6

Development on High Performance Gas Separation Process

Using Gas Adsorption
Jun Izumi*1
Nariyuki Tomonaga*1

Akinori Yasutake* 1
Hiroyuki Tsutaya*1
Nobuki Oka*1

In pressure swing adsorption (PSA), a dry gas separation process, a strong adsorbate is adsorbed and a weak
adsorbate is extracted from a mixture gas at higher pressure conditions, while a strong adsorbate in adsorbent can be
desorbed and recovered at lower pressure. This process was realized for oxygen, nitrogen, hydrogen, and dry air
separation in the early 1960s and spread rapidly. PSA was applied in different industrial fields due to the
industrialization of zeolite synthesis and energy saving vacuum type PSA, we discuss an application of zeolite
adsorbents to PSA with development of new gas separation processes such as NO2 and ozone enrichment.

1.Introduction
From the perspective of saving resources and
energy, there are great needs for highly efficient
g a s s e p a r a t i o n p r o c e s s e s . F o r m e r l y, d i s t i l l a t i o n
(cryogenic separation) and liquid phase absorption
were major processes for gas separation. Recently,
however, adsorption processes are increasingly being applied. This is based on the background that,
i n a d d i t i o n t o Te m p e r a t u r e S w i n g A d s o r p t i o n
(TSA), the technology of PSA has been established
and begun to be applied to various gas components (1) .
PSA processes have spread rapidly in fields such
as separation of oxygen, nitrogen, hydrogen, and moisture removal, since the commencement of their practical use in 1960s. As for the reason for this, it can be
pointed out that the equipment is compact, power consumption is low owing to their high separation effic i e n c y, a n d t h e r e i s n o t h e r m a l l y i n d u c e d
deterioration in adsorbents because they are operated
at a constant temperature. At the same time, the large
improvement of the adsorbing performance of zeolite
and activated carbon is considered to be another big
factor.
This report introduces a gas separation process for
enriching NO 2 and ozone, both acid gases, using high
silica zeolite as an adsorbent because of its superior
acid resistance, good hydrophobic property, and low
chemical reactivity, and applying Vacuum Pressure
Swing Adsorption (VPSA) whose electric power consumption is the lowest among the various PSA processes.

Component B
Atmospheric pressure

Component A: strong adsorbate

Component B: weak adsorbate

2. PSA process and absorbent used

2.1 Principle of the PSA process
In the initial stage of PSA as developed in the
1960s, the processes generally used for separating a
*1 Nagasaki Research & Development Center, Technical Headquarters

Tower L

Tower R

Inlet gas
(A+B)
Atmospheric
Blower
pressure

Pressure
reduced to
vacuum

Component A

Vacuum pump

Fig. 1 Principle of PSA

strong adsorbate A and weak adsorbate B were designed to repeat a cycle consisting of high-pressure
adsorption and atmospheric-pressure regeneration.
After that, in order to comply with strong needs for
reducing electric power consumption, another improved separation process spread. This process uses
a cycle of atmospheric-pressure adsorption and
vacuum regeneration as shown in Fig
Fig.. 1 , with the inlet gas fed at a pressure close to atmospheric- pressure.
Fig. 1 shows the most basic two-tower type VPSA
process, which consists of two adsorption towers, a
feed gas blower, a vacuum pump for the vacuum regeneration, valves and piping. The valves are opened
and closed by a sequence controller. When inlet gas
consisting of components A and B is fed to the adsorption tower L, an adsorption zone is formed as
shown in Fig
Fig.. 2 and it moves in the arrow's direction
with the passage of time. In the adsorption zone, the
Mitsubishi Heavy Industries, Ltd.
Technical Review Vol.39 No.1 (Feb. 2002)

Adsorbent surface
concentration

Saturated zone

Adsorption
zone

Tower
outlet

Unadsorption
zone

Fig. 2 Concentration profile of adsorbate during the

adsorption process
Adsorption state in the adsorption tower is shown.

