Ind. Eng. Chem. Res.

2007, 46, 591-599 591

High-Purity Oxygen Production by Pressure Swing Adsorption

J. C. Santos, P. Cruz, T. Regala, F. D. Magalhães, and A. Mendes*
LEPAEsDepartamento de Engenharia Quı́mica, Faculdade de Engenharia, UniVersidade do Porto, Rua Dr.
Roberto Frias, 4200-465 Porto, Portugal

The oxygen purity produced by pressure swing adsorption (PSA) processes is limited to 95%, with the rest
being essentially argon. This oxygen grade is suitable for many industrial applications. However, medical
applications, cylinder filling, oxyfuel cutting in metal fabrications, and fuel cells technology with recirculation
loop, among others, require oxygen with a higher purity (99% or above). In this paper, a study of high-purity
oxygen production by a PSA unit using a silver exchanged zeolite from Air Products and Chemicals, Inc.,
with oxygen/argon adsorption selectivity is presented. This study comprehends the determination of adsorption
equilibrium isotherms of oxygen, nitrogen, and argon as well as the simulation and optimization of a PSA
experimental unit and the corresponding experimental validation.

Introduction
Oxygen is a gas with many applications. It may be used in
chemical processing, fishing farms, medical applications, com-
bustion enhancement, oxyfuel cutting operations in metal
fabrication, bleaching in the paper industry, wastewater treat-
ment, fuel cells, etc.
Oxygen production (purity below 95%) from air, using
nitrogen selective zeolites of type A (5A) or X (13X-NaX, LiX,
or LiLSX), by means of pressure swing adsorption (PSA)
processes has noticeably increased in the past decade. However,
the concentration of the product is limited to 95% oxygen,
because of the presence of argon in air, since these adsorbents
present similar adsorption capacities for oxygen and argon.
There are some applications that require higher oxygen
purities. In the case of fuel cell technology, when 95% oxygen
is used, the average concentration of oxygen in the cathode
recirculation loop is ∼55%.1 To minimize the amount of oxygen
that is lost in the purge, which can be seen as an energy loss,
a higher concentration of oxygen may be used, which will result
in a reduction of the argon buildup and a reduction of the purge
flow rate and, thus, in a smaller requirement of this gas.2 Medical
applications, such as surgeries, in the United States require
oxygen with 99% purity and in Europe require oxygen with
99.5% purity. Thus, it is important to develop a simple and
portable technology for producing high-purity oxygen (for
example, for use in campaign hospitals).
Some research has been carried out in the past years for the
development of new adsorbents with selectivity for argon
relative to oxygen, allowing the production of oxygen with a
purity above 95% by PSA.2 In 1999, Hutson et al. suggested
the addition of silver to LiX zeolites for improving the air
separation performance, by increasing the nitrogen adsorption
capacity, and presented simulation results of a PSA unit
producing oxygen with a purity of 96.42% and a recovery of
62.74% from a feed containing 22% of oxygen and 78% of
nitrogen (no argon was used).3 Although their adsorbent does
not actually present selectivity of argon relative to oxygen, the
argon adsorption capacity was slightly increased. In 2002, Air
Products and Chemicals, Inc., patented an argon/oxygen selec-
tive X-zeolite (U.S. 6432170 B1) designated as AgLiLSX (low
silica X).4 In 2003, a vacuum and pressure swing adsorption
* To whom correspondence should be addressed. E-mail: mendes@
fe.up.pt. Phone: +351 22 5081695. Fax: +351 22 5081449.
10.1021/ie060400g CCC: $37.00 © 2007 American Chemical Society
Published on Web 12/20/2006
(VPSA) unit for the production of high-purity oxygen from air,
using AgLiLSX, was described in a patent by the same
company.5 The unit described may use one layer of AgLiLSX
or two layers of adsorbents: LiX and AgLiLSX. According to
the simulation results presented in this patent, changing the
percentage of AgLiLSX in the bed from 50 to 100% allows the
production of 99% oxygen with a recovery between 6 and 15%,
respectively. The unit is operated between 0.34 and 1.4 bar at
38 °C. According to the Air Products and Chemicals’ patent,
the recovery of a VPSA unit with unspecified volume and flow
rates and producing 99% of oxygen is ∼4% when fed with a
current of 95% oxygen and 5% argon (such as the product of
a PSA unit using a traditional adsorbent).
Two other technologies may be used for producing high-
purity oxygen from air but are more complex and make use of
two steps. Both units have a pressure swing adsorption (PSA)
unit packed with a zeolite for producing 95% of oxygen and
5% of argon. The product of this unit is fed to either a carbon
molecular sieve (CMS) membrane module or another PSA unit
packed with CMS adsorbent. In both systems, the product is
obtained at low pressure and a compressor must be used to bring
the product pressure to the operating requirements.2
The low separation factor of polymeric membranes, which
hinders the production of high-purity oxygen, has led to the
development of different configurations such as the continuous
membrane column (CMC)6-8 and the CMC in two-strippers-
in-series (TSS) mode6,8 or membrane cascades.9-11 These
multistage configurations make use of several membrane
modules, and the streams are recycled between the modules.
Many arrangements of the modules are already patented.12-21
The combination of polymeric membrane modules with PSA
units for high-purity oxygen production can also be found in
the literature.8,22
The ability of pore tailoring of the carbon molecular sieve
membranes together with its high permeability and selectiv-
ity makes the use of this material very appealing since it
allows the production of high-purity oxygen with only one
module.2 According to simulation results, a CMS membrane
module with a selectivity of oxygen relative to argon of 14,
using a feed pressure of 6 bar and a permeate pressure of 0.1
bar, is able to produce 99.5% of oxygen with a recovery of
46%.2 This technology associated with a PSA unit packed
with Oxysiv MDX is expected to yield a global recovery
∼36%.2
592 Ind. Eng. Chem. Res., Vol. 46, No. 2, 2007

