6

Development on High Performance Gas Separation Process

Using Gas Adsorption

Jun Izumi*1 Akinori Yasutake* 1

Nariyuki Tomonaga*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 Component B
Component A: strong adsorbate Atmospheric pressure
From the perspective of saving resources and Component B: weak adsorbate
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 be-
ing 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
Tower L Tower R
(TSA), the technology of PSA has been established
and begun to be applied to various gas compo-
nents (1) . Pressure
PSA processes have spread rapidly in fields such Inlet gas
reduced to
as separation of oxygen, nitrogen, hydrogen, and mois- vacuum
(A+B) Component A
ture removal, since the commencement of their prac- Atmospheric
pressure Blower
tical use in 1960s. As for the reason for this, it can be Vacuum pump
pointed out that the equipment is compact, power con- Fig. 1 Principle of PSA
sumption is low owing to their high separation effi-
c 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 strong adsorbate A and weak adsorbate B were de-
deterioration in adsorbents because they are operated signed to repeat a cycle consisting of high-pressure
at a constant temperature. At the same time, the large adsorption and atmospheric-pressure regeneration.
improvement of the adsorbing performance of zeolite After that, in order to comply with strong needs for
and activated carbon is considered to be another big reducing electric power consumption, another im-
factor. proved separation process spread. This process uses
This report introduces a gas separation process for a cycle of atmospheric-pressure adsorption and
enriching NO 2 and ozone, both acid gases, using high vacuum regeneration as shown in Fig Fig.. 1 , with the in-
silica zeolite as an adsorbent because of its superior let gas fed at a pressure close to atmospheric- pres-
acid resistance, good hydrophobic property, and low sure.
chemical reactivity, and applying Vacuum Pressure Fig. 1 shows the most basic two-tower type VPSA
Swing Adsorption (VPSA) whose electric power con- process, which consists of two adsorption towers, a
sumption is the lowest among the various PSA pro- feed gas blower, a vacuum pump for the vacuum re-
cesses. generation, valves and piping. The valves are opened
and closed by a sequence controller. When inlet gas
2. PSA process and absorbent used consisting of components A and B is fed to the ad-
2.1 Principle of the PSA process sorption tower L, an adsorption zone is formed as
In the initial stage of PSA as developed in the shown in Fig
Fig.. 2 and it moves in the arrow's direction
1960s, the processes generally used for separating a with the passage of time. In the adsorption zone, the

*1 Nagasaki Research & Development Center, Technical Headquarters Mitsubishi Heavy Industries, Ltd.
Technical Review Vol.39 No.1 (Feb. 2002)
 7

Gas phase concentration Carbon Carbon

Water dioxide monoxide Nitrogen Oxygen
+ +
+ O+ + + + N + ++ O +
+

Gas phase
+ +
+H H+ C +C+ - N - - -
-O-
Adsorbent surface --O-- -O- - - - - -O -
concentration

Tower + + + + + + + +
Unadsorption + Na + + Na + + Na + + Na +
Adsorption outlet - - - - - - - -
zone Al Si + Al - Si + Al - Si + Al -
Saturated zone zone

Zeolite
- - + Na + - + + - + +-
- - Na - Na
Fig. 2 Concentration profile of adsorbate during the Si - Al -+ Si - Al -+ Si - Al -+ Si
adsorption process - - -
Adsorption state in the adsorption tower is shown.
Fig. 3 Electrostatic charge model and
adsorption force on the zeolite surface
solid line shows the gas phase concentration which is An interaction between various adsorbate gas
slightly higher than the adsorbent surface concentra- molecules and the zeolite surface is shown.

tion denoted by the broken line thus, a mass transfer

(adsorption) from the gas phase to the adsorbent oc-
curs. When feeding the inlet gas is stopped just be-
fore the component A concentration begins to increase
in the outlet gas of tower L, the component A is com-
pletely adsorbed and entirely removed from the out-
let gas. At the same time, regeneration proceeds in
tower R. However, because component A is compara-
tively low in concentration, it cannot be desorbed ef-
ficiently 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 adsorp-
tion 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 per-
form 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 re-
quired 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 compo-
nent B increases and also the concentration of com-
ponent 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
strong positive electric field against the gas phase.
Accordingly, as shown in Fig Fig.. 3 , the gas phase compo-
nents 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 elec-
trostatic 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 polarizabil-
ity α of the gas components, and quadra-pole mo-
ment 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 con-
siderably arbitrarily.
Tabl
ablee 1 shows the zeolite adsorbents used for the
gas adsorption processes. Especially, as the ratio of
SiO 2 /Al 2 O 3 increases, the adsorbed amount of mois-
ture is reduced while the adsorbed amounts of strong
adsorbates like acid gases are little reduced. As a re-
sult, the selective adsorption of acid gases coexisting
together with moisture becomes possible. It is known
that the adsorbing performance of zeolite is remark-
ably deteriorated because Al in the network of Si-O-
Al 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 cata-
lyst, so that, when it is used as adsorbent, nitric acid
formation and ozone destruction must be prohibited
from progressing. In this perspective, high silica zeo-
lite 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)
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Table 1 Properties of zeolite

