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Ind. Eng. Chem. Res.

2001, 40, 3647-3658

3647

Air Separation by a Small-Scale Two-Bed Medical O2 Pressure


Swing Adsorption
Jeong-Geun Jee, Jong-Seok Lee, and Chang-Ha Lee*
Department of Chemical Engineering, Yonsei University, Shinchon-dong, Seodaemun-gu,
Seoul 120-749, Korea

A small-scale two-bed six-step pressure swing adsorption (PSA) process using zeolite 13X was
performed to provide oxygen-enriched air in the medical system. The binary mixture N2/O2 (79/
21 vol %) was used for PSA experiments. Cyclic behaviors of the PSA process were investigated
from unsteady- to steady-state conditions. Also, effects of various operating parameters on the
PSA performance such as the P/F ratio, adsorption pressure, feed flow rate, and adsorption
step time were investigated experimentally under the nonisothermal condition. The effect of
the P/F ratio was noticeably changed according to the adsorption pressure and feed flow rate
conditions. The higher the adsorption pressure, the slower the increasing rate of purity and the
higher the decreasing rate of recovery. However, as the adsorption pressure became higher, the
effect of the P/F ratio on the O2 purity became smaller. Furthermore, the effect of adsorption
pressure on the O2 purity and recovery was diminished gradually to the increase of the P/F
ratio. The feed flow rate also had a strong effect on the O2 purity. As for the product purity, the
low feed flow rate began to lose its advantage with an increase in the P/F ratio. The recovery
and productivity at a high feed flow rate was higher than those at a low feed rate even under
the high product purity region. The dominant operating factor to determine the O2 purity was
changed from the adsorption pressure to the feed flow rate as the P/F ratio was changed from
low to high values. The modified linear driving force (LDF) model similar to a solid-diffusion
model predicted the transition behavior of the cyclic process better than the LDF model.
Introduction
Numerous pressure swing adsorption (PSA) and
vacuum swing adsorption (VSA) processes have been
designed during the last 30 years for the production of
an oxygen-enriched air stream from ambient air.1-3 In
the industrial O2 PSA units, the dominant factor to
determine the energy requirement of a PSA cycle is the
pressure ratio of the high adsorption pressure to the low
desorption pressure. A pressure ratio of 4 or higher has
been used in industry, which has appeared to be a
barrier for PSA air separation.4 The performances of the
previous studies on the O2 PSA were about 93-99%
purity with 8-44% recovery from the O2/N2 mxiture.5-7
However, to recover the energy consumption by the high
adsorption pressure and low recovery, the VSA process8,9 was developed. The O2 VSA showed about 94%
purity with 55+% recovery.10 In addition, while the
adsorbent productivity of rapid PSA (RPSA) using the
short cycle times is much higher at the same recovery
and purity conditions than that of conventional PSA,
the energy demand is much higher than that of conventional PSA because of the frequent pressure variation.11,12
As another application of PSA, the small-scale units
of medical O2 PSA1 with higher than 80% O2 purity were
commercialized for patients with chronic pulmonary
dysfunction in the mid-1970s. Also, a small-scale application of PSA was extended to provide oxygenenriched air for the crew of a military aircraft.13 Most
small-scale units use a two-bed system, operated on a
* To whom correspondence should be addressed. Tel: +822-2123-2762. Fax: +82-2-312-6401. E-mail: leech@yonsei.ac.kr.

Skarstrom cycle, sometimes with the addition of a


pressure equalization step for a significant improvement
in recovery.3 At the scale of domestic medical O2 units,
the cost of power is a less significant consideration than
process simplicity and reliability.
Teague and Edgar13 presented the dynamic response
of the bed pressure history and prediction of transient
behavior in an on-board oxygen generation (OBOG)
system by using a mathematical model including the
feed and exhaust valves and purge orifice. They suggested that the magnitude of the temperature swing
over a cycle is significantly greater than that observed
experimentally in the OBOG system with 10-40 s cycle
time. Recently, Mendes et al.5 have focused on the
influence on the product purity and recovery of the
pressure rising rate during pressurization, pressure
lowering rate during the blowdown step, production
pressure, and intraparticle viscous flow in an O2 PSA
with zeolite 5A. They found that a higher pressurization
rate decreases the product purity and recovery, whereas
the pressure lowering rate during the blowdown step
has almost no effect. Also, they pointed out that the
production pressure has a complex effect on the product
purity and recovery. However, the influence of the
pressure rising rate on the purity and recovery was not
observed in the case of O2 PSA using very large
pressurization times (30 and 75 s), adsorbent with small
diameters, and adsorbent with large average pore
diameters.6,14,15 Also, in PSA processes with kinetic
separation effects, the pore diffusion model has been
used to enhance the simulation accuracy despite the
bulky computations.16-18 For cyclic separation processes
with short cycle periods, a modification of the linear