Table 2. Position of the Valves during the Cycle

valve
B B T
step VC1 VC2 VC1 VTC2 VF VProd
1 2f1 1f3 1f3 1f2 on off
2 2f1 1f3 1f2 1f2 on on
3 1f2 1f2 1f3 1f3 off off
4 1f3 2f1 1f2 1f3 on off
5 1f3 2f1 1f2 1f2 on on
6 1f2 1f2 1f3 1f3 off off

the bed end were used to measure the pressure variations in the
bed. The feed flow rate was measured by a mass flow meter
(Bronkhorst High-Tech, F-112AC, 0-20 dm3STP/min). The
purge and equalization flow rates were measured using two
Bronkhorst High-Tech, F-112C, 0-10 dm3STP/min mass flow
meters. The production flow was controlled using a Bronkhorst
High-Tech, F-201C, 0-0.1 dm3STP/min mass flow controller.
Figure 1. Schematic representation of the experimental PSA apparatus: In order to keep the pressure in the adsorption bed constant
FM ) flow meter; FC ) flow controller; PR ) pressure reducer; and ST during the production step, a pressure regulator (Joucomatic)
) storage tank. was installed between the feed tank and the adsorption columns.
The interchange between adsorption columns is made using two
Table 1. Characteristics of the Adsorbent, Adsorption Bed, and three-way electrovalves (ASCO: EV1, EV2) installed at the
Storage Tank columns bottom. At the columns top, there are also two three-
bed length L 27 cm way electrovalves (ASCO: EV1, EV2) in order to change
bed internal diameter d 2 cm between equalization and production steps. Two oxygen analyz-
column thickness 0.175 cm ers were used: one from M&C, model PMA22, from 0 to 100%
bed porosity b 0.36 with an accuracy of 0.1% FS, and another from Sable Systems,
storage tank length LST 27 cm
storage tank diameter dST 2 cm
model PA-1B, also from 0 to 100% with an accuracy of 0.01%
adsorbent porosity p 0.471 FS. The analyzers were calibrated each run using pure oxygen
adsorbent diameter dp 1.01 mm as span and a calibrated mixture of 90% oxygen, 5% nitrogen,
Peclet number for mass transfer Pe 600 and 5% argon as zero.
Table 2 presents the position of the valves during the cycle.
The third technology referred to before for producing high- The left column was packed with 101.86 g of AgLiLSX from
purity oxygen, i.e., a PSA unit packed with zeolite followed by Air Products and Chemicals and the right column was packed
another PSA unit packed with carbon molecular sieve adsorbent, with 101.37 g of AgLiLSX.
can also be readily found in the literature.23-34 In 2005, Jee et
al.29 presented a PSA unit packed with a CMS from Takeda,
Mathematical Model
producing 99.5% of oxygen from a feed mixture of 95% of
oxygen and 5% of argon. This unit had a recovery ∼57% if the The mathematical model used for describing the operation
product was obtained at a pressure close to the atmospheric of the pressure swing adsorption unit was based on the following
pressure or ∼80% if the product was obtained at low pressure.29 assumptions: perfect gas behavior, axially dispersed plug flow,
However, from the three technologies proposed before, this one uniform bed properties along the axial coordinate, negligible
should result in the largest unit. pressure drop, negligible radial gradients, interparticle mass
The choice of the most suitable technology depends on the transport described by the linear driving force (LDF) ap-
application characteristics. For small systems, the PSA unit with proximation,35 and adsorption equilibrium between gaseous and
AgLiLSX should be the most adequate. For systems where size adsorbed phases described using the Langmuir-Freundlich
is not so important, an economical balance should be made to equation. Cruz et al.36 showed that isothermal operation is a
find out which of these technologies is the best solution. reasonable hypothesis for oxygen separation from air, so this
In this paper, high-purity oxygen production using a zeolite was also considered here. According to these assumptions, the
patented by Air Products and Chemicals, Inc., AgLiLSX, is model equations can be written as follows,
presented. This adsorbent allows the production of high-purity
oxygen (above 95%) using only a single separation step, directly Total mass balance
from air, which makes this technology very appealing for many
∂cT ∂(ucT) nc
applications.
∂t
)-
∂z
- ∑
i)1
Ni (1)
PSA Experimental Apparatus
Partial mass balance

