jafari a, S. Amiri a, S. Raeissi a
a
Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran
b
Department of Chemical Engineering and Materials Science, University of California, Davis, 1 Shields Avenue, Davis, CA 95616, United States

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 The PSA unit of a domestic

petrochemical plant is simulated.
 An unsteady-state heterogeneous
mathematical model is used for
simulation.
 Three suitable sub cycle time for
three different operating conditions
are estimated.
 The optimal feed flow rate is obtained
for enhancement of hydrogen
recovery.
 The optimal cycle time is obtained for
enhancement of hydrogen recovery.

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

Article history: In this work a mathematical model is employed to simulate the industrial layered PSA unit of domestic
Received 3 January 2013 petrochemical plant which operates for purification of hydrogen. The outlet stream of this plant has
Received in revised form 25 March 2013 about 99.99% purity in hydrogen and the hydrogen recovery is about 75%. A good agreement was
Accepted 10 April 2013
observed between the simulation results and the plant data. Moreover, in this study, the effect of cycle
Available online 19 April 2013
time and feed flow rate on hydrogen recovery and product purity is investigated and an optimal value
is estimated for cycle time and feed flow rate. The optimal sub cycle time causes to reduce the pollution
Keywords:
load of the sorbents. Reduction of pollution load of adsorbents increases the absorber life time and con-
Pressure swing adsorption
Adsorption in layered beds
sequently, decreases operating cost of PSA unit of domestic petrochemical plant that allocates for purge
Hydrogen purification of adsorbents. The results show that by applying the optimal cycle time and optimal feed flow rate as the
Gas separation operating conditions, hydrogen recovery of the PSA unit increases from 75% to 80% and 77.5% respec-
tively, and hydrogen purity of the product stream slightly reduces. This phenomenon increases purified
hydrogen that is fed to hydrogenation unit.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction
Energy supply and demand play a vital role in our modern life.
Among various energy supplies, fossil fuels such as coal, oil and gas
⇑ Corresponding author at: Department of Chemical Engineering, School of
Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran. Tel.:
+98 711 2303071; fax: +98 711 6287294.
E-mail address: rahimpor@shirazu.ac.ir (M.R. Rahimpour).
are the most common ones. Although these energy sources are
used extensively for different purposes such as generating electric-
ity in a large scale, their application should be limited due to grow-
ing environmental concerns. Fossil fuels are the largest greenhouse
gas emitters in the world, contributing approximately 3/4 of all
carbon, methane and other greenhouse gas emissions. Burning coal
also produces sulfur dioxide which contributes to acid rain [1,2].
Considering these disadvantages of using fossil fuels, there is an
increasing interest in modernizing energy supplies.

1385-8947/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.04.029
 M.R. Rahimpour et al. / Chemical Engineering Journal 226 (2013) 444–459
Nomenclature
q gas density (kg/m3)
t time (s)
m gas velocity (m/s)
e bed porosity
qi the amount of component I adsorbed (kgadsorbed/kgadsor-
bent)
z axial bed coordinate (m)
DZ axial dispersion coefficient (m2/s)
Ci the molar concentration of component I (mol/m3)
a1,i adsorption isotherm constant for component I
(kgadsorbed/kgadsorbent)
a2,i adsorption isotherm constant for component I (K)
b0,i adsorption isotherm constant for component I (1/mm
Hg)
b1,i adsorption isotherm constant for component I (K)
qi,eq the amount of I adsorbed component in equilibrium
conditions (kgadsorbed/kgadsorbent)
P pressure (Pa)
1.1. Hydrogen
At the recent years, application of hydrogen as an alternative to
fossil fuel has been investigated widely. There is an increasing
interest in using hydrogen as an energy carrier for the near future.
Hydrodealkylation, hydrodesulphurization, and hydrocracking
are the main consumers of H2 in the petroleum plants. H2 is used
as hydrogenating agent and in production of methanol. In addition,
it has many applications in physics and engineering. For example it
is used as shielding gas such as atomic hydrogen welding [3] and as
a rotor coolant in electrical generators. Pure hydrogen or mixed
hydrogen with nitrogen is employed as a tracer gas.
Hydrogen is produced by different methods. Haber process
which is used for ammonia production and electrolysis of brine
to yield chlorine are used for hydrogen production. Catalytic steam
reforming of natural gases is also a common method for hydrogen
production in industrial plants. It is noteworthy that during these
processes, the obtained product is a mixture of hydrogen, as desir-
able product, and one or additional gases. Thus, separation of these
mixtures to obtain purified hydrogen is an important issue that has
been investigated by researchers in recent years. During the recent
years, several researchers have been studied on hydrogen purifica-
tion by membrane technology. For example, Cheng et al. have
investigated the Hydrogen separation from a commercial Town
gas mixture consists of H2, CH4, CO2 and CO by alumina, zeolite
(ZSM-5), palladium and Pd–Ag alloy membranes. Their study
showed that using ZSM-5 membrane with using thin palladium
and Pd–Ag alloy membranes increases ability of adsorption of
hydrogen compared with using commercial alumina membrane
alone [4].
According to important role of Pd membranes (which are made
from Pd with the other component), in hydrogen purification, sev-
eral researchers were interested in investigation of different meth-
ods of preparation of this type of membrane. For example,
preparation of Pd/Vycor composite membranes using electro less
plating from both typical hydrazine-based and formaldehyde mod-
ified baths was investigated by Yeung et al. [5]. Moreover, Yeung
et al. has made dense Pd/SS-316L composite membranes using
conventional electro less plating and a new synthesis procedure
based on electro less plating with osmosis. This prepared mem-
brane has about five times higher hydrogen permeation rate and
better thermal stability [6].
445
Ki the overall mass transfer coefficient (1/s)
TF temperature of feed stream
Xi the molar fraction of component I in the gas phase
Xi,in the molar fraction of component I in inlet stream
Tin the temperature of the inlet stream
mf the average velocity at feed entrance
Pads adsorption pressure
PD purge pressure
Pout pressure in the exit of the bed which is providing purge
gas
Kf set time coefficient
Ri adsorbent vessel internal radius
VP gas velocity at product end
X H2 ;P hydrogen molar fraction at product stream
X H2 ;f hydrogen molar fraction at feed stream
1.2. Pressure swing adsorption (PSA)
There are various commercial methods for gas separation such
as extraction, distillation, and adsorption. Adsorption processes,
particularly pressure swing adsorption (PSA) are the most impor-
tant tools for gas separation. Pressure swing adsorption is a suit-
able, low cost and energy-efficient technology for gas separation
which is used in industrial plants. So, there is an increasing interest
in using this process in order to purify various types of gases such
as hydrogen.
By considering the advantages of using PSA method for gas sep-
aration, there has been significant development in pressure swing
adsorption system [7]. For example, layered bed technology, con-
sisting of different sorbents, is a novel and attractive alternative
for multicomponent gas separation [8–12]. In this new method,
at the inlet of the column a weak sorbent is followed by stronger
layer. This arrangement helps the reduction of absorbent size and
increases the use of each sorbent. Considering the advantages of
using this technology, researchers have been interested in investi-
gating the effect of various parameters on operation of this meth-
od. For example, Chlendi and Tondeur showed that relative layered
length has a significant effect on yield and the productivity of the
PSA unit consisting of double layered columns [13].
Binary separation in layered beds has been studied by Pigorini
and LeVan [14]. They showed that ratio of the two layers has obvi-
ous effect on the separation process. At the recent years, Park et al.
[15] has analyzed a mathematical model in order to minimize the
bed size and enhance the efficiency of sorbents. Moreover, a novel
compact layered pressure swing adsorption (LPSA) that was used
for removing carbon dioxide and nitrogen from a gas mixture has
been investigated by Cavenati et al. [16]. Rege et al. [17] have
investigated the performance of a pressure swing adsorption unit
that was employed for air separation. Single bed containing one
type of adsorbent and layered bed containing two different adsor-
bents was analyzed by these researchers. The main objective of
their study was to estimate an optimal value for amount of adsor-
bents that are used for particular bed operating conditions. CO2
separation by pressure swing adsorption is an attractive issue
which has been analyzed by several researchers in recent years
[18,19].
In 2002, Gomes et al. have investigated Carbon dioxide removal
by pressure swing adsorption (PSA) processes to obtain the optimal
446 M.R. Rahimpour et al. / Chemical Engineering Journal 226 (2013) 444–459

to obtain an optimal time for sub cycle of adsorption that leads

to reduction of the pollution load of the sorbents. Reduction of pol-
lution load of sorbents enhances the sorbents lifetime that is an
important issue in industrial plants. Moreover, in this study the ef-
fect of cycle time on hydrogen recovery and hydrogen purity in
outlet stream is analyzed. The inlet stream of this system is con-
taining about 94% hydrogen on a typical day. The main impurities
of inlet stream are methane, nitrogen and carbon monoxide. PSA
unit investigated in the current work consists of five beds which
each of them are composed of five different sorbents layers. The
experimental data’s are employed to validate the mathematical
Fig. 1. The block flow diagram of the olefin plant.
model that predicts the performance of this unit.