10.1021/ie010101l CCC: $20.00 2001 American Chemical Society


Published on Web 07/10/2001

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Ind. Eng. Chem. Res., Vol. 40, No. 16, 2001

driving force (LDF) equation has been suggested by


Nakao and Suzuki (1983)19 and Alpay and Scott (1993).20
Moreover, Kim and co-workers21-23 suggested both the
linear and higher approximations based on the biporous
diffusion model for short cycle periods, which are
functions of the cycle period alone.
In this study, a binary mixture that consisted of 21%
by volume O2 and 79% by volume N2 was separated by
a small-scale two-bed PSA with a small-size zeolite 13X
(20-32 mesh) as an adsorbent. The PSA process was
performed to produce higher than 80% O2 purity using
the traditional Skarstrom cycle with an equalization
step to improve the energetic performance. The effects
of typical operating parameters on a medical O2 PSA
performance, such as the adsorption pressure, P/F ratio,
and adsorption step time, were studied experimentally.
Also, the effects of both the adsorption pressure and feed
flow rate on the purity, recovery, and productivity were
investigated at a constant P/F ratio. Because the medical O2 producing system needs to supply oxygen very
fast, the PSA cycle time applied for this study was less
than 36 s/cycle. The predicted results by a LDF model
were compared to those by the modified LDF model
based on the pore diffusion model. The dynamic characteristics of the PSA process were also investigated
through the values such as the temperature history in
the bed, pressure, and concentration variations from
unsteady- to steady-state conditions.
Mathematical Models
To understand the dynamic behaviors of the adsorption bed during the PSA running, the mathematical
models were developed by the following assumptions:
(i) the gas phase behaves as an ideal gas mixture, (ii)
radial concentration and temperature gradients are
negligible, (iii) thermal equilibrium between adsorbents
and bulk flow is assumed, (iv) the flow pattern is
described by the axially dispersed plug-flow model, (v)
the mass-transfer rate is represented by the LDF and
modified LDF models, and (vi) the pressure drop along
the bed was considered by using the Ergun equation.
The assumption of neglecting the radial gradient was
widely accepted by numerous studies, and the others
are also common assumptions in simulating the adsorption process.24,25
The material balance for the bulk phase in the
adsorption column is represented by

-DL

2Ci
z

(uCi) Ci
1 -  qi
+
+ Fp
)0
z
z

t

2 P
z

+P

()

t T

+u

z
+u

( )]

z T

P
z

+ PT -DL

+ FpRT

( )
1-


()

2 1

i)1

qi
t

) 0 (2)

yi

+u

z2

yi

z
Fp

( )(

RT 1 -  qi
P

- yi

qi

i)1 t

) 0 (3)

where DL is the axial dispersion coefficient calculated


from the following Wakao equation.26,27

DL
20
+ 0.5
)
2uRp ReSc

(4)

Another characteristic of the adsorption process is the


temperature variation caused by the heat of adsorption.
In this system, the energy balance for the gas phase
includes the heat transfer to the column wall:

-KL

2T

+ FpCpg u

z2

FBCpg)

+T

z
n

- FB(-Hi)

qi

i)1 t

+ (tFgCpg +

2hi
RBi

(T - Tw) ) 0 (5)

where t is the total void fraction [) + (1 - )p], FB is


the bed density, [)(1 - )Fp], and hi is the internal heattransfer coefficient.
To consider the heat loss through a wall and the heat
accumulation in the wall, another energy balance for
the wall of the adsorption bed was used.

FwCpwAw

Tw
) 2RBihi(T - Tw) t
2RBoho(Tw - Tatm) (6)

where Aw ) (RBo2 - RBi2).


However, in this study, the adsorption bed was
constructed by an aluminum pipe for heat dissipation.
Therefore, if the system is operated at near isothermal
condition, eqs 5 and 6 can be neglected to save the
calculation time.
To consider the pressure drop effect across the bed,
Erguns equation was introduced as a momentum balance.28

dP
) au + bFu|u|
dz

(7-1)

(1)

When the ideal gas law (ci ) Pyi/RT) is applied to eq


1, the overall and component mass balances can be
represented as follows:

-DL

-DL

2yi

a)

1-
150 (1 - )
, b ) 1.75
3
2
4Rp

2Rp23

(7-2)

where u is the interstitial velocity.


The boundary and initial conditions of mass and
energy balances are presented below. The well-known
Danckwerts boundary conditions are applied.29

Boundary conditions for feed pressurization and


adsorption steps
-DL

( )|
yi
z

z)0

) u(yi|z)0- - yi|z)0+);

( )|
yi
z

z)L

)0
(8-1)

Ind. Eng. Chem. Res., Vol. 40, No. 16, 2001 3649

-KL

(Tz )|

(Tz )|

) Fg(Cp)gu(T|z)0- - T|z)0+);

z)0

z)L

)0

(8-2)

where yi|z)0- is the feed composition for component i.