( )
A schematic representation of the experimental apparatus is
presented in Figure 1. The adsorption beds are made of stainless ∂ci ∂ ∂(ci/cT) ∂(uci)
) DaxcT - - Ni, i ) 1, nc (2)
steel and are packed with AgLiLSX supplied by Air Products ∂t ∂z ∂z ∂z
and Chemicals, Inc. The characteristics of the adsorbent and
sorption bed are listed in Table 1. The feed tank has an internal where cT is the total molar concentration, u is the average
volume of ∼60 dm3. (interstitial) molar velocity, z is the spatial coordinate, Dax is
A pressure transducer located in the feed stream and two the effective axial dispersion coefficient, Ni is the ith component
pressure transducers (Druck, PMP 4010, 0-7 bar) located at molar flow rate, ci is the ith component molar concentration in
 Ind. Eng. Chem. Res., Vol. 46, No. 2, 2007 593

Figure 2. Schematic form of finite volume method discretization.

parabolic profile inside the particle.41 This equation is a first-

Figure 3. Definition of local variables.
order delay in mass transfer from the bulk gas phase to the
adsorbed phase and is easily coupled to the conservation
equation in the bulk gas phase.
The molar velocities across the valve orifices are described
by42,43

Table 3. Parameters of the Monocomponent Sips Equation for

up ) Kvf(pu, pd, T, M) (5)
Oxysiv 5 and AgLiLSX at the Reference Temperature T0 ) 20 °C
where Kv is proportional to the valve parameter, Cv, and is given
Oxysiv 5 AgLiLSX
by
N2 O2 Ar N2 O2 Ar
qmax,ref 3.091 3.091 3.091 2.636 5.481 7.270 1 pSTP
(mol kg-1) Kv ) (2.035 × 10-2) ‚ STPCv (6)
bA T
bref (bar-1) 0.1006 0.03670 0.03365 0.2581 0.0301 0.0230
Q/R (K) 2501.07 1767.86 1791.15 2740.70 1873.82 1771.33

{
1/nref 1 1 1 0.4856 0.9484 0.9216 and
R 0 0.3007

x
β 0 0.0112
pu2 - pd2 p > 0.53p
1.179 T d u
the fluid phase, t is the time variable, and nc is the number of p dM
components in the mixture.
f(pu, pd, T, M) )

x
1 pd e 0.53pu
The mass exchange rate between the particle and its sur- pu T
roundings (ith component molar flow rate), assuming the pdM
(7)
accumulation in the intraparticle (nonadsorbed) gas-phase is
negligible, is given by the following equation, where pu and pd are the upstream and downstream pressures,
respectively, A is the area, T is the temperature, and M is the
p(1 - b) ∂qi molecular weight of the gas passing through the orifice. The
Ni ) Fs (3) superscript “STP” stands for standard temperature and pressure
b ∂t
conditions.
where p is the particle porosity, qji is the average molar The molar velocity, u, across the orifice in the feed, in the
concentration in the adsorbed phase, and cji is the molar average vent, before the storage tank, and across the purge and equal-
concentration in the fluid phase. The intraparticle mass transfer ization orifices was considered to be given by
is described using the linear driving force (LDF) approxima-
tion,35 Feed: uinp ) KvFf(pH, p, T, M)