feed flow rate and cycle time [20]. Their study showed that Zeolite
13X is a suitable sorbent for CO2 sequestration. A pressure swing
2. Domestic petrochemical plant
adsorption, which was employed for hydrogen recovery from coal
gas, was simulated by Ahn et al. [21]. Their simulation showed that
Olefins are the building blocks in manufacturing of polymers
using the higher zeolite ratio in layered beds increases the hydro-
and elastomers or converted into derivatives such as aldehydes,
gen production with higher purity in the PSA operation. Grant and
alcohols, and glycols. The olefin important produced is ethylene.
Douglas have developed a mathematical model to investigate the
Ethylene production witnessed a dramatic growth in the late
sensitivity of breakthrough of adsorption beds to operation param-
20th century from 29 million lb to 180 billion lb. As a result, it is
eters [22]. They employed the sensitivity data in order to obtain
known that even a small improvement in ethylene production pro-
the optimized conditions for a two-layer, two-bed PSA system.
cess may lead to a remarkable profit for the petrochemical industry
As illustrated, hydrogen is among the most important novel en-
[31,32].
ergy carriers. So hydrogen purification by pressure swing adsorp-
In domestic petrochemical plant thermal cracking of alkanes
tion is an attractive issue at the recent years [23–26]. By
such as ethane, propane, butane, naphtha and gas oil is used to pro-
considering the importance of hydrogen production as an energy
duce ethylene. The block flow diagram (Fig. 1) shows how the ole-
carrier, many researchers have studied PSA process in order to im-
fin plant is work to produce ethylene and acetylene. As it is shown
prove the performance of this technology. For example, Lopes et al.
in Fig. 1 the unit consists of two main parts: 1 – Cracking furnaces
employed a mathematical model to simulate a 10 steps one-col-
(hot section) 2 – Compressors and separators (cold section). In first
umn VPSA system [27]. Moreover, their mathematical model was
part the olefins are primarily produced by steam cracking of large
used to investigate the influence of operation conditions and the
hydrocarbon molecules in furnaces. Various hydrocarbon products
effect of step times on performance of PSA technology.
could form through 1400 chemical reactions in coils of the fur-
A compact pressure swing adsorption was employed for
naces. The high concentration of acetylene in the feed stream of
adsorption of CO and CO2 in mixtures of H2/CO/CO2 by Majlan
polymerization plants not only contaminates the catalysts but also
et al. [28]. In this system the pure hydrogen was used for fuel cell.
forms metal acetylides which are extremely explosive. So, in the
Their study showed that CPSA system is a suitable system for cre-
second part the output stream from furnaces are fed to separation
ation the required specifications of hydrogen purity. In order to
towers and hydrogenation catalytic reactors to convert acetylene
investigate a hydrogen purification process from steam methane
to ethylene. In domestic petrochemical plant some portion of the
reforming off gas, a multi-bed pressure swing adsorption has been
ethylene is used as the feedstock of poly-ethylene production unit
simulated by Nikolic et al. [29]. Temperature is an important
and the rest is exported in the liquid phase. The feed and product
parameter which can influence the adsorption process. A non-iso-
components are shown in Fig. 1.
thermal multicomponent pressure swing adsorption system which
was used for separation of CH4 and H2 on active carbon has been
analyzed by Tańczyk and Warmuziński [30].
3. Process description of olefin unit
1.3. Objective
A simplified schematic diagram of complicated olefin unit of
In the present work an industrial hydrogen purification unit, domestic petrochemical plant is shown in Fig. 2. Each part of this
(PSA unit of domestic petrochemical plant) is simulated in order figure is described in details in the following sections.

Fig. 2. Simplified diagram of olefin unit of domestic petrochemical plant.

 M.R. Rahimpour et al. / Chemical Engineering Journal 226 (2013) 444–459 447

3.1. Cracking furnaces Table 2

Outlet compositions of gas furnaces.

In this process, a mixture of steam and hydrocarbons including Component Mole fraction % Rate of flow (Ton/h)
ethane, propane, butane, isobutane, naphtha, and gas oil is intro- Water 00.00 11.916
duced into furnaces in order to produce olefins. The cracking fur- Hydrogen 3.89 1.546
naces are the heart of the whole ethylene manufacturing process. Methane 4.75 1.886
Both gas and liquid furnaces are used in order to produce olefins Carbon monoxide 0.04 0.018
Carbon dioxide 0.01 0.005
in domestic petrochemical plant. A wide variety of feedstock for Sum C0/C1’ 8.7 15.37
furnaces can be employed with ethane and naphtha being the most Acetylene 0.34 0.136
common. Ethane is fed to the gas furnaces and naphtha to the li- Ethylene 50.75 20.156
quid furnaces. The desired products from the furnaces are light ole- Ethane 35.55 14.12
Sum C2’s 86.64 34.411
fins, i.e., ethylene, propylene and butadiene. However, depending
C3H4’s 0.02 0.009
on the nature of the feedstock, a wide array of by-products can Propylene 1.12 0.443
be produced. Tables 1 and 2 provide information about the prod- Propane 0.2 0.08
ucts of liquid and gas furnaces from this company, respectively. Sum C3’s 1.34 0.532
It is noticeable that gas furnace produces 1.5 times more ethylene Vinyl acetylene 0.03 0.014
Butadiene 1.2 0.478
than liquid furnace.
Butenes 0.16 0.063
In domestic petrochemical plant, a mixture of ethane and steam Butanes 0.37 0.149
goes through two passes in gas furnaces. Table 3 shows flow rates Sum C’4s 10.34 0.703
of ethane and steam in each pass during a run length of reactor. Sum C’s 0.4 0.16
Benzene 0.77 0.304
C6 non aromatics 0.03 0.011
3.2. Transfer line exchanger and quench tower Sum C6’s 0.79 0.315
Toluene 0.1 0.038
The fast reduction of temperature of output stream from fur- C7 non aromatics 0.01 0.002
Sum C7’s 0.1 0.04
naces is very critical to prevent unwanted side reactions. The side Xylene 00.00 0.001
reactions include formation of polymers from monomers in high Ethyl benzene 00.00 0.001
temperature. So, Products leave the furnaces and cool down Styrene 0.08 0.031
quickly in the transfer line exchanger (TLE). C8 non aromatics 00.00 00.00
Sum C8’s 0.08 0.033
Sum C9’s 0.01 0.004
3.3. Compressors Sum C10’s 0.17 0.066
Total 100 66,584
The products from quench tower are compressed in centrifugal
compressors. High pressure is necessary for producing pure

Table 1 Table 3
Outlet compositions of liquid furnaces. Flow rate of ethane and dilution steam during a run length of reactor.