solid line shows the gas phase concentration which is

slightly higher than the adsorbent surface concentration denoted by the broken line thus, a mass transfer
(adsorption) from the gas phase to the adsorbent occurs. When feeding the inlet gas is stopped just before the component A concentration begins to increase
in the outlet gas of tower L, the component A is completely adsorbed and entirely removed from the outlet gas. At the same time, regeneration proceeds in
tower R. However, because component A is comparatively low in concentration, it cannot be desorbed efficiently from the adsorbent only by a simple pressure
reduction.
Therefore, a countercurrent gas purge method is
applied. In the method, by purging component B gas
countercurrently from the top of tower R at a vacuum
pressure through the pressure-reducing valve, the
mass transfer (desorption) of adsorbate A from the
adsorbent to the gas phase is started, and the adsorption zone moves from the top to the bottom of tower R
and finally tower R returns to the initial state of the
adsorption process. (Towers L and R alternately perform adsorption and regeneration.) Here, if a purge
gas amount G p required for the countercurrent purge
is given, the mass balance in the PSA process can be
estimated. The purge gas amount was proposed by
Skarstrom (2) who devised the PSA process, and its required amount is expressed by Equation (1), when
component A concentration is low.
G p = k G 0 P d / P a (k = 1 .2 to 1.5)
(1)
From the equation, it is known that, as desorption
pressure decreases, the recovered amount of component B increases and also the concentration of component A in the regenerated gas increases because the
purge gas amount G p decreases.
2.2 Zeolite adsorbent
The chemical formula of zeolite having Na as a
cation is expressed as (Na 2 O 3 ) m (Al 2 O 3 ) m (SiO 2 ) n .
Because the network structure consisting of Al-O-Si
and Si-O-Si reaches an excess electron state at Al
sites, the network structure combines with cations
like Na so as to neutralize such a state and forms a

Carbon Carbon
Water dioxide monoxide
+ O+ + +
+ +
+C+
+H H+
C
-O--O--O- -

Nitrogen Oxygen
+ +
+
+ N + ++ O +
- N - - - -O -

+ +
+ +
+ +
+ +
+ Na +
+ Na +
+ Na +
+ Na +
Al
Si + Al - Si + Al - Si + Al - +
+
+ Na + +
+- Na
- Na
Si - Al -+ Si - Al -+ Si - Al -+ Si
-

Fig. 3

Zeolite

Gas phase concentration

Gas phase

Electrostatic charge model and

adsorption force on the zeolite surface

An interaction between various adsorbate gas

molecules and the zeolite surface is shown.

strong positive electric field against the gas phase.

Accordingly, as shown in Fig
Fig.. 3 , the gas phase components attached to zeolite are influenced by the strong
electric field of zeolite to polarize (furthermore to form
quadra-pole) and produce a Coulomb's force. Because
the adsorbing energy E produced between the electrostatic field of zeolite and the gas components can
be expressed by Equation (2), and if the electrostatic
field intensity of zeolite V /r and the polarizability of the gas components, and quadra-pole moment Q are known, the adsorbing energy E can
usually be estimated to a certain extent.
(2)
Accordingly, the adsorption intensity of a zeolite
adsorbent used for PSA is adjustable by the ratio of
SiO 2 /Al 2 O 3 and the electro-negativity of the cation,
so that the adsorption intensity can be selected considerably arbitrarily.
Tabl
e 1 shows the zeolite adsorbents used for the
able
gas adsorption processes. Especially, as the ratio of
SiO 2 /Al 2 O 3 increases, the adsorbed amount of moisture is reduced while the adsorbed amounts of strong
adsorbates like acid gases are little reduced. As a result, the selective adsorption of acid gases coexisting
together with moisture becomes possible. It is known
that the adsorbing performance of zeolite is remarkably deteriorated because Al in the network of Si-OAl constituting the crystal structure reacts with acid
gases absorbed on zeolite and it is released from the
crystal lattice.
On the other hand, high silica zeolite shows a very
strong acid resistance because it contains little Al.
However, zeolite is also known to be an excellent catalyst, so that, when it is used as adsorbent, nitric acid
formation and ozone destruction must be prohibited
from progressing. In this perspective, high silica zeolite has an outstanding advantage distinguished from
others by its capability to prevent side reactions. In
Mitsubishi Heavy Industries, Ltd.
Technical Review Vol.39 No.1 (Feb. 2002)