Linear driving force model Storage tank: uST ST

) KST ST
in p v f(p, p , T, M)

∂qi
) ki(qi,s - qi) (4) Purge: upurgep ) upurge,other columnpother column ) KPv f
∂t
(p, pother column, T, M)
where ki ) 15DM,i e
/rp2 is the ith component LDF coefficient,37
which is directly proportional to the effective macropore Vent: uout,ventp ) CVv f(p, pL, T, M)
e
diffusivity coefficient, DM,i is the effective homogeneous
diffusion coefficient, rp is the particle radius, and qi,s is the molar Equalization: uequalizationp ) KEv f(p, pother column, T, M)
concentration in the particle surface (adsorbed phase), which is
related to the molar concentration in the interparticle gas phase The mass balance equation in each storage tank is given by
through the adsorption equilibrium isotherm, qi,s ) f(pT, ci). The
value of DM,i was estimated using the following equation:38 DM,i ∂cST
T
) pDep,i/(p + Fs dq/dc), where Dep,i is the effective diffusivity V ST
outcT - uin cT )
) -(uST ST ST ST
(8)
in the pores. The effective diffusivity in the pores was calculated
∂t
using the Bosanquet equation:38 1/Dep,i ) 1/DK,i e
+ 1/Di,je
, where where VST is the volume of the storage tank (ST).
e e
DK,i is the effective Knudsen diffusivity and Di,j is the effective The boundary conditions of eqs 1 and 2 change with the
molecular diffusivity. The effective Knudsen diffusivity is given process steps. The unit operates with a standard cycle with six
by39 DK,ie
) 3.068rpore/τ xT/Mi and the effective molecular steps and with a top-to-top equalization (TE). In step 1, column
diffusivity was obtained using the Chapman-Enskog equation.40 1 is being pressurized while column 2 is depressurizing. In step
Equation 4 can be deduced from the intraparticle mass balance 2, column 1 produces and column 2 is being purged. In step 3,
equation, which is a partial differential equation, considering column 1 provides equalization to column 2. In step 4, column
594 Ind. Eng. Chem. Res., Vol. 46, No. 2, 2007

1 depressurizes and column 2 pressurizes. In step 5, column 1 LSODA.44 The routine LSODA solves initial boundary problems
is being purged while column 1 produces. Finally, in step 6, for stiff or nonstiff systems of first-order ordinary differential
column 1 receives equalization from column 2. equations (ODEs). For nonstiff systems, it makes use of the
When column 1 is pressurizing and column 2 is depressur- Adams method with variable order (up to 12th order) and step
izing (step 1), the boundary conditions are as follows: size, while for stiff systems it uses the Gear (or BDF) method
with variable order (up to 5th order) and step size.
Column 1 In the finite volume method, the values of the conserved
Kv F variables (for example, molar concentration) are averaged across
1 ∂ci
z ) 0: ) u(ci - ci,in); uin ) f(pH, p1, T, M) the volume and the conservation principle is always assured.
Dax ∂z p1 Figure 2 presents the finite volume discretization method in a
schematic form. ukF is the velocity in the face k, and cF,i
k
is the
∂ci concentration of i species in the face k.
z ) L: ) 0; u ) 0
∂z The equivalent total mass balance equation using the finite
volume method is given by the following equation,
Column 2
KVv ∂k
ckT k
(ukFcT,F - uk-1 k-1
F cT,F )
nc

∑
∂ci
z ) 0: ) 0; u ) - f(p2, pL, T, M) )- - kki ,
N k ) 1, n (9)
∂z p2 ∂t ∆x k
i)1

∂ci where ∆xk is the volume in k stage. From eq 9, assuming

z ) L: ) 0; u ) 0 negligible pressure drop, we obtain the velocity profile, i.e.,
∂z
When column 1 is producing and column 2 is purging (step
2), the following boundary conditions change:

Column 1
c )
t
T ∑
n

k)1
( )
k kT
∂c
∂t
∆x )
k
∑
n

∑
k)1 i)1
nc
kki ∆xk) - cT(uout - uin)
(N
(10)

KPv uST
in p
ST
∆xk nc
z ) L: u )
p1
f(p1, p2, T, M) +
bp1
ukF ) uk-1
F -
cT
(cTt + ∑
i)1
Nki ), k ) 1, n - 1 (11)