Component Mole fraction % Rate of flow (Ton/h) Parameters Value

Water 00.00 22.182 Pressure (bar) 25
Hydrogen 1.12 0.498 Temperature (Start-Of-Run) (°C) 35
Methane 19.93 8.843 Temperature (End-Of-Run) (°C) 69.5
Carbon monoxide 0.13 0.058
Components Outlet (wt.%) Inlet (wt.%)
Carbon dioxide 0.01 0.005
Sum C0/C1’ 21.2 31.587 Methane 0.01 0.0099
Acetylene 0.86 0.397 Acetylene 0.0 0.83
Ethylene 34.11 15.134 Ethylene 68.3 67.88
Ethane 3.44 1.525 Ethane 31.34 31.02
Sum C2’s 38.4 17.038 MAPDa 0.0 0.000429
C3H4’s 1.19 0.528 Propylene 0.34 0.2481
Propylene 15.39 6.828 Propane 0.004 0.0047
Propane 0.85 0.378 SUM 100 100
Sum C3’s 17.43 7.734 a
Methyl acetylene, propadiene.
Vinyl acetylene 0.12 0.054
Butadiene 4.66 2.069
Butenes 4.01 1.788
Butanes 1.55 0.686
hydrogen which is used in hydrogenation reactors. The compres-
Sum C’4s 10.34 4.587
Sum C’s 2.4 1.064 sion ratio should be low enough to prevent polymer production
Benzene 5.18 2.3 in the output at high temperature.
C6 non aromatics 0.5 0.223
Sum C6’s 5.69 2.523
Toluene 1.57 0.695 3.4. Acid gas removal unit
C7 non aromatics 0.1 0.044
Sum C7’s 1.67 0.739 By considering the existence of byproducts such as carbon mon-
Xylene 0.26 0.115 oxide, carbon dioxide and sulfur contaminants in gas cracker efflu-
Ethyl benzene 0.02 0.01
Styrene 0.57 0.251
ents, separation processes are used for eliminating these
C8 non aromatics 00.00 0.002 components. The existence of carbon dioxide could cause hydrate
Sum C8’s 0.57 0.379 formation and sulfur can poison catalysts of the reactors. The con-
Sum C9’s 0.25 0.112 centration of carbon dioxide should be less than 0.1 ppm for
Sum C10’s 1.77 0.785
increasing the final ethylene product purity which is fed to the
Total 100 66,584
polymerization unit.
448 M.R. Rahimpour et al. / Chemical Engineering Journal 226 (2013) 444–459

Removing acid gas is done in the caustic tower. This tower is
placed after compressors because absorption process increases
with increasing the pressure. The following reactions occur in the
caustic tower:
H2 S þ 2NaOH ! Na2 S þ 2H2 O
CO2 þ 2NaOH ! Na2 CO3 þ H2 O
3.5. DE-Methanizer and PSA unit
The output of caustic tower is directed to a DE-Methanizer for
methane separation. Methane is the outlet stream of the top of
the DE-Methanizer bed. Also, the bottom gas stream which con-
sists of hydrogen is fed to the PSA unit. Hydrogen which is needed
for hydrogenation unit is purified by PSA unit. Another outlet
stream of PSA unit is fed to hydrogenation unit to convert the acet-
ylene to the ethylene and the other alkanes to the olefins. The de-
tails of PSA unit will be discussed later in Section 4.
4. The PSA unit of domestic petrochemical plant
The first step in this work is to simulate the PSA unit of domes-
tic petrochemical plant. The PSA unit is used for hydrogen purifica-
tion in olefin unit of domestic petrochemical plant. In the PSA unit
there are normally 5 adsorbers in operation, called D01A, D01B,
D01C, D01D and D01E. Each adsorber is cycled through an identical
adsorption-regeneration sequence. The cycles are staggered, so
that at all of the times 1 adsorber is on the adsorption step and
the other 4 are in various stages of regeneration. In order to in-
crease the reliability of the unit, the system can switch from 5-
bed to 4-bed operation, either manually (by the operator) or auto-
matically (by the control logic). Manual switchover will be used for
maintenance reasons, periodical check of vessel and maintenance
on valve set.
Automatic switchover to 4-bed operation will happen when the
control system detects a major failure to an adsorber, the related
valves or instrumentation or I/O card. The regeneration is carried
out in three stages: depressurization to purge pressure, purge at
low pressure and repressurization to adsorption pressure. One to-
ð1Þ tal adsorption and regeneration cycle is called a complete cycle and
has no further meaning. One sub cycle is divided into three steps,
ð2Þ named steps 1, 2, and 3 (identical in 5- and 4-bed operation).
The steps of this unit followed a predefined rule which is shown
in Table 4.
Each vessel is filled with five different commercial adsorbent
layers which are called H5-2, H2-10, H1, H14 and H1, respectively.
These sorbents are different in their composition. For example,
zeolite is the main component of H1 and H14 and alumina oxide
is the principal component of H5-2. The commercial specifications
of these adsorbents are tabulated in Table 5. There is a specified
arrangement for these five different sorbent layers. H5-2 which is
at the feed entrance is followed by an active carbon layer called
H2-10. After this layer, H1, H14 and H1 are used respectively as
sorbents for hydrogen purification. It may be questionable that
why different sorbents with this arrangement are used in each
column.
Commercial sorbents are able to separate special components.
Actually one type of sorbent is not able to adsorb all the chemical
components. According to selectivity property of commercial sor-
bents, in industrial plants, PSA units which are utilized to separate
just one component from a mixture, one type of sorbent should be
used. But in cases that several components shall be separated from
a gas mixture, two or more types of sorbents are utilized for
adsorption process.
In the PSA unit investigated in this study, CO, CO2, CH4, C2H4,
C2H6 and N2 are separated from inlet gas mixture. So, as illustrated,
different types of sorbents are used for adsorption. Moreover,
when concentration of components is not considerable, escaping
components from empty regions of the bed is more possible. Con-
sequently, in this case, in order to increase the driving force, more

Table 4
Sequence of the steps of a complete PSA cycle.

Bed Step
1 Adsorption Providing purge Dump Purge Repressurization
2 Repressurization Adsorption Providing purge Dump Purge
3 Purge Repressurization Adsorption Providing purge Dump
4 Dump Purge Repressurization Adsorption Providing purge
5 Providing purge Dump Purge Repressurization Adsorption

Table 5
Commercial specifications of the adsorbents.