Boundary conditions for purge, pressurizing


pressure equalization steps
-DL
-KL

( )|
yi
z

(Tz )|

z)L

) u(yi|z)L+ - yi|z)L-);

( )|
yi
z

z)0

)0
(9-1)

) Fg(Cp)gu(T|z)L+ - T|z)L-);

z)L

(Tz )|

z)0

) 0 (9-2)

where yi|z)L+ is the volume-averaged composition of the


effluent stream during the adsorption step for the purge
step and a temporal effluents composition during a
depressurizing pressure equalization step for the pressurizing pressure equalization step, respectively. The
fluid velocity is inherently negative during these steps.

Depressurizing pressure equalization and


countercurrent depressurization steps

( )| ( )|
yi
z

z)0

T
z

z)0

) 0;

( )|
yi
z

)
z)L

( )|
T
z

z)L

)0
(10)

In this study, the pressure history obtained during a


PSA experiment at the product end was fitted by
polynomials used as a boundary condition for the
momentum balance.
The sorption rate into an adsorbent pellet is described
by the LDF model with a single lumped mass-transfer
parameter:

KDe
qi
) i(q/i - qi), i )
t
R2

(11)

where i is a lumped mass-transfer coefficient inside


the adsorbent and De is the effective diffusivity defined
in a homogeneous solid-diffusion model.30 Also, the
below modified LDF model22 was applied for the sorption rate instead of eq 11 because the cycle time in this
study was relatively short. The modified LDF model is
obtained from the high-order approximation of a pore
diffusion model, while the LDF model is the first-order
approximation. Therefore, it is reported that the modified LDF model is sufficiently accurate compared to the
pore diffusion model and is as easy as the LDF model
to use.22

qi
) i(-105qi + z1 + 42q/i )
t
z1
) i(945)(q/i - qi)
t
where

i ) De/Rp2

(12)

Table 1. Characteristics of Adsorbents and Adsorption


Bed
adsorbent

zeolite 13X

type
normal pellet size [mesh]
average pellet size, Rp [cm]
pellet density, Fp [g/cm3]
heat capacity, Cps [cal/gK]
particle porosity, R
bed density, FB [g/cm3]

sphere
20-32
0.07
1.17
0.32
0.21
0.713

Adsorption Bed
length, L [cm]
inside radius, RBi [cm]
outside radius, RBo [cm]
heat capacity of the column, Cpw [cal/gK]
density of the column, Fw [g/cm3]
internal heat-transfer coefficient, hi [cal/cm2Ks]
external heat-transfer coefficient, ho [cal/cm2Ks]

50
2.5
2.75
0.216
2.7
9.2 10-4
3.4 10-4

The multicomponent adsorption equilibrium was predicted by the following extended Langmuir-Freundlich
model:

qmiBiPini

qi )

1+

(13)

BjPnj

j
j)1

where qm ) k1 + k2T, B ) k3 exp(k4/T), and ni ) k5 +


k6/T.
Experimental Section
The characteristics of the adsorbent and adsorption
bed are shown in Table 1. The adsorbent used in this
study was zeolite 13X (20 32 mesh, Oxy5). A moisturefree commercial gas mixture (O2/N2, 21/79 vol %) was
used as the feed gas.
The adsorption isotherms of pure O2 and N2 on zeolite
13X were measured at three different temperatures
(293, 303, and 313 K) by using a high-pressure volumetric apparatus up to 650 kPa. This apparatus consists
of two stainless steel vessels: a doser cell and an
adsorber cell. The pressure variations of these cells were
measured by pressure transmitters (Heise 621). The
adsorbent was regenerated at 623 K in a furnace after
every experiment.
The cyclic sequence and step time for the six-step
process and a simple flow diagram are illustrated in
Figure 1. A typical six-step, two-bed PSA process was
applied for the oxygen product from air: (I) feed
pressurization (FP), (II) high-pressure adsorption (AD),
(III) depressurizing pressure equalization (DPE), (IV)
countercurrent depressurization (DP), (V) purge with
a light product (PG), and (VI) pressurizing pressure
equalization (PPE).31 All of the PSA experiments were
performed at the same cyclic step time with 10 s
adsorption step time and purge step time. However, to
investigate the effect of step time, the two step times
were changed from 10 to 5 s only in the effects of the
adsorption step-time section. The duration of nonisobaric steps such as FP, PE, and DP steps was determined at 4 s, which was a minimum time to reach a
stable pressure at each step.
Also, the schematic diagram of the PSA unit used in
this study is shown in Figure 2. A two-bed PSA unit
constructed in this study was similar in size to that of
a medical oxygen generation system. It was possible to

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Ind. Eng. Chem. Res., Vol. 40, No. 16, 2001

Figure 2. Flow diagram and cycle sequence of a six-step PSA


process. Values in parentheses are step times.
Figure 1. Schematic diagram of the apparatus for a two-bed O2
PSA process.
Table 2. Operating Conditions for O2 PSA Experiments
run
no.

adsorption
time [s]

1
2
3
4

10

adsorption
pressure [atm]
3

5
6
7
8
9
10
11
12
13
14
15
16

17
18
19
20
21
22

P/F
ratio

feed flow rate


[L(STP)/min]

