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3647
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.
3648
-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)
DL
20
+ 0.5
)
2uRp ReSc
(4)
-KL
2T
+ FpCpg u
z2
FBCpg)
+T
z
n
- FB(-Hi)
qi
i)1 t
+ (tFgCpg +
2hi
RBi
(T - Tw) ) 0 (5)
FwCpwAw
Tw
) 2RBihi(T - Tw) t
2RBoho(Tw - Tatm) (6)
dP
) au + bFu|u|
dz
(7-1)
(1)
-DL
-DL
2yi
a)
1-
150 (1 - )
, b ) 1.75
3
2
4Rp
2Rp23
(7-2)
( )|
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)
( )|
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)
( )| ( )|
yi
z
z)0
T
z
z)0
) 0;
( )|
yi
z
)
z)L
( )|
T
z
z)L
)0
(10)
KDe
qi
) i(q/i - qi), i )
t
R2
(11)
qi
) i(-105qi + z1 + 42q/i )
t
z1
) i(945)(q/i - qi)
t
where
i ) De/Rp2
(12)
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
3650
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
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
Ind. Eng. Chem. Res., Vol. 40, No. 16, 2001 3651
O2
6.705
-1.435
3.253
1428
-0.3169
387.8
3060
0.62
0.04133
3652
O2 productivity )
O2 recovery )
P/F ratio )
Ind. Eng. Chem. Res., Vol. 40, No. 16, 2001 3653
3654
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
3656
Ind. Eng. Chem. Res., Vol. 40, No. 16, 2001 3657
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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