Column 2 where uout and uin are the outlet and inlet velocities (uout ) uFn
1 ∂ci and uin ) u0F), given by eq 5. The partial mass balance is given
z ) L: ) u(ci - ci|z ) L,column1); by
Dax ∂z
KPv kki
∂c k
cT,F (cki /ckT)′F - cT,F
k-1 k-1 k-1 ′
(ci /cT )F
u ) - f(p1, p2, T, M) ) Dax -
p2 ∂t ∆x k

In the top-to-top equalization (column 1 provides equalization (ukFci,F

k
- uk-1 k-1
F ci,F )
k
-N
k ki (12)
to column 2, step 3), the boundary conditions are as follows: ∆x
Column 1 k
c ki is the cell average concentration that is a function of cki as
dci follows:45
z ) 0: ) 0; u ) 0
dz (∆xk)2 k (∆xk)4 k (iv)
cki ) cki +
k (ci )′′ + (c ) + ... (13)
dci KEv 24 1920 i
z ) L: ) 0; u ) f(p1, p2, T, M)
dz p1 (cki /ckT)′F is the derivative of (cki /ckT) in the face k and is a
function of the neighboring cells. Using a second-order ap-
Column 2 proximation (central difference schemesCDS2), we obtain
dci
z ) 0: ) 0; u ) 0 i /cT ) - (ci /cT)
(ck+1 k+1 k k
dz (cki /ckT)′F ) (14)
1
/2(∆xk+1 + ∆xk)
1 ∂ci
z ) L: ) u(ci - ci|z ) L,column1); k
Dax ∂z ci,F is the concentration of species i in the face k and is a
KEv function of the neighboring cells, as follows:
u) f(p , p , T, M)
p2 1 2 k
ci,F ) f(ck-1 k k+1 k+2
i , ci , ci , ci ) (15)
Numerical Methods Several methods have been proposed in the literature for the
k
The discretization of eqs 1 and 2 was performed in two stages. calculation of ci,F (concentration of species i in the face k),
First, the space derivatives appearing in the right-hand side were such as the first-order upwind differencing scheme (UDS) of
computed using the finite volume method. Then, the resulting
k
Courant el al.,46 ci,F ) cki , i ) 1, ..., nc; the second-order linear
initial value problem was integrated explicitly in order to obtain upwind scheme (LUDS) of Shyy,47 ci,F k
) 3/2cki - 1/2ck-1
i , i ) 1,
the grid point values at the next time step using the package ..., nc; or the third-order QUICK scheme of Leonard,48 ci,F k
)
 Ind. Eng. Chem. Res., Vol. 46, No. 2, 2007 595

Figure 4. Adsorption equilibrium isotherms for nitrogen (4), oxygen (0), and argon (O) at 11.7 °C for (a) Oxysiv 5 and (b) AgLiLSX.

Table 4. Operating Conditions of the Experiments with AgLiLSX at Table 5. Experimental and Simulation Results of the PSA Unit with
30 °C AgLiLSX
feed composition (%) experimental results (%) simulation results (%)
tpress tprod teq product flow rate run Pur Rec Pur Rec
run O2 Ar N2 (s) (s) (s) (mLSTP/min)
1 100 19.80 100 19.76
1 21 0 79 6.6 8.28 2.1 100 2 100 20.41 100 20.35
2 21 0 79 6.6 48.28 32.1 30 3 100 5.65 100 5.50
3 21 0 79 6.6 8.28 2.1 30 4 98.73 5.64 98.71 5.60
4 21 1 78 6.6 8.28 2.1 30 5 98.64 7.60 98.55 7.45
5 21 1 78 6.6 8.28 2.1 50 6 98.73 7.42 98.75 7.45
6 95 5 0 6.6 18.28 12.1 80 7 99.80 2.94 99.92 3.03
7 95 5 0 6.6 18.28 12.1 30 8 99.65 2.93 99.80 3.10
8 95 5 0 6.6 19.28 16.1 30 9 98.98 4.29 99.93 4.33
9 95 5 0 6.6 12.28 16.1 50
1/ (ck+1
2 i + cki ) - 1/8(ck+1
i + 2cki + ck-1
i ), i ) 1, ..., nc, which are The normalized face value, ỹF, is calculated using an
all upwind biased. Central schemes are often used, such as the appropriate nonlinear limiter. As an example, we present the
second-order central differences (CDS2), ci,F k
) 1/2(ck+1
i + cki ), SMART58 limiter (third-order convergence in smooth regions),