Commercial Ingredient %Weight Diameter (mm) Pore size (Å) Shape Surface area (m2/gr) Bulk density Crush strength Porosity
name
H14 Zeolites >70 2–4 8 Pellet – 680–710 40–48 (N/cm) 0.4
Mineral <30
Binder <2
Quartz
H1 Zeolites >70 1.6–1.8 5 Pellet – 670–720 40–50 (N/cm) 0.4
Mineral <30
Binder <1
Quartz
H2–10 Activated carbon 100 2 – Granule 930–950 490–510 – 0.38–0.4
H5–2 Aluminum oxide <95 3–5 – Sphere 300–320 680–700 120–145 (N/Granule) 0.38–0.4
Water <15
Sodium oxide <10
 M.R. Rahimpour et al. / Chemical Engineering Journal 226 (2013) 444–459
value of sorbents shall be used in each column. According to these
reasons (separation of different chemical components and low
concentration of impurities), in this PSA unit, four types of sorbents
have been used.
The first sorbent layer (H5-2), operates as a guard bed and is
used to prevent the entrance of some components such as mercury
and arsine. The second sorbent layer (H2-10), which consists of ac-
tive carbon (100%), is an inexpensive sorbent which is used for
adsorption of hydrocarbons such as acetylene, ethylene and CO2.
This phenomenon is indicated later in Fig. 6c. As it is shown in this
figure, most of the value of ethylene, acetylene and CO2 is adsorbed
by H2-10.
As illustrated in the paper, carbon monoxide is a toxic compo-
nent for hydrogenation unit. The outlet stream of the PSA unit is
fed to the hydrogenation unit and consequently must be separated
by PSA unit. The third, fourth and fifth sorbent layers (H1–H14 and
H1, respectively), which consist of zeolite mainly are high-perfor-
mance and expensive sorbents to adsorb components such as
methane and CO. Consequently, because of high-performance of
zeolite and importance of CO separation, this type of sorbent is
used three times in each column. Size of particles of H1 and H14
is 5 and 8 Å, respectively and actually H14 is more inexpensive
than H1. Therefore using a layer of H14 sorbent between two H1
layers instead of using H1 layer completely is more economically
without any decreasing in adsorption efficiency. This fact is the
main reason of arrangement of H1 and H14.
Because of the ability of zeolite to adsorb all the components
one may ask that why zeolite is not used in each column com-
pletely instead of combination of active carbon and zeolite. Active
carbon is more inexpensive than zeolite and is able to adsorb some
types of hydrocarbons. So adsorption of components by active car-
bon is more economically.
The effect of arrangement of sorbent layers which is an impor-
tant operating parameter and sometimes seems ineffective on
operating of PSA units has been investigated by several research-
ers. For example, Simone Cavenati et al. have studied on effect of
the ratio of adsorbent layers.
In the PSA unit investigated in this study, by considering the
weak interaction of hydrogen with five sorbent layers, it is consid-
ered as an inert gas, during the performance of the PSA unit.
Fig. 3. Simplified diagram of the PSA unit of domestic petrochemical plant.
449
As illustrated, the PSA unit which is investigated in this study
consists of five beds that follow a specified sequence. Fig. 3 shows
a brief description of this unit. The way the beds are connected one
to another and exchange of gas between columns in each step is
obvious in this figure. The valves open and close automatically to
change the performance of the PSA unit from one step to another
based on the rule that is shown in Table 4. In order to follow the
predefined rule illustrated in Table 4, an automatic system is used
to control the interconnection of valves.
Moreover, in order to illustrate the operation of PSA unit more
obviously, the time-evolution of pressure in the five columns dur-
ing each sub cycle is shown by Fig. 5. Step sequence which is indi-
cated in Fig. 3 and Table 4 for each bed, can be followed in Fig. 5.
Exchange of gas between columns in the first sub cycle is described
in the following paragraphs.
As it shown in the Fig. 5, during the first sub cycle, bed ‘‘A’’ oper-
ates as an adsorber bed. Moreover, as indicated in this figure, in the
second sub cycle time, bed ‘‘B’’ shall operate as the adsorber col-
umn. So its pressure must be increased in the first sub cycle for
preparation of this bed for adsorption step in the second sub cycle.
During the first sub cycle, bed ‘‘E’’ (The last bed which has oper-
ated as an adsorber column in the last sub cycle and must be pre-
pared for purge step) by accumulated hydrogen, increases the
pressure of bed ‘‘B’’ through EQvalve’s (equalization). Consequently,
pressure of bed ‘‘E’’ and ‘‘B’’ decreases and increases to 20.2 bar
respectively. Actually the pressure of bed ‘‘B’’ and ‘‘E’’ are equal-
ized. After increasing the pressure of bed ‘‘B’’, a portion of feed
stream enters to the bottom of this bed changing pressure from
20.2 bar to 32.3 bar (repressurization) and finally the bed is ready
for adsorption step completely.
As illustrated, pressure of bed ‘‘E’’ must be decreased to 4.6 bar
for purge step. A portion of pressure drop is done during the equal-
ization step. The remained hydrogen in bed ‘‘E’’ enters the top of
beds ‘‘C’’ and ‘‘D’’ for purging these beds. Consequently, the pres-
sure of bed ‘‘E’’ decreases from 20.2 to 9.3 bar and this bed is pre-
pared for purge step approximately. In the next sub cycle, by
discharging the remained hydrogen in bed ‘‘E’’ (dump), its pressure
decreases to favorable pressure (4.6 bar). It is necessary to illus-
trate that before purging of bed ‘‘D’’ by ‘‘E’’ in the first sub cycle,
by discharging the remained gas in bed ‘‘D’’ to the tail gas header
450 M.R. Rahimpour et al. / Chemical Engineering Journal 226 (2013) 444–459
Fig. 4. Simplified schematic of each bed.
(dump), this bed is prepared for purge step and its pressure de-
creases to 4.6 bar.
Schematic of 5 adsorbers, called D01A, D01B, D01C, D01D and
D01E are the same. Fig. 4 shows the simplified schematic of these
beds and arrangement of sorbent layers in these columns.
Inlet mixture of PSA unit of domestic petrochemical plant is
comprised of seven components. These components are hydrogen,
nitrogen, ethylene, acetylene, methane, carbon monoxide and car-
bon dioxide. The outlet stream of this industrial unit with 99.99%
purity in hydrogen is used for hydrogenation unit of domestic pet-
rochemical plant. The PSA unit investigated in this study operates
under various conditions on different days. The molar flow rate,
impurity of components, and sub cycle time are different in various
days. For example, mole fraction of methane is in the range of 4–
15%. The common operation condition of PSA unit of domestic pet-
rochemical plant is tabulated in Table 6.
By considering this complicated process, several operating
parameters can be effective on mole fraction of components in in-
let stream of the PSA unit. For instance, the temperature varies on
different days. Consequently, the mole fraction of methane in
which fed to the PSA unit is not the same on various operating
days. Six different temperatures which create various mole fraction
of methane in inlet stream of PSA unit are tabulated in Table 7.
Mole fraction of components in outlet stream of the liquid and
gas crackers are not the same. For instance, the production of acet-
ylene and methane by liquid furnaces is higher compared with gas
crackers. Whiles, mole fraction of hydrogen in outlet stream of gas
cracker is higher than liquid cracker. This difference for liquid and
gas furnaces was shown in Tables 1 and 2, respectively. Gas Chro-
matography ASTM D2504 Test method is used for analysis of non-
condensable gases in C2 and lighter hydrocarbon products. Other
components are analyzed by ASTM D6159 method. According to
these statements, the number of liquid and gas crackers is another
operating parameter that has the direct effect on amount of
cracked components which are the feed of separation units such
as PSA unit. In normal conditions, five gas crackers and four liquid
crackers are used for cracking process. The arrangement of liquid
and gas crackers depends on the produce capacity and shortage
of liquid or gas feed of the crackers. For example, Sometimes it is
more desirable to produce the higher ethylene compared with
the other olefins. Consequently, it is necessary to increase the
number of the gas furnace. On specific days, liquid feed is less com-
pared with the other days. So, it is suitable to decrease the number
of liquid furnace.
5. Mathematical model
For simulating PSA unit a set of partial differential and algebraic
equations are used to develop a mathematical model. These partial
differential equations (PDE’s) are converted by method of line to a
set of ordinary differential equations (ODE’s). After this conversion,
programming with MATLAB has been used to solve this set of or-
 M.R. Rahimpour et al. / Chemical Engineering Journal 226 (2013) 444–459 451

Table 6
Common operation condition of PSA unit of domestic petrochemical plant.

Conditions Feed Product Tail gas

Composition, mol%
H2 94.84 99.99 82.15
N2 0.01 Balance 0.02
CO 0.29 0.03 ppm 1
CO2 10 ppm Balance 0
CH4 4.86 16.93
C2H6 10 ppm 0
C2H4 10 ppm 0
Unit recovery % 75
Pressure (Bar a) 32.3 31.6 4.6
Pressure (mm Hg) 24,548 24,016 3496
Temperature (°C) 35 40 25
Molar weight (kg/kmol) 2.78 2.02 4.65
Flow rate (m3/s) 10.1 7.575 3.0735
Flow rate (kg/h) 4606.16 2381.51 224.64
Flow rate (kmol/h) 1859.02 1180.18 478.84

Table 7
Temperature of the cold box and mole fraction of the
methane in outlet stream of the cold box.

Temperature (°C) Mole fraction of methane %

161.1 4.9
159 6.811
155 8.071
153.5 9.1
150 11.31
148 18.5

Table 8
axial dispersion coefficient of component in other components, feed and product
stream.

Mixture Axial dispersion coefficient (m2/s)

H2–N2 2.340972981  106
H2–CO 3.407304156  107
H2–CO2 3.449411471  106
H2–CH4 2.394843971  106
H2–C2H6 1.66888255  106
H2–C2H4 2.199535736  106
N2–CO2 5.57541587  106
N2–CH4 7.700675474  107
N2–C2H6 7.314549878  108
CO–CO2 5.471361901  107
CO–CH4 7.608597619  107
CO–C2H6 5.20887691  107
CO–C2H4 6.38831239  107
CO2–C2H4 4.802162009  107
CH4–C2H4 6.881944674  107
C2H6–C2H4 4.5682055  107
H2-Feed stream 3.7465738  105
H2-Product stream 6.364444  106
CO-Feed stream 5.27483726  106
CO-Product stream 1.36758373  106
CO2-Feed stream 5.736475849  105
CO2-Product stream 3.6465825  107
CH4-Feed stream 8.0372026  106
CH4-Product stream 3.64738272  105
C2H4-Feed stream 4.26202620003  106
Fig. 5. time-evolution of pressure during a complete cycle for (a) bed A, (b) bed B, C2H4-Product stream 4.2092002  105
(c) bed C, (d) bed D, (e) bed E. C2H6-Feed stream 3.006248  105
C2H6-Product stream 5.28364748  105

dinary differential equations. The following assumptions are used

in the modeling:
– The gas mixture is considered as an ideal gas.
– Laminar plug flow is employed for gas mixture with dispersion
in axial direction of the column. Radial gradients are negligible.
– Thermal effects are not considered.
– Fluid velocity is not constant along the column and is a function
of time and location in the bed. It is estimated with by balance
equation.
452 M.R. Rahimpour et al. / Chemical Engineering Journal 226 (2013) 444–459

Table 9
The Langmuir coefficient of components.