8
Table 1
Crystal
A type
Adsorbent
3A
4A
5A
name
Chemical
K 12(AlO 2 Na12(AlO2 Ca86(AlO 2
formula
-SiO 2)12
-SiO 2)12
-SiO 2)12
Crystal
Cubic system
structure
Lattice
12.3
constant ()
Si/Al
0.91.0
formula
True
1.69
1.52
1.48
density
Window
3.0
3.8
4.3
diameter ()
Adsorbed
gas

NH3,
H2 ,
H2 O

CO 2, Ar,
O 2, N 2
Kr, Xe
CH4

Properties of zeolite

Faujasite
X
Na86 (AlO 2)86
(SiO 2)106

Pentasil
Y
ZSM-5
Silicalite
(including USY)
Na86 (AlO 2)86
Nam(AlO 2)m(SiO 2)n
(n/m>10)
(SiO 2)136

Cubic system

Rhombic system

Mordenite
(including
USM)
Na8(AlO 2)8
(SiO 2)40
Rhombic
system

Mesoporous
silicate

Amorphism

12.5

12.35

13.4100

7.5100

12100

1.01.5

1.5100

10

5100

1.54

1.541.42

1.76

1.70

1.70

8.1

8.1

5.45.6, 5.15.5

6.77.0

1090

C 3 H6 ,
CF2Cl2,
CF4,
i-butane

N2, O 2, Kr, Xe,

acid gas,
organic solvent gas

N2, O 2, Kr, Xe,

acid gas,
organic solvent gas

the high silica zeolites being practically used, there

are Silicalite, Ultra Stable Y-type Zeolite (USY),
mesoporous silica (MPS). Silicalite is pentasil zeolite
having a SiO 2/Al 2O 3 ratio of 100:1. USY is a high silica
zeolite that is obtained by de-alminating Y-type zeolite in ammonia- containing water vapor and has the
highest SiO 2/Al 2 O 3 ratio, as high as about 200:1. This
is effective for the adsorption of macromolecules
l a r g e r t h a n 5 , w h i c h S i l i c a l i t e c a n n o t a d s o r b .
Mesoporous silica is a silica group porous medium
having a specific surface of about 1 600 m 2/g or more.
It is effective for adsorption of macromolecules because it has large micro pores and a large specific
surface.
However, because of having large micro pores, its
adsorption intensity is weaker than Silicalite and
USY. Therefore, it must be applied selectively for each
adsorbate gas.

3. Gas separation utilizing the PSA process

3.1 NO2 enrichment
The investigation of PSA-NO 2 is described below
as an example of the applications of high silica zeolite.
In off-gas from chemical plants like nitric acid
plants, NOx is contained in higher concentration, and
presently it is washed and removed by alkaline water. However, this method has problems peculiar to
wet processing, namely (1) low removal efficiency at
low NO 2 concentrations, (2) troublesome treatment of
the absorption liquid, and (3) corrosion in the liquid
contact parts of equipment. These problems can be
solved by dry processing that, after the moisture in
the off-gas is removed by PSA, dried NO 2 is enriched
to 50 vol% or more by PSA-NO 2, cooled to 268 to 273
K, and liquefied to be recovered.
Fig
Fig.. 4 shows the isotherms of NO 2 adsorption. Adsorbent for NO 2 recovery by PSA requires both avoid-