0.67
0.75
0.82
0.90

7.5

0.60
0.63
0.69
0.75
0.84
0.94

9.5

0.63
0.70
0.75
0.76
0.83
0.93
0.60
0.67
0.70
0.76
0.83
0.94

23
24
25
26
27
28
29

30
31
32
33
34
35

10

11.5

0.60
0.64
0.69
0.73
0.78
0.85
0.92
5.5

0.66
0.71
0.72
0.77
0.83
0.90

13.1

implement step changes in the following operating


variables: feed pressure, feed rate, purge rate, and cycle
time.
The adsorption beds were made of an aluminum pipe
with a 50 cm length, 5 cm i.d., and 0.49 cm wall thickness. The calibrated three resistance temperature detectors (RTD; Pt 100 ) were installed at the center

Figure 3. Isotherms of (a) pure O2 and (b) pure N2 at zeolite 13X.

radial positions of 10, 25, and 40 cm from the feed end


to measure temperature variations inside the bed. The
bed pressure and pressure drop were measured by the
two pressure transducers located at the feed and
product ends. The feed flow rate was controlled by a
metering valve, and the other feed line was used to
reach the desired pressure in a feed pressurization step.
Also, the surge tank with the same size of adsorption
bed was equipped to prevent flow fluctuation. The

Ind. Eng. Chem. Res., Vol. 40, No. 16, 2001 3651

Figure 4. Experimental and predicted temperature curves in the


middle of the adsorption bed at 4 atm adsorption pressure and
9.5 L(STP)/min feed flow rate.

Figure 6. Experimental and predicted O2 concentration curves


at 5.5 atm, 13.1 L(STP)/min, and 0.77 P/F ratio.

Figure 5. Experimental and predicted O2 concentration curves


at 4 atm, 9.5 L(STP)/min, and 0.75 P/F ratio.
Table 3. Isotherm Parameters, LDF Coefficient i
()KDe/Rp2), and Modified LDF Coefficient i ()De/Rp2) for
Zeolite 13X
N2
L-F Isotherm Parameter
k1 103 (mol/g)
12.52
k2 105 (mol/gK)
-1.785
k3 105 (1/atm)
2.154
k4 (K)
2333
k5
1.666
k6 (K)
-245.2
heat of adsorption, QI (cal/mol)
4390
Mass-Transfer Coefficient
LDF coefficient, i (s-1)
0.197
modified LDF coefficient, i (s-1)
0.01203

O2
6.705
-1.435
3.253
1428
-0.3169
387.8
3060
0.62
0.04133

metering valve installed at a pressure equalization line


was used to control the flow rate and the step time
during a pressure equalization step. The total amounts
of feed flow and the flow rate of each step were
measured by a wet gas meter. To keep the bed pressure
constant, a back-pressure regulator was installed between the adsorption bed and the product line. The
concentrations of the influent and effluent flows were
analyzed by a portable oxygen analyzer (Teledyne

Figure 7. O2 concentration profiles along the adsorption bed at


4 atm, 9.5 L(STP)/min, and 0.70 P/F ratio (20th cycle) in (a)
isothermal and (b) nonisothermal conditions.

Analytical Instruments, 320B/RC-D). The PSA unit and


supporting equipment were connected by a 1/4 in. copper
tube. The system was fully automated by a personal
computer with a developed control program, and all
measurements including pressure, temperature, and O2
purity were saved on the computer through an AD
converter.
After the bed was packed with the adsorbent regenerated at 613 K (during) overnight, the bed was kept at
1.5 atm O2 condition to prevent contamination from the
impurities in the atmosphere. Prior to each experimental run, the adsorption bed was vacuumed up to 10-3
mmHg for 2 h. The operating region corresponded to

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Ind. Eng. Chem. Res., Vol. 40, No. 16, 2001

Figure 8. Pressure variation history in the cyclic operation at 3


atm adsorption pressure.

Figure 10. O2 concentration profiles along the adsorption bed at


(a) the unsteady-state cycle (second cycle) and (b) the steady-state
cycle (20th cycle) under 4 atm, 9.5 L(STP)/min, and 0.76 P/F ratio.

The adsorption isotherms of N2 and O2 on zeolite 13X


are shown in Figure 3. The adsorption isotherm parameters and the LDF and modified LDF coefficients of N2
and O2 on zeolite 13X are also shown in Table 3.
Results and Discussion

Figure 9. Comparisons of concentration variation using the


modified LDF model among three different P/F ratios of (a) 0.60,
(b) 0.67, and (c) 0.83 at 4 atm and 11.5 L(STP)/min.

an adsorption pressure of 3-5.5 atm, a feed flow rate


of 7.5-13.1 L(STP)/min, and a P/F ratio of 0.60-0.94.
These operating ranges were investigated in the previous studies related to O2 PSA.4,7,13 The more detailed
operating conditions are shown in Table 2.
O2 purity was defined as the volume-average amount
of the product in the adsorption step. O2 productivity
and recovery were defined as follows.3

O2 productivity )
O2 recovery )

O2 [mole] in the product


kg of adsorbentcycle

O2 amount in the product


O2 amount in the feed

Also, the P/F ratio was defined as follows.