Sorbent layer Component ai;j  103 ðmol=grÞ ai;2 ðKÞ bi;0  107 ð1=mm HgÞ bi;1 ðKÞ

H-1 H2 1.24 0.36 2.2 1159.3

CO 0.58 0.83 2.53 2616.3
N2 0.23 1.015 6.38 1859
CO2 2.09 0.63 0.67 3994.3
CH4 0.29 1.04 6.44 1862.1
C2H6 2.075 0.59 0.63 3865.7
C2H4 1.095 0.61 0.65 3795.9
H-14 H2 1.23 0.357 2.19 1157.4
CO 0.56 0.81 2.57 2592.6
N2 0.198 1.017 6.37 1795
CO2 2.075 0.624 0.659 3989
CH4 0.28 1.036 6.53 1865
C2H6 2.073 0.58 0.629 3867.4
C2H4 1.084 0.63 0.643 3893
H-2-10 H2 4.32 0.0 6.72 850.5
CO 0.92 0.52 7.86 1730.9
N2 1.75 1.95 25.9 1439
CO2 14.2 6.63 33.03 1496.6
CH4 1.78 1.98 26.6 1446.7
C2H6 12.6 6.1 31.8 1385
C2H4 11.95 6.9 28.9 1375.3

– Because of low temperature difference between inlet and outlet

Table 10
The overall mass transfer coefficient of components on (a)
streams, the Langmuir isotherm is used for computation of mul-
H-2-10, (b) H-1 and (c) H-14 layers. ticomponent adsorption equilibrium.
– The amount of adsorbed hydrogen is negligible.
Component Overall mass transfer
coefficient (s1)
– A linear driving force equation (LDF equation) is used for esti-
mation of mass transfer rate.
(a)
– No heat is lost to the surroundings.
N2 0.15
CO 0.3
CO2 0.1 5.1. Balance equations
C2H4 0.09
C2H6 0.095
Overall mass balance for gas phase is described by the following
CH4 0.4
H2 1
equation:
(b) @q @ðmqÞ ð1  eÞ X
n1
@qi
N2 0.2 ¼  ð3Þ
CO 0.15
@t @z e i¼1 @t
CO2 0.05
C2H4 0.04 where ‘‘q’’, ‘‘m’’, ‘‘z’’, ‘‘t’’, ‘‘qi’’, are the gas density, gas stream velocity,
C2H6 0.039 axial dimension, time and the ratio of amount of adsorbed compo-
CH4 0.4 nent to the amount of sorbent (kgi/kgsorbent) respectively.
H2 1 In this equation, ‘‘e’’ is the porosity of the sorbents layers. In this
(c) equation, e is the porosity of the sorbents layers. Porosity of each
N2 0.19 sorbent layer with the other physical properties are tabulated in
CO 0.147
CO2 0.046
Table 5.
C2H4 0.037 The following equation derived from mass balance for compo-
C2H6 0.041 nent i:
CH4 0.42
H2 1 @ci @ 2 ci @ðm  ci Þ 1  e @qi
¼ Dz 2   ð4Þ
@t @z @z e @t

Table 11
Boundary conditions employed for simulation.

Boundary
conditions
Fluid entering the bed Xi = Xi,in T = Tin
Fluid leaving bed and closed end (Ci/@Z) = 0 (T/@Z) = 0
Adsorption Z = 0 ? m = mf Z = L ? P = Pads
Pressure equalizations, repressurization and provide purge: Z=0?m=0 Z = L ? P = P(t)
Blow down Z = 0 ? P = P(t) Z=L?m=0
Purge Z = 0 ? P = PD Z = L ? m = mout (Pout/PL)
Intersection of the second and the third layers P2(xi) = P3(xi) V2(xi) = V3(xi) T2(xi) = T3(xi) Ci,2(xi) = Ci,3(xi)
Intersection of the third and the fourth layers P3(xi) = P4(xi) V3(xi) = V4(xi) T3(xi) = T4(xi) Ci,3(xi) = Ci,4(xi)
Intersection of the fourth and the Fifth layers P4(xi) = P5(xi) V4(xi) = V5(xi) T4(xi) = T5(xi) Ci,4(xi) = Ci,5(xi)
 M.R. Rahimpour et al. / Chemical Engineering Journal 226 (2013) 444–459 453

where ‘‘Ci’’ is the molar concentration of component ‘‘i’’ in the gas As indicated in this equation, before calculation of axial dispersion
phase and ‘‘Dz’’ is the axial dispersion coefficient of component coefficient of component ‘‘A’’ in gas mixture, axial dispersion coeffi-
‘‘A’’ in gas mixture which is calculated by the following equation cient of component ‘‘A’’ in other components shall be estimated by
[33]: Wilke Lee equation which has been derived by modification of Hir-
X
n schfelder–Bird–Spotz method [34]:
N A  yA Ni h qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffii qffiffiffiffiffi 
i¼A 104 1:084  0:249 1
MA
þ M1B ðTÞ3 =2 1
MA
þ M1B
DA;m ¼ ð5Þ DAB ¼   ð6Þ
X
n
1
ðyi NA  yA Ni Þ ðPtotal ÞðrAB Þ2 f eKT
Di AB
i¼A

1.01 0.05
(a) 0.045 (b) simulation
1 experimental
Mole fraction of hydrogen

Mole fraction of methane

0.04
0.99 0.035
0.03
0.98
0.025
0.97
0.02

0.96 0.015
0.01
0.95 simulation
experimental 0.005

0.94 0
0 0.5 1 1.5 2 2.5 3 3.5 0 0.5 1 1.5 2 2.5 3 3.5
z-direction z-direction
-3
x 10
-5 3
x 10
3.5 (d)
Mole fraction of CO2, C2H4, C2H6

simulation
3
(c) simulation 2.5 experimental
Mole fraction of monoxide

experimental
2.5
2
2

1.5 1.5

1
1
0.5

0 0.5
-0.5
0
-1
0 0.5 1 1.5 2 2.5 3 3.5 0 0.5 1 1.5 2 2.5 3 3.5
z-direction z-direction
-4
x 10
1.2
(e) simulation
1 experimental
Mole fraction of N2

0.8

0.6

0.4

0.2

0
0 0.5 1 1.5 2 2.5 3 3.5
z-direction

Fig. 6. Mole fraction variation of (a) hydrogen, (b) methane, (c) carbon dioxide + ethylene + acetylene, (d) carbon monoxide and (e) nitrogen along the bed axial direction that
operates in adsorption step at 56 s.
454 M.R. Rahimpour et al. / Chemical Engineering Journal 226 (2013) 444–459

Fig. 7. Comparison of amount of adsorbed (a) nitrogen, (b) carbon monoxide, (c) carbon dioxide + ethylene + acetylene, (d) methane estimated by simulation and
corresponded plant data during the operating time of adsorption step at the end of second layer.