N2, O 2, Kr, Xe, N2, O 2, Kr, Xe,

acid gas,
acid gas,
organic solvent organic solvent
gas
gas

ing (1) deterioration due to a trace amounts of nitric

acid entrained into NO 2 gas and (2) that due to a trace
moisture co-adsorbed together with NO 2 , and also
ensuring (3) a reversible adsorbed amount of NO 2 .
Silicalite shows the largest NO 2-adsorbed amount and
excellent acid resistance, thus, it has been concluded
to be the most suitable as an adsorbent for PSA-NO 2.
Fig
Fig.. 5 shows the schematic diagram of a two-stage
system composed of PSA-moisture desorption and
PSA-NO 2, in which 50 vol% or more NO 2 enriched from
8 vol% NO 2 emitted from chemical plant off-gas is
cooled to 268-273 K and liquefied to be recovered as
NO 2 .
3.
2 Ozone enrichment
3.2
Since ozone is one of the strongest oxidizing agents
and residual ozone is decomposed to stable oxygen,
its use is expanding. In order to improve ozone-processing efficiency, the generation of highly enriched
ozone is required. At present, for generating highly
enriched ozone, silent-discharge-type ozone generators are most commonly used, and these generators

50

: Silicalite (SiO2/Al2O3 ratio: 400)

: USY (SiO2/Al2O3 ratio: 70)
: USM (SiO2/Al2O3 ratio: 70)

40

: Silica gel

30
20
10

10

15

20

25

30

NO2 concentration (vol%)

Fig. 4 Adsorption isotherms of various silica zeolite

(Adsorption temperature: 298 K, NO2 reversible
adsorbed amount)
NO2 concentrations and adsorbed amounts are measured at
the same temperature for various high silica zeolites.

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Technical Review Vol.39 No.1 (Feb. 2002)

NOx-free gas

NO2 8.3vol%
PSA-NO2

PSA dryer

Process off-gas

Blower

Vacuum pump
NO2 25vol%
NOx condenser

Vacuum
pump

NO2 8vol%
N2O 4vol%
Residual gas

Exhaust
gas

NO2 50vol%

Liquid transfer pump

Recovered NOx

Fig. 5 Schematic diagram of NO 2 recovery system

The system organization and schematic diagram for a practical application are shown.
Waste oxygen recycle

Ozone adsorption
tower
240 K
Tower A
Tower
B
Liquefied
oxygen or
PSA-O3

Ozone
Ozone
5wt%
Pa=120 kPa
generator
Blower

Refrigerator
Freezing
store
Vacuum
pump

Product
ozone
20 wt%

Pa=5 kPa
Ozone reflux line

Fig. 6 Schematic diagram of PSA-O3

System organization and schematic diagram of PSA-O3 for a practical application

are shown.

are commonly designed to enrich ozone concentration

by increasing the energy density of the discharge electrodes.
However, there is a problem in that electric power
consumption increases with an increase in ozone concentration and the achievable upper limit of the concentration is only about 20 wt% (3)(4).
Another process proposed is to produce high purity ozone by refrigerating and liquefying ozone produced by the silent discharge, with oxygen being
separated at about 100 K. Furthermore, an ozone-enriching process by the gas phase adsorption is also
possible. This process has been accomplished as a
temperature-swing process in which ozone adsorbed
at a low temperature of 210 K or lower using silicagel as an adsorbent is desorbed and recovered as
highly enriched ozone by heating the ozone- adsorbed

silica-gel to room temperature (5)(6) . This process requires a considerable amount of cooling energy for
the low- temperature adsorption and heated regeneration, and its cycle time exceeds one hour, so that
the adsorption tower requires a considerably large
capacity.
Therefore, the process is not commonly used as a
highly enriched ozone generator. The pressure swing
adsorption process (PSA) is worth considering as one
of other gas phase separation processes, although it
has not yet been practically applied. In comparison
to silica-gel, a high silica zeolite, like Silicalite, having a large SiO 2 /Al 2 O 3 ratio is capable of adsorbing a
large amount of ozone and has a low ozone decomposing rate.
Fig
Fig.. 6 shows the schematic diagram of the investie 2 lists the properties of the
gated system and Tabl
able
Mitsubishi Heavy Industries, Ltd.
Technical Review Vol.39 No.1 (Feb. 2002)