Crystal A type Faujasite Pentasil Mordenite
Mesoporous
Adsorbent Y (including
3A 4A 5A X ZSM-5 Silicalite silicate
name (including USY) USM)
Chemical K 12(AlO 2 Na12(AlO2 Ca86(AlO 2 Na86 (AlO 2)86 Na86 (AlO 2)86 Nam(AlO 2)m(SiO 2)n Na8(AlO 2)8
−
formula -SiO 2)12 -SiO 2)12 -SiO 2)12 (SiO 2)106 (SiO 2)136 (n/m>10) (SiO 2)40
Crystal Rhombic
Cubic system Cubic system Rhombic system Amorphism
structure system
Lattice
12.3 12.5 12.35 13.4−100 7.5−100 12−100
constant (Å)
Si/Al
0.9−1.0 1.0−1.5 1.5−100 10−∞ 5−100 4−∞
formula
True
1.69 1.52 1.48 1.54 1.54−1.42 1.76 1.70 1.70
density
Window
3.0 3.8 4.3 8.1 8.1 5.4×5.6, 5.1×5.5 6.7×7.0 10−90
diameter (Å)
CO 2, Ar, C 3 H6 , N2, O 2, Kr, Xe, N2, O 2, Kr, Xe,
NH3, N2, O 2, Kr, Xe, N2, O 2, Kr, Xe,
Adsorbed O 2, N 2 CF2Cl2, acid gas, acid gas,
H2 , acid gas, acid gas,
gas Kr, Xe CF4, organic solvent organic solvent
H2 O organic solvent gas organic solvent gas
CH4 i-butane gas 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 zeo-
lite 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 Å, 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 be-
cause 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 zeo-
lite.
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 wa-
ter. 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
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.
3.22 Ozone enrichment
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-pro-
cessing efficiency, the generation of highly enriched
ozone is required. At present, for generating highly
enriched ozone, silent-discharge-type ozone genera-
tors are most commonly used, and these generators
: Silicalite (SiO2/Al2O3 ratio: 400)
: USY (SiO2/Al2O3 ratio: 70)
50
: USM (SiO2/Al2O3 ratio: 70)
40 : Silica gel
30
20
10

contact parts of equipment. These problems can be

solved by dry processing that, after the moisture in 0 5 10 15 20 25 30
the off-gas is removed by PSA, dried NO 2 is enriched NO2 concentration (vol%)
to 50 vol% or more by PSA-NO 2, cooled to 268 to 273 Fig. 4 Adsorption isotherms of various silica zeolite
K, and liquefied to be recovered. (Adsorption temperature: 298 K, NO2 reversible
adsorbed amount)
Fig
Fig.. 4 shows the isotherms of NO 2 adsorption. Ad- NO2 concentrations and adsorbed amounts are measured at
sorbent for NO 2 recovery by PSA requires both avoid- the same temperature for various high silica zeolites.

Mitsubishi Heavy Industries, Ltd.

Technical Review Vol.39 No.1 (Feb. 2002)
 9

NOx-free gas

NO2 8.3vol%

PSA dryer PSA-NO2

Blower Vacuum NO2 25vol% Vacuum pump

Process off-gas pump
NOx condenser
NO2 8vol%
N2O 4vol% Exhaust
NO2 50vol%
Residual gas gas

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 Refrigerator
B Freezing
Ozone store
Liquefied Ozone 5wt% Product
oxygen or generator Pa=120 kPa Vacuum ozone
PSA-O3 pump 20 wt%

Blower
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 elec-
trodes.
However, there is a problem in that electric power
consumption increases with an increase in ozone con-
centration and the achievable upper limit of the con-
centration is only about 20 wt% (3)(4).
Another process proposed is to produce high pu-
rity ozone by refrigerating and liquefying ozone pro-
duced by the silent discharge, with oxygen being
separated at about 100 K. Furthermore, an ozone-en-
riching 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 silica-
gel 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 re-
quires a considerable amount of cooling energy for
the low- temperature adsorption and heated regen-
eration, 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, hav-
ing a large SiO 2 /Al 2 O 3 ratio is capable of adsorbing a
large amount of ozone and has a low ozone decompos-
ing rate.
Fig
Fig.. 6 shows the schematic diagram of the investi-
gated system and Tabl able e 2 lists the properties of the

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Technical Review Vol.39 No.1 (Feb. 2002)
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Table 2 Performance of PSA-

PSA- O3 (1 kg O3 /h class)
Adsorption pressure 120 kPa
Regeneration pressure 5 kPa 2 000

Ozone adsorption load (m 3 N/h)

Adsorption temperature 240 K
Cycle time 5 min
Ozone enrichment ratio Max 12 times 1 500
Set maximum ozone concentration 20 wt%
Loaded amount of adsorbent 20 kg (10 kg×2 towers)
Adsorbent Silicalite 1 000
Electric power consumption per unit product 0.5 kWh/kg･O2
500
Table 3 Reduction of electric power cons
consmption per unit product
for PSA-
PSA-O3
0
Conventional process Ozone enrichment 200 220 240 260 280 300
Ozone generator 7.5 7.5
Temperature (K)
PSA-O2 7.5 2.5
Fig. 7 Performance of PSA-O 3
PSA-O3 - 0.5
Ozone enrichment rate and adsorption
Total 15 10.5 amount at various operation conditions
Concentration of are shown.
5 wt% 20 wt%
product ozone

system. Since the performance (enrichment rate, elec-
tric power consumption per unit product, required
adsorbent amount, etc.) of the ozone enrichment sys-
tem changes according to (a) regenerating pressure,
(b) adsorption temperature, etc., here as a typical
example, the relationship between adsorption tempera-
tures 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 gen-
erator 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 oxy-
gen can be improved to largely save the inlet oxygen
amount. The ozone enrichment system requires an
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 adsorp-
tion will be constantly improved in performance by
refinement in the high-temperature adsorption prop-
erty of ozone adsorbents and increase in the oxygen
recovery ratio due to application of argon adsorbents
Tabl
(T e 3 ).
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)