[ (
i ) 1, ..., nc, or the fourth-order central differences (CDS4).
All these methods, with the exception of the first-order UDS, x̃F(1 - 3x̃P + 2x̃F) x̃F(1 - x̃F)
ỹF ) max ỹP, min ỹP, ỹ +
suffer from lack of boundedness, and for highly convective x̃P(1 - x̃P) x̃P(1 - x̃P) P

)]
flows, the occurrence of unphysical oscillations is usual. The
x̃F(x̃F - x̃P)
UDS scheme is referred to in the literature using different , 1 (17)
names: successive stages method, mixed cells in series model, 1 - x̃P
or cascade of perfectly mixed tanks. It is well-known in the
and the MINMOD limiter54 (second-order convergence in
context of separation processes;49-52 however, it has only first-
smooth regions),
order accuracy and is not normally recommended.53

[ ( 1 - x̃F x̃F - x̃P

)]
In order to overcome the occurrence of nonphysical oscilla- x̃F
tions, an extensive amount of research has been directed toward ỹF ) max ỹP, min ỹP, ỹP + (18)
the development of accurate and bounded nonlinear convective
x̃P 1 - x̃P 1 -x̃P
schemes. Several discretization schemes were proposed on the
where the normalized variables ỹP, x̃P, and x̃F are calculated using
total variation-diminishing framework (TVD)47,54 and, more
recently, on the normalized variable formulation (NVF)55 and yP - yU x P - xU x F - xU
its extension, the normalized variable and space formulation ỹP ) , x̃P ) , x̃F ) (19)
(NVSF) of Darwish and Moukalled.56 yD - yU xD - xU xD - xU
Two different bounded approaches are nowadays commonly
used: high-resolution schemes (HRS) and weighted essentially More details on this issue, and other high-resolution schemes,
nonoscillatory (WENO) schemes. In this work, we use bounded can be found in the works of Darwish and Moukalled56 and
higher-order schemes following the χ scheme formulation Alves et al.59
proposed by Darwish and Moukalled,57 which are briefly Although these high-resolution schemes are very efficient and
described below. bounded, for systems with more than two components, their
Considering a general grid, as illustrated in Figure 3, the use may result in inconsistencies in the mass balances and may
labeling of the nodes depends on the local velocity, uF, lead to unphysical solutions. For these cases, the χ-schemes
calculated at face F. For a given face F, the U and D nodes should be used. The χ-schemes are a new class of high-
refer to the upstream and downstream points, relative to node resolution schemes that combine consistency, accuracy, and
P, which is itself upstream to the face F under consideration, boundedness across systems of equations.57 This new formula-
as shown in Figure 3. tion is based on the observation that the upwind scheme and
According to the NVSF, the face values are interpolated as56 all high-order schemes are consistent. So, if the high-resolution
(HR) scheme at a control volume face is forced to share across
yF ) yU +ỹF(yD - yU) (16) the system of equations the same linear combination of high-
order (HO) schemes, then it will be consistent.57 Otherwise, the
where y is the convected variable (for example ci). mass balance may not be consistent. In this formulation, the
596 Ind. Eng. Chem. Res., Vol. 46, No. 2, 2007

Table 6. Valve Coefficients of the PSA Unit with AgLiLSX

run CPv CEv run CPv CEv
1 0.0004 0.0020 6 0.0010 0.0048
2 0.0004 0.0020 7 0.0010 0.0048
3 0.0006 0.0050 8 0.0010 0.0015
4 0.0005 0.0030 9 0.0016 0.0017
5 0.0010 0.0020

value at a control volume face using a high-resolution scheme

is written as

F ) ỹU + χ( ỹF - ỹU)

ỹHR HR
(20) Figure 5. Simulated and experimental pressure history, inside the columns,

{
achieved on the unit studied for run 5 ((- - -) simulation, (0) experi-
The NVF form of the SMART scheme is written as57 mental).

1
3ỹU 0 < ỹU <
6
3 3 1 5
+ ỹ < ỹU <
ỹF ) 8 4 U 6 6 (21)
5
1 < ỹU < 1
6
ỹU elsewhere