where M is the axial dispersion coefficient of each component in where ‘‘P’’ is the pressure of gas stream which varies with time dur-
other components and the axial dispersion coefficient of each com- ing each step. ‘‘PL’’, ‘‘PH’’ and ‘‘tstep’’ are the minimum pressure, the
ponent in feed and product stream are tabulated in Table 8: maximum pressure and the total duration of each step respectively.
In this work, Langmuir isotherm is used for computation of
multicomponent adsorption equilibrium:
5.2. Initial conditions
qisat bi Pi
qieq ¼ P ð7Þ
1 þ nj¼1 bj Pj A number of initial conditions are needed in order to solve the
model which is developed in this study. At the beginning of the PSA
a2;i cycle, the absorbents are considered clean. The bed temperature is
qisat ¼ a1;i þ ð8Þ
T considered to be equal to the temperature of the inlet stream.
  The following initial conditions are used to solve the coupled
b1;i partial differential and algebraic equations for simulation of PSA
bi ¼ b0;i exp ð9Þ
T unit of domestic petrochemical plant:
The Langmuir coefficients of components which are used in Eqs.
C i ðzÞ ¼ 0; i ¼ 1; . . . ; n  1 z ¼ ð0; lÞ ð12Þ
(7)–(9) are tabulated in Table 9.
Mass transfer rate is estimated by the following equation (LDF
equation): PðZÞ ¼ initial pressure of bed z ¼ ð0; lÞ ð13Þ
@qi
¼ K i ðqieq  qi Þ ð10Þ qi ðzÞ ¼ 0; i ¼ 1; . . . ; n  1 z ¼ ð0; lÞ ð14Þ
@t
The overall mass transfer coefficients of components on H-2-10, H-1
and H-14 layers are summarized in Table 10a–c respectively.
5.3. Boundary conditions
Pressure variation with time in equalization, providing purge,
dump and repressurization steps is estimated by the following
Although the balance equations used for simulation of all steps
equation:
of the process such as pressurization and equalization are the
" 2 #
t 2t same, but boundary conditions are different. The boundary condi-
P ¼ PðtÞ ¼ PL þ ðPH  PL Þ  þ1 ð11Þ tions employed to solve the model developed in this study are tab-
t step t step
ulated in Table 11:
 M.R. Rahimpour et al. / Chemical Engineering Journal 226 (2013) 444–459
Fig. 8. Comparison of amount of adsorbed (a) nitrogen, (b) carbon monoxide, (c) carbon dioxide + ethylene + acetylene, (d) methane estimated by simulation and
corresponded plant data during the operating time of adsorption step at the end of third layer.
6. Results and discussion
6.1. Model validation
In this work, a set of coupled partial differential equations was
solved for simulation of PSA unit of domestic petrochemical plant.
The model developed in this work, was validated against corre-
sponded plant data which were reported by domestic petrochem-
ical plant. Fig. 6a–e shows the variation of mole fraction of
components along axial direction of the bed which operates in
adsorption step at a certain time (56 s). The comparison showed
that the variations of operating parameters are well predicted by
the model.
It is obvious that Analysis of mole fraction of components in
gas stream is impossible along the bed axial direction. Conse-
quently, mole fraction of components along the bed axial direc-
tion estimated by simulation at a certain time (56 s), have been
compared with mole fraction of components reported by domes-
tic petrochemical plant at the end of the column at the same time
(Fig. 6).
Moreover, the developed simulation in this study is used to esti-
mate the amount of adsorbed components at the end of each layer
during the adsorption step. As depicted in Figs. 7g–9, amount of
adsorbed components estimated by simulation at the end of sec-
ond, third and fourth sorbent layers, respectively, have been com-
pared with those of reported by domestic petrochemical plant
during the adsorption time.
As illustrated in Table 6, methane is the main impurity of inlet
stream of PSA unit of domestic petrochemical plant. For example
on a typical day, the inlet stream has about 4.86%, 0.01% and
455
0.29% impurity in methane, nitrogen and carbon monoxide, respec-
tively. Moreover, there is a significant difference between the over-
all mass transfer coefficient for methane and the other components
in gas mixture. Consequently, as is shown in Figs. 7–9, the amount
of adsorbed methane is higher than the other components. Because
of the time limitation in the adsorption step, sampling at the each
end of the sorbent layer in numerous moments is impossible. As
depicted in Figs. 7–9, sampling was possible just at three different
moments.
Also, simulation is used for estimating the hydrogen recovery
and product purity. Consequently, comparison between hydrogen
recovery and product purity predicted by simulation and corre-
sponded plant data for the same operating conditions is another
suitable way for validation of simulation (Table 12). As shown in
Table 11, the hydrogen recovery and product purity are well pre-
dicted by simulation. So, simulation creates suitable facility to
investigate the effect of operating parameters on variation of
hydrogen recovery and hydrogen purity that have direct effect on
operating and total costs.
Application of simulation of PSA unit is not limited to adsorp-
tion step. In the current work, purge step is modeled by proper ini-
tial and boundary conditions. Consequently, simulation could be
used to determine a predictable mole fraction of components and
amount of components adsorbed during the purge step. Compari-
son between mole fractions of components along the axial direc-
tion of the column at a certain time with corresponded plant
data, during the purge step is another alternative to validate the
simulation. Fig. 10a and b shows the variation of mole fraction of
hydrogen and methane, respectively along the axial direction of
the column during the purge step.
456 M.R. Rahimpour et al. / Chemical Engineering Journal 226 (2013) 444–459
Fig. 9. Comparison of amount of adsorbed (a) nitrogen, (b) carbon monoxide, (c) carbon dioxide + ethylene + acetylene, (d) methane estimated by simulation and
corresponded plant data during the operating time of adsorption step at the end of fourth layer.
Table 12
Comparison between hydrogen recovery and product (Hydrogen) purity predicted by
simulation and corresponded plant data for the same operating conditions.
Simulation Plant data
Hydrogen recovery 74.68% 75.03%
Product purity 99.873 99.983
The cycle time of PSA unit of domestic petrochemical plant is
about 350 s. The hydrogen purity estimated by simulation in dif-
ferent moments during a complete cycle and corresponded plant
data are tabulated in Table 13. As illustrated in this table, there
is no significant difference between mole fractions of hydrogen
in different moments of a cycle. Changing the system from one step
to another in a short time is the main reason of this equality. In
other words, preparation of a bed for adsorption step in a short
time (less than 290 s), causes the sorbents of the PSA unit to be
fresh for adsorption process all the moments during a sub cycle.
Consequently, there is not significant slump in activity of sorbents
during a cycle and subsequently there is not considerable reduc-
tion in amount of adsorbed components in different moments.
6.2. Obtaining the optimal time for adsorption step
The costs of valve installation and maintenance in industrial
plans are considerable compared with the other equipment. So
each valve damage increases the operating costs that are allocated
to valves maintenance. Shifting system from one step to another in
duration less than 50 s damages the valve structure. In special
cases, shifting a PSA unit from one step to another in duration less
than 50 s decreases the pollutant absorption by sorbent without
any change in purity and efficiency. But in these cases, because
of the enhancement of the operating costs, it is more suitable to in-
crease the transition with duration of more than 50 s. According to
these statements, obtaining a suitable time step has direct effect on
pollution load and operating costs. As illustrated, the operating
conditions of PSA unit on various days are different. So it is not pos-
sible to set the time of each step to constant value. In other words,
time steps estimated for different operating conditions of a PSA
unit are not the same. Consequently, estimation of suitable time
for each step of PSA cycle that has direct effect on operating costs
and pollution load of sorbents is an important issue in the PSA unit
of domestic petrochemical plant and the other PSA units which
operates in different conditions.
Simulation is used to obtain an optimal time for adsorption
step. The plant data reported by domestic petrochemical plant
for three different days are tabulated in Tables 14–16. As is shown
in these tables, the inlet stream of PSA unit on these days has var-
ious impurities in methane, ethylene, acetylene, nitrogen, carbon
monoxide and carbon dioxide. It is obvious that obtaining a partic-
ular time for adsorption step, which operates in different operating
conditions, is necessary. The suitable times estimated by simula-
tion for adsorption step of PSA unit investigated in this study
which operates in three different operating conditions are visible
in Tables 14–16.
 M.R. Rahimpour et al. / Chemical Engineering Journal 226 (2013) 444–459 457

1 Table 13
Comparison between hydrogen purity estimated by simulation and corresponded
(a) plant data in different moments of a cycle.
0.99
Mole fraction of hydrogen

Time (s) Product purity% Product purity%

Simulation Plant data

0.98 23 99.9984 99.99865

37 99.997689 99.99856
57 99.99688 99.9985587
0.97 74 99.9995 99.99754
95 99.999498 99.99679
110 99.9994987 99.99869
0.96 150 99.9994978 99.99898
167 99.998 99.99789
245 99.9976 99.99578
0.95 296 99.9985 99.9975578
simulation 320 99.9989 99.998976
experimental 365 99.99768 99.99857547
0.94 380 99.995647 99.99856909
0 0.5 1 1.5 2 2.5 3 3.5 4
z-direction

0.05 Considering the value of hydrogen as a novel energy carrier,

every change in hydrogen production has a considerable effect
0.045
(b) on ecumenical price of hydrogen and world economy. The
Mole fraction of methane