10
Performance of PSAPSA- O3 (1 kg O3 /h class)
120 kPa
5 kPa
240 K
5 min
Max 12 times
20 wt%
20 kg (10 kg2 towers)
Silicalite
0.5 kWh/kgO2

Table 3 Reduction of electric power cons

consmption per unit product
for PSAPSA-O3
Ozone generator
PSA-O2
PSA-O3
Total
Concentration of
product ozone

Conventional process
7.5
7.5
15

Ozone enrichment
7.5
2.5
0.5
10.5

5 wt%

20 wt%

system. Since the performance (enrichment rate, electric power consumption per unit product, required
adsorbent amount, etc.) of the ozone enrichment system changes according to (a) regenerating pressure,
(b) adsorption temperature, etc., here as a typical
example, the relationship between adsorption temperatures and ozone adsorbent loads (an inlet ozone gas
rate treatable by 1 ton of adsorbent loaded) is shown
in Fig
Fig.. 7 . At present the adsorption temperature is
set to be 255 K, because, as adsorption temperature
decreases, the cooling load increases while the ozone
adsorbent load increases and ozone-decomposing rate
decreases. The total electric power consumption per
unit product in the silent discharge type ozone generator is estimated to be about 15 kWh/kg-O 3 (7.5 kW/
kg-O 3 for an ozone generator and 7.5 kWh/kg-O 3 for
PSA oxygen) at an ozone concentration of 5w%. Here,
if waste oxygen effusing from the adsorption tower of
the ozone enrichment system is refluxed to the inlet
of the ozone generator, the utilizing efficiency of oxygen can be improved to largely save the inlet oxygen
amount. The ozone enrichment system requires an

Ozone adsorption load (m 3 N/h)

Table 2

Adsorption pressure
Regeneration pressure
Adsorption temperature
Cycle time
Ozone enrichment ratio
Set maximum ozone concentration
Loaded amount of adsorbent
Adsorbent
Electric power consumption per unit product

2 000

1 500

1 000
500

0
200

220

240

260

280

300

Temperature (K)

Fig. 7 Performance of PSA-O 3

Ozone enrichment rate and adsorption

amount at various operation conditions
are shown.

electric power consumption per unit product of 0.5

kWh/kg-O 3, for enriching ozone from 5 wt% to 20 wt%.
On the other hand, the electric power consumption
per unit product in PSA-oxygen is reduced to one third
of the conventional one, so that it can be expected that
the total power consumption is remarkably reduced
to 10.5 kWh/kg-O 3 . In the future, it can be expected
that ozone enrichment processes based on gas adsorption will be constantly improved in performance by
refinement in the high-temperature adsorption property of ozone adsorbents and increase in the oxygen
recovery ratio due to application of argon adsorbents
Tabl
e 3 ).
(T
able
References
(1) Kawai, T., Generals of Pressure Swing Adsorption (1986)
(2) Skarstrom, C. W., US Patent 2944627 (1960)
(3) Tuji, Y., Water Treatment Using Ozone Oxidation (2), PPM
(1997/1)
(4) Vacuum Products, High concentration ozone generation unit,
JITA NEWS No.11 (1998)
(5) Maeda, Ozone supply at a constant concentration, Japan
Patent 50-116389
(6) Tabata et-al., Ozone generation with oxygen recycle, Japan
Patent 53-6409

Mitsubishi Heavy Industries, Ltd.

Technical Review Vol.39 No.1 (Feb. 2002)