{
The equivalent χ formulation is57

16ỹU 1
0 < ỹU <
3 - 2ỹU 6
Figure 6. Simulated and experimental pressure history, inside the columns,
1 5 achieved on the unit studied for run 9 ((- - -) simulation, (0) experi-
1 < ỹU <
χ) 6 6 (22) mental).
8(1 - ỹU) 5
< ỹU < 1
3 - 2ỹU 6
For Oxysiv 5, the multicomponent adsorption equilibrium was
0 elsewhere
predicted using the Sips multicomponent equation since the
saturation capacity and the parameter n are the same for the
Consistency is ensured by forcing all the related equations to
three species, which indicates consistency from a thermody-
have the same values of χ at any control volume face.57
namic point of view.39 For AgLiLSX, these parameters are not
the same, and so the multicomponent adsorption equilibrium
Adsorption Equilibrium was predicted using the ideal adsorption solution theory
The single-component adsorption equilibrium isotherms for (IAST).39
AgLiLSX and for Oxysiv 5 were obtained experimentally by The experimental adsorption data for oxygen, nitrogen, and
the gravimetric method using a Rubotherm magnetic suspension argon at 11.7 °C for Oxysiv 5 and AgLiLSX are presented in
balance,60 at three different temperatures (11.7, 23.0, and 29.9 Figure 4.
°C for AgLiLSX and 11.7, 19.9, and 36.4 °C for Oxysiv 5). The pore-size distribution was determined using a mercury
The adsorption equilibrium was described using the Sips porosimeter from Quantachrome (model Poremaster 60). This
equation,39 porosimeter allows one to determine the pore-size distribution
ranging from 200 µm to 35 Å, by analyzing both intrusion and
(bp)1/n extrusion of mercury in the pores. The average diameter of the
q ) qmax (23) pores obtained for both adsorbents was 0.5 µm. The porosity
1 + (bp)1/n
obtained was 0.336 for Oxysiv 5 and 0.471 for AgLiLSX.
where

[ ( )] ( )
Results and Discussion
Q Tref 1 1 Tref
b ) bref exp -1 , ) +R 1- , For avoiding any contamination of the adsorbent, mixtures
RTref T n nref T

[(
T concentrations: 78.12% of nitrogen, 20.95% of oxygen, and
and qmax ) qmax,ref exp β 1 -
Tref
bref is the affinity constant at the reference temperature, Tref (in
this work, it was considered to be 20 °C), Q is the heat of
adsorption, T is the temperature, qmax,ref is the maximum
adsorption capacity at the reference temperature, and nref, R,
and β are empirical parameters. The experimental values at the
three different temperatures were used for obtaining the Lang-
muir-Freundlich equation parameters, presented in Table 3.
)]
of pure gases were prepared in the feed tank with the following
0.93% of argon (similar to air) and 95% of oxygen and 5% of
argon (such as a product from a PSA unit).
Table 4 presents the operating conditions of the experiments
with AgLiLSX at 30 °C (runs 1-3 were conducted with pure
reconstituted air).
The experimental and simulation results (purity, Pur, and
recovery, Rec) of the runs presented in Table 4 are presented
in Table 5. As can be seen in Table 5, this adsorbent allows the
production of high-purity oxygen.
 Ind. Eng. Chem. Res., Vol. 46, No. 2, 2007 597