0.04 enhancement of hydrogen recovery contributes to increase the

PSA unit economics and improves its efficiency. Consequently, it
0.035
is very important to investigate the suitable alternative for
0.03 enhancement of hydrogen recovery. The cycle time is an important
variable that has direct effect on the unit performance and operat-
0.025
ing parameters. Cycle time is the sum of the step times. So, the ob-
0.02 served increasing in cycle time is because of increasing the step
0.015
times. The enhancement of the step time, causes to enhance the
pollution load of sorbent and consequently decreases the ability
0.01 of the sorbents for adsorption of the impurities. Although the
simulation
0.005 experimental
increasing of cycle time decreases the ability of sorbents and prod-
uct purity, it would increase hydrogen recovery. According to these
0 statements, obtaining an optimal cycle time is an attractive alter-
0 0.5 1 1.5 2 2.5 3 3.5 4
native to increase the hydrogen recovery with slight reduction in
z-direction
product purity.
Fig. 10. Mole fraction variations of (a) hydrogen and (b) methane along the bed As illustrated, the outlet stream of PSA unit is used for hydroge-
axial direction that operates in purge step at 45 s. nation unit. Carbon monoxide is a toxic composition for hydroge-
nation unit and existence of carbon monoxide in product stream
The obtained optimal times for adsorption step in different
is an unfavorable phenomenon in this unit. Consequently, it is very
operating conditions (step 1, 2 and 3) have been allocated to PSA
important to consider that by enhancement of the cycle time, the
unit and the similar results are achieved. Actually, by allocating
increasing in impurity of other components except carbon monox-
optimal sub cycle time, pollution load of sorbents for purification
ide is allowable. Optimal cycle time has strength relation with mo-
of hydrogen to 99.99% vol. is minimized.
lar flow rate of inlet stream and other operation parameters. So it is
impossible to estimate a constant optimal time for various operat-
6.3. The effect of cycle time on hydrogen recovery and product purity
ing conditions.
As shown in Fig. 11, an optimal cycle time is obtained (670 s) for
In a PSA unit, hydrogen recovery and product purity are two
PSA unit of domestic petrochemical plant that operates in condi-
important and key parameters. The performance of the unit is con-
tions tabulated in Table 6. For these conditions allocation of
trolled by the variation of these parameters. It is obvious that gas
670 s to complete the cycle, decreases product purity and increases
purification by sorbents is the main objective of a PSA unit. The
hydrogen recovery to 99.8% and 0.8%, respectively, without any
mole ratio of hydrogen to total product which collected from the
enhancement of mole fraction of carbon monoxide in the outlet
product line in the last cycle duration is called product purity.
stream.
Product purity is described by the following equation:
The variation of cycle time is a controversial issue in the indus-
R T cycle trial PSA units. There is a reverse relation between sub cycle time
0 p  R2i  e  V P  X H2 p  dt
Product purity ¼ R T cycle ð15Þ (T) and feed flow rate which is described by the following
0 p  R2i  e  V P  dt equation:
As illustrated, the hydrogen recovery of the PSA unit investigated in
this study is about 75%. The mole ratio of hydrogen collected from 1000  feed flow ratedesign  T subcycledesign
T subcycle ¼ ð17Þ
the product line to total hydrogen that is fed to the bed entrance in K f  feed flow rateactual
the last cycle duration is called hydrogen recovery. Hydrogen recov-
ery is defined by the following equation: In other words, control systems use feed flow rate and Kf to estimate
R T cycle the sub cycle time automatically. Kf is a set time coefficient which is
p  R2i  e  V P  X H2 p  dt changeable by operators. Operators are allowed to change Kf to reg-
Hydrogen recovery ¼ R0T ð16Þ
cycle
p  R2i  e  mf  X H2 f  dt ulate the desired feed flow rate or sub cycle time. For instance,
0
maybe in a specific day consumer of PSA unit requests higher prod-
458 M.R. Rahimpour et al. / Chemical Engineering Journal 226 (2013) 444–459

Table 14
Estimated adsorption time for a possible operating condition (set 1).

Component Inlet stream (Mole fraction%) Outlet stream Sub-cycle time for Optimized time
(Mole fraction%) adsorption step(s)
Hydrogen 86.7 99.99 75 68.3
Methane 13.04 0.000002
Carbon Monoxide 0.097 0
Nitrogen 0.014 0
Acetylene 0.00065 0
Ethylene 0.00083 0
Carbon Dioxide + HC 0.00001 0

Table 15
Estimated adsorption time for a possible operating condition (set 2).

Component Inlet stream (Mole fraction%) Outlet stream Sub cycle time for Optimized time
(Mole fraction%) adsorption step(s)
Hydrogen 87.87 99.99 67 61
Methane 11.88 0.000006
Carbon Monoxide 0.083 0
Nitrogen 0.023 0
Acetylene 0.065 0
Ethylene 0.079 0
Carbon Dioxide + HC 0.00001 0

Table 16
Estimated adsorption time for a possible operating condition (set 3).

Component Inlet stream (Mole fraction%) Outlet stream Sub cycle time for Optimized time
(Mole fraction%) adsorption step(s)
Hydrogen 85.5 99.99 74 66
Methane 14.21 0.000005
Carbon Monoxide 0.087 0
Nitrogen 0.042 0
Acetylene 0.082 0
Ethylene 0.079 0
Carbon Dioxide + HC <0.00001 0

1 0.85 1 0.82

0.9995 0.81

0.999
Hydrogen recovery
0.8
Hydrogen recovery

Hydrogen purity
Hydrogen purity

0.9985 0.79
0.998 0.8
0.998 0.78

0.9975 0.77

0.997 0.76

0.996 0.75 0.9965 0.75

350 400 450 500 550 600 650 700 750 800 8 10 12 14 16 18 20
Cycle time Feed flow rate

Fig. 11. Variation of hydrogen recovery and product purity as a function of cycle Fig. 12. Variation of hydrogen recovery and product purity as a function of feed
time. flow rate.