P/F ratio )

O2 amount in the purge step


O2 amount in the adsorption step

Cyclic Steady State of a Small-Scale O2 PSA.


Along with the concentration of the effluent stream, the
temperature variation inside the adsorption bed represented a cyclic behavior of a PSA process. The temperature variation located at 25 cm from the feed end is
presented in Figure 4. The temperature excursion at the
initial cycle showed a relatively small extent of temperature swing. This implied that the concentration
wave fronts did not proceed much from the feed end
because of the vacuum initial condition. However, the
temperature excursion of the second cycle was higher
than that of the first one because a considerable amount
of adsorbates at this location underwent adsorption and
desorption during the cycle. Then, the maximum temperature of the temperature swing was decreased with
an increase in the cycle. As shown in Figure 4, the
temperature variation did not approach a cyclic steady
state even after 20 cycles. However, the range of the
temperature swing was about 2 K, and the difference
between temperature excursions was less than 0.5 K
after 15 cycles. The experimental data were compared
with the simulated results using the LDF model in eq
11 and the modified LDF model in eq 12. The modified
LDF model predicted accurately the experimental results more than the LDF model. Because this modified
LDF model is the higher approximation of the pore

Ind. Eng. Chem. Res., Vol. 40, No. 16, 2001 3653

Figure 11. Comparisons of O2 (a) purity, (b) recovery, and (c)


productivity between 3 atm, 9.5 L(STP)/min and 4 atm, 9.5 L(STP)/
min at various P/F ratios.

diffusion model, this model showed better prediction


than the LDF model for the relatively fast cycle process.
Also, the predicted temperature curve by the modified
LDF model showed a more symmetric form than that
of the LDF model, even though the difference between
the predicted results by both models was small. This is
because the PSA system with a very short cycle time
showed a linear increase and a linear decrease in the
concentration and temperature, showing almost a symmetric curve.22,32
Figures 5 and 6 show a representative cyclic behavior
by comparing the experimental concentration with the
predicted concentration variation. Compared to the
temperature variation in Figure 4, the composition of
the effluent stream approached rapidly to a cyclic steady
state. After approximately 15 cycles, the performance
difference between the last two cycles was less than
0.05%. As can be expected in Figure 3, the selectivity
change in the experimental range using zeolite 13X is
almost negligible under the condition of less than 2 K
temperature excursion. This implies that the system
behaves almost isothermally, as was already observed
by Kapoor and Yang (1989)33 and Mendes et al. (2000).5
Therefore, the composition variation was not affected
by the temperature variation after certain cycles. Also,
the product purity predicted by the modified LDF model
was more accurate than that of the LDF model as shown
in Figures 5 and 6. In the present study, all of the
experimental data were collected at above 15 cycles.
Figure 7 shows a comparison between isothermal and
nonisothermal oxygen concentration profiles. Because
the bed temperature was steeply increased by the
adsorption of N2 during a short FP step time (4 s), the
concentration profile in the nonisothermal condition

Figure 12. Effects of adsorption pressure on O2 concentration


profiles along the adsorption bed in the adsorption step at 9.5
L(STP)/min feed flow rate, (a) low P/F ratio (0.65) and (b) high
P/F ratio (0.90) conditions.

proceeded to the product end more than that in the


isothermal condition. Except for this step, the concentration profiles at the same step under both conditions
showed very similar behaviors. Because of the small
heat of adsorption and the aluminum pipe with a high
heat-transfer rate, it is implied that this PSA system
was operated at near isothermal condition.
In cyclic operation, the prediction of cyclic pressure
variation is very important because the pressure variation has a great effect to determine adsorption amounts
and adsorption rates. Figure 8 shows the pressure
profile at the feed end during the cyclic operation. To
effectively predict the pressure variation in cyclic operation, an empirical polynomial model obtained from an
experimental pressure profile was applied to the simulation. As can be seen in Figure 8, the predicted pressure
profile agreed satisfactorily with the experimental
value. Furthermore, the predicted pressure history by
neglecting Erguns equation was almost the same as
that of Erguns equation even though a short cycle time
and a densely packed bed were used. This result implies
that the pressure drop in this system can be neglected
because of the short length and large diameter of the
bed.
Figure 9 shows the effect of the P/F ratio on the
concentration variation from unsteady to steady state.
While the product purity at the first cycle was little
affected by the P/F ratio, the effect of the P/F ratio on
the purity was very conspicuous with an increase in the
cycle. Also, the higher the P/F ratio, the longer the time
to reach the steady state.
The predicted O2 concentration profiles in the gas
phase at the end of each step are presented in Figure

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Ind. Eng. Chem. Res., Vol. 40, No. 16, 2001

Figure 13. Comparisons of O2 (a) purity, (b) recovery, and (c)


productivity between 7.5 and 9.5 L(STP)/min feed flow rates at 3
atm and various P/F ratios.

Figure 14. Comparisons of O2 (a) purity, (b) recovery and (c)


productivity between 9.5 and 11.5 L(STP)/min feed flow rates at
4 atm and various P/F ratios.