Table 6 presents the valve coefficients determined experi- A PSA unit using the Skarstrom cycle with top-to-top
mentally (obtained measuring the flow rate passing through the equalization allowed the production of high-purity oxygen
valves at different pressures) for the runs presented before. directly from air.
The feed, CFv , vent, CVv , and storage tank, CTv , valve param- The simulator was able to represent accurately a real unit
eters were determined in the same way and are, respectively, using a feed without carbon dioxide and water vapor. With the
0.025, 0.025, and 0.02. optimization strategy, it was possible to achieve better operating
Figures 5 and 6 present the simulated and experimental conditions and design characteristics that improved the perfor-
pressure histories for runs 5 and 9, respectively. mance of the units. An optimal recovery of 5.03% was obtained
By analyzing Table 5 and Figure 5, it is possible to conclude for producing 99.5% of oxygen from air with a PSA operating
that the simulator was able to accurately represent the experi- between 1 and 3 bar at 30 °C.
mental results. It is worth mentioning that the other runs also
show a good match between the simulation and experimental Acknowledgment
results. The work of João Carlos Santos and Paulo Cruz was
supported by FCT, Grants SFRH/BD/6817/2001 and POSI
PSA Optimization SFRH/BPD/13539/2003, respectively. The research was also
supported by funds from Growth GRD1-2001-40257 and FCT
This PSA unit was optimized by simulation, minimizing the project POCTI/EQU/38067/2001.
recovery, for producing 50 mLSTP/min of 99.5% of oxygen from
air, operating between 1 and 3 bar at 30 °C. The optimization Acknowledgment
procedure described by Cruz et al.36 was used, and the
optimization variables were the pressurization time, tpress, the The authors would like to acknowledge Air Products and
production time, tprod, the equalization time, teq, the purge valve Chemicals, Inc., and Dr. Roger D. Whitley for offering the
adsorbent.
coefficient, CPv , and the equalization valve coefficient, CEv . An
optimum recovery of 5.03% was obtained for tpress ) 6.6 s, tprod
Nomenclature
) 8 s, teq ) 3.1 s, CPv ) 0.0015, and CEv ) 0.0020.
As mentioned in the Introduction, Jee et al. presented a PSA A ) area, m2
unit with two adsorption columns with ∼380 mL packed with b ) Langmuir affinity constant, bar-1
CMS adsorbent from Takeda.29 The feed was 95% of oxygen c ) fluid-phase molar concentration, mol m-3
and 5% of argon, and its flow rate was 4 LSTP/min. The high Cv ) valve parameter
pressure was 5 bar. This unit produces ∼1.6 LSTP/min of 99.87% Dax ) effective axial dispersion coefficient, m2 s-1
oxygen with a recovery of 56.90%. This unit coupled with a DeM ) effective homogeneous diffusion coefficient, m s-1
PSA unit packed with Oxysiv 5 would have a global recovery d ) diameter, m
∼17%.2 It would be composed by two columns with ∼2 L k ) iteration or LDF coefficient, ki ) 15DM,ie/rp2, s-1
(packed with Oxysiv 5) and two columns with 380 mL (packed Kv ) valve parameter
with CMS adsorbent).2 If Oxysiv MDX was used instead, it L ) column length, m
would have a global recovery ∼45%.2 It would be composed M ) molecular weight, kg mol-1
by two columns with ∼1 L only (packed with Oxysiv MDX) n ) empirical parameter from Langmuir-Freundlich equation
and two columns with 380 mL (packed with CMS adsor- N ) molar flow rate, mol s-1
bent).2 The drawback of this technology is that the product is nc ) number of mixture components
obtained at a pressure close to the atmospheric pressure, and p ) pressure, bar
so, a third compressor might be needed to pressurize it. With Pur ) product purity
AgLiLSX and with the cycle presented to produce 1.6 LSTP/ Q ) heat of adsorption, J mol-1
min of 99.5% oxygen, only two columns with ∼3.2 L would q ) molar concentration in the adsorbed phase, mol kg-1
be needed. qmax ) isotherm parameter, maximum adsorption capacity, mol
Although the recovery given by this combination of two units kg-1
is high, the unit is large and complex. In some applications rp ) particle radius, m
where the size is important, it might be advisable to use R ) universal gas constant, J mol-1 K-1
AgLiLSX to directly produce high-purity oxygen or even a Rec ) product recovery
combination of a PSA with Oxysiv MDX, for example, with t ) time variable, s
another PSA with AgLiLSX (although this combination is also T ) temperature, K
complex, the product is obtained at high pressure). u ) average (interstitial molar) velocity, m s-1
z ) spatial coordinate, m
Conclusions Greek Symbols
A study about the high-purity oxygen production from air in R ) empirical parameter from Langmuir-Freundlich equation
a single stage by pressure swing adsorption (PSA) using an β ) empirical parameter from Langmuir-Freundlich equation
adsorbent patented by Air Products and Chemicals was pre- b ) bed void fraction (ratio between the free volume and the
sented. The adsorption equilibrium measurements indicate that total volume)
this adsorbent has large nitrogen, oxygen, and argon capacities p ) particle porosity
and selectivities. Fs ) apparent particle density, kg m-3
The adsorbents studied (Oxysiv 5 and AgLiLSX) showed to τ ) tortuosity factor
have similar average pore diameters, 0.5 µm; however, they
presented different porosities: 0.336 for Oxysiv 5 and 0.471 Subscripts
for AgLiLSX. d ) downstream
598 Ind. Eng. Chem. Res., Vol. 46, No. 2, 2007
eq ) equalization
i ) component
in ) feed stream (inlet)
out ) outlet stream
p ) particle
pres ) pressurization
prod ) production
purg ) purge
ref ) reference
T ) total
u ) upstream
Superscripts
E ) equalization
F ) feed
H ) high
L ) low
P ) purge
ST ) storage tank
STP ) standard temperature and pressure conditions
V ) vent
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ReceiVed for reView March 30, 2006
ReVised manuscript receiVed November 2, 2006
Accepted November 13, 2006
IE060400G