uct stream compared with the other days. Enhancement of product
stream contributes to increase in feed stream. Based on Eq. (17) and
by considering the Kf regulated by operators, sub cycle time is esti-
mated and applied for PSA unit automatically. But sometimes a
questionable event takes place in PSA unit of industrial plants
jointly. It is better to give an example for more obvious explanation
of this event. On a specific day, desired amount of hydrogen which
must be collected in outlet stream of PSA unit of domestic petro-
chemical plant and Kf factor are not changed, whiles feed flow rate
and sub cycle time are changed simultaneously. On this specific day,
 M.R. Rahimpour et al. / Chemical Engineering Journal 226 (2013) 444–459
enhancement of mole fraction of methane in the inlet stream of PSA
unit is the only considerable variation of inlet operating variables.
In this condition, feed flow rate increases to compensate for hydro-
gen reduction in feed stream. On based of the equation 17 and by
considering the constant Kf, sub cycle time decreases automatically.
Consequently, variation of mole fraction of components in inlet
stream of PSA unit causes cycle time to be changed automatically.
6.4. The effect of feed flow rate on hydrogen recovery and product
purity
Feed flow rate is an important operating parameter that influ-
ences on hydrogen recovery and product purity. As the feed rate in-
creases in a constant cycle time, bed utilization is enhanced. In
other words, fraction of polluted bed increases. This phenomenon
decreases the ability of sorbents for adsorption of impurities and
consequently decreases product purity. On the other hand,
enhancement of feed flow rate increases the hydrogen recovery
slightly. According to these statements, obtaining an optimal feed
flow rate is an attractive alternative to increase the hydrogen
recovery with slight reduction in product purity.
It is impossible to estimate a specific optimal feed flow rate for
PSA unit of domestic petrochemical plant which operates in differ-
ent operating conditions. As shown in Fig. 12 an optimal feed flow
rate is obtained (11.3 m3/s) for PSA unit that operates under condi-
tions tabulated in Table 6.
For these conditions allocation of 11.3 m3/s as the feed flow
rate, decreases product purity and increases hydrogen recovery
to 99.776% and 77.5%, respectively, without any enhancement of
mole fraction of carbon monoxide in the outlet stream.
7. Conclusions
By considering the importance of hydrogen production as a
modern energy carrier and world price of hydrogen there is
increasing interest in hydrogen purity in PSA units.
In this work, the PSA unit of domestic petrochemical plant was
simulated. The results were in good consistency with the unit data.
The main goal of this simulation is to find the suitable time for
adsorption step of three different operating conditions. Hydrogen
recovery and product purity are two important parameters affect-
ing the performance of the PSA unit. Feed flow rate and cycle time
are two operating variables that have direct effect on hydrogen
recovery and product purity. In this study, the optimal value of
feed flow rate and cycle time is estimated for PSA unit of domestic
petrochemical plant that operates under certain operating
conditions.
In specific operating conditions, the optimal value of cycle time
and feed flow rate is 670 s and 11.3 m3/s respectively. The opti-
mum cycle time increases hydrogen recovery to 80% with slight
reduction of hydrogen purity in product stream. The optimum feed
flow rate contributes to increase hydrogen recovery to 77.5% with
slight reduction of hydrogen purity. The impurity of carbon mon-
oxide dos not increases due to enhancement of cycle time. Conse-
quently, allocating the 670 s to performance of complete cycle of
PSA unit is allowable and non-harmful for hydrogenation unit.
References
[1] B. Wang, W.D. Goodman, G.F. Froment, Kinetic modeling of pure hydrogen
production from decalin, J. Catal. 253 (2008) 229–238.
[2] N. Kariya, A. Fukuoka, T. Utagawa, M. Sakuramoto, Y. Goto, M. Ichikawa,
Efficient hydrogen production using cyclohexane and decalin by pulse-spray
mode reactor with Pt catalysts, Appl. Catal. 247 (2003) 247–259.
[3] A. Durgutlu, Experimental investigation of the effect of hydrogen in argon as a
shielding gas on TIG welding of austenitic stainless steel, Mater. Des. 25 (2003)
19–23.
459
[4] Y.S. Cheng, M.A. Peña, J.L. Fierro, D.C.W. Hui, K.L. Yeung, Performance of
alumina, zeolite, palladium, Pd–Ag alloy membranes for hydrogen separation
from Towngas mixture, J. Membr. Sci. 204 (2002) 329–340.
[5] K.L. Yeung, J.M. Sebastian, A. Varma, Novel preparation of Pd/Vycor composite
membranes, Catal. Today 25 (1995) 231–236.
[6] K.L. Yeung, R. Aravind, J. Szegner, A. Varma, Metal composite membranes:
synthesis, characterization and reaction studies, Stud. Surface Sci. Catal. 101
(1996) 1349–1358.
[7] D.M. Ruthven, S. Farooq, K.S. Knaebel, Pressure Swing Adsorption, VCH
Publishers, New York, U.S.A., 1994.
[8] G. Klein, T. Vermeulen, Cyclic performance of layered beds for binary ion
exchange, A.I.Ch.E. 71 (1975) 69–76.
[9] D.D. Frey, A model of adsorbent behavior applied to the use of layered beds in
cycling zone adsorption, Sep. Sci. Technol. 17 (1983) 1485.
[10] P.C. Wankat, D. Tondeur, Use of multiple sorbents in pressure swing
adsorption, parametric pumping and cycling zone adsorption, A.I.Ch.E. 81
(1985) 74.
[11] M. Chlendi, D. Tondeur, in: M.D. LeVan (Ed.), Dynamics of Two-Adsorbent Beds
with Flow-Reversal for Gas Separation, Fundamentals of Adsorption, Kluwer
Academic Publishers, Boston, U.S.A., 2009, pp. 187–194.
[12] C.F. Watson, R.D. Whitley, M.I. Meyer, Multiple zeolite adsorbent layers in
oxygen separation U.S. Patent. 5, 1996, pp. 529–610.
[13] M. Chlendi, D. Tondeur, Dynamic behavior of layered columns in pressure
swing adsorption, Gas. Sep. Purif. 9 (1995) 231.
[14] G. Pigorini, M.D. LeVan, Equilibrium theory for pressure swing adsorption, 2.
Purification and enrichment in layered beds, Ind. Eng. Chem. Res. 36 (1997)
2296.
[15] J.H. Park, J.N. Kim, S.H. Cho, J.D. Kim, R.T. Yang, Adsorber dynamics and optimal
design of layered beds for multicomponent gas adsorption, Chem. Eng. Sci. 53
(1998). 3951-63.
[16] S. Cavenati, C.A. Grande, A.E. Rodrigues, Separation of CH4/CO2/N2mixtures by
layered pressure swing adsorption for upgrade of natural gas, Chem. Eng. Sci.
61 (2006) 3893–3906.
[17] S.U. Rege, R.T. Yang, K. Qian, M.A. Buzanowski, Air-prepurification by pressure
swing adsorption using single/layered beds, Chem. Eng. Sci. 56 (2001) 2745–
2759.
[18] Y. Takamura, S. Narita, J. Aoki, S. Hironaka, S. Uchida, Evaluation of dual-bed
pressure swing adsorption for CO2 recovery from boiler exhaust gas, Sep. Purif.
Technol. 24 (2001). 519-28.
[19] T. Takeguchi, W. Tanakulrungsank, T. Inui, Separation and/or concentration of
CO2 from CO2/N2 gaseous mixture by pressure swing adsorption using metal-
incorporated microporous crystals with high surface area, Gas Sep. Purif. 7
(1993) 3–9.
[20] V.G. Gomes, K.W.K. Yee, Pressure swing adsorption for carbon dioxide
sequestration from exhaust gases, Sep. Purif. Technol. 28 (2) (2002) 161–171.
[21] S. Ahn, Y.W. You, D.G. Lee, K.H. Kim, M. Oh, C.H. Lee, Layered two-and four-bed
PSA processes for H2 recovery from coal gas, Chem. Eng. Sci. 68 (2012) 413–
423.
[22] T.G. Glover, M.D. LeVan, Sensitivity analysis of adsorption bed behavior:
examination of pulse inputs and layered-bed optimization, Chem. Eng. Sci. 63
(8) (2008) 2086–2098.
[23] R.P. Lively, N. Bessho, D.A. Bhandari, Y. Kawajiri, W.J. Koros, Thermally
moderated hollow fiber sorbent modules in rapidly cycled pressure swing
adsorption mode for hydrogen purification, Int. J. Hydrogen Energy 37 (20)
(2012) 15227–15240.
[24] S.J. Doong, R.T. Yang, Hydrogen purification by the multibed pressure swing
adsorption process, Reactive Polymers, Ion Exchangers, Sorbents 6 (1987) 7–
13.
[25] T. Saitou, K. Sugiyama, Hydrogen purification with metal hydride sintered
pellets using pressure swing adsorption method, J. Alloys Compd. 231 (1995)
865–870.
[26] S.E. Iyuke, W.R.W. Daud, A.B. Mohamad, A.A.H. Kadhum, Z. Fisal, A.M. Shariff,
Application of Sn-activated carbon in pressure swing adsorption for
purification of H2, Chem. Eng. Sci. 55 (2000) 4745–4755.
[27] V.S.L. Carlos, A. Grande, E.R. Alírio, Activated carbon for hydrogen purification
by pressure swing adsorption: multi component breakthrough curves and PSA
performance, Chem. Eng. Sci. 34 (2011) 2771–2777.
[28] E.H. Majlan, W.R.W. Daud, S.E. Iyuke, A.B. Mohamad, A.A.H. Kadhum, A.W.
Mohammad, M.S. Takriff, N. Bahaman, Hydrogen purification using compact
pressure swing adsorption system for fuel cell, Int. J. Hydrogen Energy 34 (6)
(2009) 2771–2777.
[29] D. Nikolic, A. Giovanoglou, M.C. Georgiadis, E.S. Kikkinides, Modelling and
simulation of multi-bed pressure swing adsorption processes, Computer Aided
Chem. Eng. 24 (2007) 159–164.
[30] M. Tańczyk, K. Warmuziński, Multicomponent pressure swing adsorption. Part
II. Experimental verification of the model, Chem. Eng. Process. 37 (1998) 301–
315.
[31] M. Masoumi, M. Shahrokhi, M. Sadrameli, J. Tpwfighi, Modeling and Control of
a Naphtha Thermal Cracking Pilot Plant, American Chemical Society,
Washington, DC, ETATS-UNIS, 2006.
[32] A. Tarafder, B.C.S. Lee, A.K. Ray, G.P. Rangaiah, Multiobjective Optimization of
an Industrial Ethylene Reactor Using a Nondominated Sorting Genetic
Algorithm, American Chemical Society, Washington, DC, ETATS-UNIS, 2005.
[33] C.R. Wilk Lee, Chem. Eng. Progr. 45 (1949) 218.
[34] C.R. Wilke, C.Y. Lee, Ind. Eng. Chem. 47 (1955) 1253.