10a for the unsteady-state cycle and Figure 10b for the
steady-state cycle. In Figure 10a, the O2 concentration
wave front at the end of a pressurization step proceeded
at the end of the bed. The unfavorable wave front had
a detrimental effect on the adsorption step because the
mass-transfer zone (MTZ) was very wide even at the
adsorption step. However, about a 65% O2 purity stream
at the end of a DPE step was introduced to the next
bed, and the N2-rich stream at the end of the DP step
was exhausted at the feed end. In the early cycle, the
purge step to increase the product purity affected the
concentration profile mostly at the product end, but the
concentration profile of a DP step keeps more or less
its shape at the feed end. Also, the concentration profiles
at all steps showed concave shapes except at a PPE step.
At the end of a PPE step, the product end was contaminated again with a convex shape of the O2 concentration
profile. This lowers the product purity at the beginning
of the adsorption step until the cyclic steady state.
However, in a cyclic steady state as shown in Figure
10b, the O2 concentration profile at each step showed
an asymptotic shape with a high O2 purity at the
product end.10 Especially, the concentration profile at
an FP step located behind that of an AD step and the
O2 concentration wave fronts at PPE and FP steps
became steeper than those in the cyclic unsteady state.
This played a very important role in producing a highpurity product because the contamination of the product
end by strongly adsorbed components during the desorption steps had bad effects on the adsorption step of
the next cycle. Therefore, the product purity was
increased from the cyclic unsteady state to the cyclic
steady state as shown in Figure 7.

Effects of the Operating Variables on SmallScale O2 PSA. In this study, the effects of the operating
variables on a PSA performance such as the P/F ratio,
adsorption pressure, feed flow rate, and adsorption step
time were studied experimentally and numerically
under the cyclic steady-state condition.
(i) Effects of the P/F Ratio. The effect of the P/F
ratio on the O2 purity, recovery, and productivity is
shown in Figures 11, 13, 14, 16, and 18. In all of the
figures, as the P/F ratio was increased, the O2 purity
was improved and the O2 recovery was decreased
linearly.4 However, at each adsorption pressure, the
purity was not increased despite an increment in the
P/F ratio above the limiting P/F ratio (about 0.8-0.9).
However, the O2 productivity was decreased linearly to
the increment of the P/F ratio. The purging of the bed
with the product allowed for a sharper O2 wave front
during the feed step by cleaning the bed of the impurity,
thus increasing the product purity. Although the purity
of oxygen depicted in all of figures exceeded 99% purity,
argon in real air should be considered. Hence, the actual
purity of O2 that would be obtained in a real case is
about 95-96%.
(ii) Effects of the Adsorption Pressure. Figure 11
shows the effect of an adsorption pressure on O2 PSA
performance under various P/F ratios. In Figure 11a,
the adsorption pressure in the range of low P/F ratio
affected significantly the product purity, while the
product purity was not affected by the adsorption
pressure in the range of high P/F ratio. The difference
of the recovery and productivity between both operating
conditions decreased with an increase in the P/F ratio.
The decline of recovery with an increase in the adsorption pressure is mostly due to the loss of O2 in the feed

Ind. Eng. Chem. Res., Vol. 40, No. 16, 2001 3655

Figure 15. Effects of the feed flow rate on O2 concentration


profiles along the adsorption bed in the adsorption step at 3 atm,
(a) low P/F ratio (0.65), and (b) high P/F ratio (0.90) conditions.

Figure 16. Comparisons of O2 (a) purity, (b) recovery, and (c)


productivity among three different adsorption pressure and feed
flow rate conditions at various P/F ratios.

end during a DP step. In the low P/F ratio region, the


O2 productivity at 4 atm adsorption pressure was larger
than that at 3 atm adsorption pressure in Figure 11c
because the total capacity for O2 product and the O2
purity was increased with pressure. However, in the
high P/F ratio region, the difference of productivity
between both operating pressure conditions became
almost the same because the difference of product purity
and recovery was notably diminished.
These results can be clearly explained by Figure 12,
which represents the predicted axial profiles of the O2
mole fraction in the gas phase at the end of the
adsorption step. Because the slope of the MTZ became
steeper at higher pressure, beds can be used more
effectively and at the same time the product purity
becomes higher. In the case of the low P/F ratio, the
difference between concentration profiles becomes smaller
as the pressure becomes higher than 4 atm in Figure
12a. Meanwhile, Figure 12b shows that this difference
in high P/F ratio becomes small from above 3 atm.
Therefore, because the large amount of O2 in the purge
step was consumed at the high P/F ratio region and the
difference of O2 loss at both adsorption pressure conditions during a DP step was relatively small, the difference of recovery and productivity between both adsorption pressure conditions became smaller with an increase
in the P/F ratio as shown in Figure 11.
(iii) Effects of the Feed Rate. Figures 13 and 14
show the effects of the feed rate on the product purity,
recovery, and productivity at two adsorption pressure
conditions. In these two figures, the purity at low feed
rate was higher than that at high feed rate because the
contact time between feed flow and adsorbent was
increased when the feed gas flowed slowly. Also, the

results showed that the difference of purity between two


feed rates at 4 atm adsorption pressure was smaller
than that at 3 atm adsorption pressure. This implies
that the effect of the feed flow rate was gradually
diminished with an increase in the adsorption pressure
due to the limiting amount of adsorption.
In Figures 13b and 14b, O2 recovery was decreased
in the low feed flow rate because the large purge amount
was needed to remove the strongly adsorbed N2. The
recovery difference between the two feed rates decreased
with an increase in the adsorption pressure. Also, this
difference in the recovery was maintained almost constantly independent of the change of the P/F ratio. This
is because the net amount of product at the high feed
rate was larger than that at the low feed rate.
Figures 13c and 14c show productivity in the range
of the experimental P/F ratio. The productivity of the
higher feed rate process was higher than that of the
lower feed rate independent of the adsorption pressure.
Also, although the product purity was changed by the
P/F ratio, the productivity showed a parallel decrease
in both feed rate processes due to the parallel decrease
in the recovery. It is noted that the recovery and
productivity at the higher feed rate process was higher
than those at the lower feed rate even under the high
product purity region, which is different from the effects
of the adsorption pressure in Figure 11.
However, as for the product purity, the low feed rate
process began to lose its advantage with an increase in
the P/F ratio. This result was confirmed by the O2 mole
fraction curves of adsorption step at various feed flow
rates in Figure 15. In the low P/F ratio condition, the
MTZ of O2 became wide with an increase in the feed

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Ind. Eng. Chem. Res., Vol. 40, No. 16, 2001

Figure 17. Effects of adsorption pressure and feed flow rate on


O2 concentration profiles along the adsorption bed in the adsorption step at (a) low P/F ratio (0.65), (b) intermediate P/F ratio
(0.75), and (c) high P/F ratio (0.90) conditions.

rate due to the small amount of the purge. Therefore,


the product end at the adsorption step was significantly
contaminated by the increased feed rate. On the contrary, as shown in Figure 15b, the product end section
was kept clean in the high P/F ratio condition by
keeping the concentration wave fronts far from the
product end until 9.5 L(STP)/min. Also, the MTZ of O2
showed almost the same interval with an increase in
the feed rate. Consequently, the need to make the
product end section clean by large amounts of purge was
reduced at this operating condition.
(iv) Simultaneous Effects of the Feed Flow Rate
and Adsorption Pressure. Figure 16 shows a change
of the process performance with a change of both
adsorption pressure and feed flow rate. As can be seen
in this figure, the O2 purity in the low P/F ratio was
higher at higher adsorption pressure and feed flow rate
conditions. However, the purity was crossed over with
an increase in the P/F ratio. As mentioned in Figures
11, 13, and 14, the effect of the P/F ratio on the purity
was delineated with an increase of the adsorption
pressure or feed flow rate. This phenomenon caused the
crossover in the O2 purity. Figure 17 shows the O2 mole
fraction curves of the adsorption step after 20 cycles.
When parts a and b of Figure 17 are compared, the
product end at 4 atm operating condition became
cleaner than that at 5.5 atm operating condition. Also,
at high P/F ratio in Figure 17c, the difference among
O2 MTZs at each operating condition was very small.
The recovery in Figure 16b was higher as the adsorption
pressure was lower. This result implies that the high
adsorption pressure still caused low O2 recovery because
of large amounts of desorbed O2 at the blowdown and

Figure 18. Comparisons of O2 (a) purity, (b) recovery, and (c)


productivity between two different adsorption step times at 4 atm,
11.5 L(STP)/min, and various P/F ratios.

purge steps. However, the recovery was crossed over at


the high P/F ratio region. Contrary to the recovery, the
productivity was increased with an increase in the feed
flow rate and the crossover was not found. This is
because high adsorption pressure and high feed flow
rate caused enlargement of the adsorption capacity and
absolute O2 supply in the system.
(v) Effects of the Adsorption Step Time. Figure
18 shows the effect of the adsorption step time on the
O2 purity, recovery, and productivity. Only the adsorption step time in the cycle was diminished from 10 to 5
s. As shown in this figure, the purity of O2 was improved
but the recovery of O2 was decreased due to the short
adsorption step time. Because of the reduced adsorption
step time, the N2 amount at the adsorption step in the
bed was smaller than that at 10 s adsorption step time.
Therefore, compared with the case of 10 s adsorption
time, a relatively low purge rate at the reduced adsorption step time led to a high purity. However, the reduced
adsorption step time also caused a low product amount.
Hence, the recovery and productivity were decreased
greatly compared to the operating condition with 10 s
adsorption step time under the same adsorption pressure and feed flow rate conditions.
To sum up, when the performance of the small-scale
medical O2 PSA process was compared with that of the
previous O2 PSA studies5-7,10 in the range of 95-99.5
vol % O2 purity; the 25-50% recovery obtained from this
study was equal to or slightly higher than the others.
Conclusions
Dynamic characteristics and performances of the
medical O2 PSA process were studied through the

Ind. Eng. Chem. Res., Vol. 40, No. 16, 2001 3657

experimental and theoretical approaches. The predicted


results from a mathematical model in this study agreed
well with the experimental data.
Cyclic behaviors of the PSA process were investigated
thoroughly from unsteady- to steady-state conditions.
The composition variation reached cyclic steady state
after approximately 15 cycles while the temperature
variation did not even after 20 cycles. Because the
performances of cyclic operation were not affected by
the temperature variation after certain cycles, the
system behaves almost isothermally. The effect of the
P/F ratio on purity became conspicuous with an increase
in cycles. The O2 concentration wave fronts at the PPE
and FP steps in the cyclic steady state became steeper
than those in the cyclic unsteady state. Also, the higher
the P/F ratio, the longer the time to reach the steady
state. The modified LDF model predicted the temperature and concentration variation better than the LDF
model. However, the difference between the predicted
results by both models at the steady state was almost
negligible.
As the P/F ratio was increased, the purity was improved and the recovery and productivity were decreased because of a loss of O2 in the product stream.
Also, there was limiting P/F ratio (about 0.8-0.9) to
have a meaningful effect on the O2 purity. Especially,
the effect of the P/F ratio was significantly coupled with
the variation of the adsorption pressure, feed rate, and
adsorption step time. In the case of low P/F ratio, the
difference between concentration profiles at the adsorption step becomes smaller as the pressure becomes
higher than 4 atm. However, this difference in the high
P/F ratio becomes small from above 3 atm. Therefore,
the difference of the process performances by the
adsorption pressure was decreased with an increase in
the P/F ratio.
The effect of the feed flow rate was gradually diminished with an increase in the adsorption pressure due
to the limiting amount of adsorption. However, as for
the product purity, the low feed rate began to lose its
advantage with an increase in the P/F ratio. O2 recovery
was increased in the low feed flow rate because the large
purge amount was needed to remove the strongly
adsorbed N2. The higher the feed flow rate, the higher
the productivity. Also, the difference of recovery was
maintained almost constantly independent of the P/F
ratio. This is because at a high feed flow rate condition,
the net amount of product was larger than that at a
low feed flow rate. When both the adsorption pressure
and feed flow rate changes simultaneously, the product
purity was higher at higher adsorption pressure and
feed flow rate conditions in the low P/F ratio. However,
the purity was crossed over with an increase in the P/F
ratio. The adsorption step time also had a considerable
effect on the O2 purity, recovery, and productivity. As
the adsorption step time was diminished to 5 s, the O2
purity was improved because the N2 amount at the
adsorption step in the bed was smaller than that at 10
s adsorption step time. However, the recovery and
productivity were greatly decreased in this condition.
Hence, the reduced adsorption step time also caused a
low product amount.
Acknowledgment
Financial assistance and support from KOSEF (952-10-01-01-3) and Daesung Sanso Co. are gratefully
acknowledged.

Nomenclature
Aw ) cross-sectional area of the wall (cm2)
B ) equilibrium parameter for Langmuir-Freundlich
model (atm-1)
ci ) i component concentration in the bulk phase (mol/cm3)
Cpg, Cps, Cpw ) gas, pellet, and wall heat capacity, respectively (cal/gK)
De ) effective diffusivity defined by the solid-diffusion
model (cm2/s)
DL ) axial dispersion coefficient (cm2/s)
-H ) average heat of adsorption (cal/mol)
k ) parameter for the LRC model
K ) proportionality parameter for the LDF model
KL ) axial thermal conductivity (cal/cmsK)
L ) bed length (cm)
P ) total pressure (atm)
PA, PD ) final adsorption and desorption partial pressures,
respectively (atm)
Pc ) critical pressure (atm)
q, q*, q
j ) amount adsorbed, equilibrium amount adsorbed,
and average amount adsorbed, respectively (mol/g)
qm ) equilibrium parameter for the Langmuir-Freundlich
model (mol/g)
r ) radial distance in the pellet (cm)
R ) gas constant (cal/molK)
Rp ) radius of the pellet (cm)
RBi, RBo ) inside and outside radius of the bed, respectively
(cm)
t, tst ) time and stoichiometric breakthrough time, respectively (s)
TA, TD ) final adsorption and desorption temperatures,
respectively (K)
Tatm ) temperature of the atmosphere (K)
Tc ) critical temperature (K)
T, Tw ) pellet or bed temperature and wall temperature,
respectively (K)
u ) interstitial velocity (cm/s)
wc ) wave velocity for concentration front (cm/s)
yi ) mole fraction of species i
z ) axial distance in the bed from the inlet (cm)
Greek Symbols
, t ) voidage of the adsorbent bed and total void fraction,
respectively
Fg, Fp, FB, Fw ) gas density, pellet density, bulk density,
and bed wall density, respectively (g/cm3)

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Received for review February 6, 2001


Revised manuscript received May 16, 2001
Accepted May 16, 2001
IE010101L