Gas Sep. Purif Vol. 9, No. 2, pp.

137-145, 1995
Copyright % 1995 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0950-4214/95 $10.00 + 0.00

Investigation and improvement of cryogenic

adsorption purification of argon from oxygen

A. N. Fedorov

NPO Cryogenmash, Balashiha-7, Moscow Region, Russia

The intensification of argon purification from oxygen by cryoadsorption is feasible by

cooling the adsorbent in an argon medium and by dehydration under decreased temperature.
A modified NaA zeolite is used as an adsorbent. The argon purification process has been
investigated at an oxygen concentration of 3% at 90 K and at a degree of purification
of 1 ppm. The conditions of the occurrence of argon capillary condensation have been
considered. The zeolite modification with the best adsorption performance has been defined
and an improved method of argon purification from oxygen has been developed.
The calculated relations for defining the value of the adsorbent dynamic capacitance as
a function of the rate of flow, and the argon preadsorption as a function of the adsorbent
cooling time have been obtained and a plot has been constructed for defining the coefficient
of dynamic capacitance decrease under decreased temperature of dehydration. As a result,
a calculation formula is proposed for defining the adsorber protective action time under
argon purification from oxygen with allowance for the rate of flow, the argon preadsorption
value and the temperature of dehydration.

Keywords: cryogenic purification; adsorption; argon; oxygen; zeolite

Nomenclature
a Constant value (cm3 g-i) T Temperature (K)
a0 Equilibrium adsorption value (cm3 g- ‘) ta Adsorption layer value (nm)
a cap Value of argon capillary condensation wo Ultimate volume of adsorption space
(cm3 gg’) (cm3 g- ‘)
adyn Dynamic capacity (%) (cm3 g-‘)
Calpreads Ultimate value of adsorption (cm” g- ‘) Greek letters
spreads Amount of preadsorbed argon (cm3 g- ‘)
4, Amount of adsorbed argon (cm3 g- ‘) e Coefficient of affinity
B Structural constant (Ke2) A Mean effective mass transfer coefficient
C Breakthrough concentration of oxygen (%) (1 min - ‘)
co Initial concentration of oxygen (%) PO Mass transfer coefficient (1 min-‘)
D Diffusion coefficient (m’ min- ‘) Aa Constant value (cm3 g- ‘)
a Mean diameter of adsorbent grains (m) P Dynamic viscosity (Pa s)
K Coefficient (cm3 g-l min m-i) P Gas density (kg m-“)
K deer Coefficient of dynamic capacitance decrease o Surface tension of liquid argon (mH m- ‘)
K preads Coefficient of preadsorption Cooling time (min)
(cm” gg’ min-‘) ET,, Ultimate cooling time (min)
L Adsorbent layer length (m) V Molar volume of adsorbed oxygen
LO Length of heat exchange zone (m) (cm3 mmoll ‘)
P Gas pressure (MPa) VCI, Specific volume of liquid argon
PS Saturated vapour pressure (kPa) (m3 tt’)
r Capillary radius (m) w Rate of flow (m min- ‘)

Gas Separation & Purification 1995 Volume 9 Number 2 137

Cryogenic adsorption purification of argon from oxygen: A. N. Fedorov

Introduction
In cryogenic air separation plants the production of
argon is connected with its purification from nitrogen
(down to 10%) and oxygen (down to 5%). In this case
purification from nitrogen will be performed by low-
temperature distillation. Separation from oxygen may be
carried out by means of distillation, adsorption or cata-
lytic hydrogenation ‘3’ . The pressure swing adsorption
(PSA) technique is also an option.
There is no need to review here the various methods
of argon production since they may be rationalized 6 12 13 7 17 1 2 3 1819 8 9 10

depending on the particular application conditions and Figure 1 Schematic diagram of the experimental plant: 1,
on the requirements of efficiency. If the optional method adsorber; 2, tank with refrigerant: 3, electric heater; 4, cylinder with
the initial mixture of argon and oxygen; 5, tank with liquid argon;
of argon separation is limited by the requirements of the 6, cylinder with oxygen; 7, 8, gas analysers; 9, vacuum pump; IO.
extent of purification, then the cryogenic adsorption gas meter; 11, shut-off and control valves; 12, flow meter; 13,
method is preferred because it seems to have no limita- rotameter; 14, compound pressure and vacuum gauge; 15, 16.
pressure regulators; 17, coil; 18. 19, upper and lower end plates
tions on the purification extent. For comparison, with
the distillation and catalytic methods, the purification
degree is not less than l-5 ppm, and with the PSA plant makes it possible to vary and control the mixture
method it amounts to a fraction of a per cent of the parameters: flow rate, pressure, temperature and con-
residual admixtures. centration of the components. Provision is made for
A promising method for separating pure argon is the possible desorption of the admixtures and cooling of the
use of an improved cryogenic adsorption method. This adsorbent with simultaneous evacuation of the adsorber
involves purification of argon from nitrogen and oxygen space as well as for cooling in an argon medium and an
by means of adsorption, with the adsorbent cooling in argon flow. When the admixtures are being adsorbed,
an argon medium. It features two switching adsorbers in the heating temperature is controlled within a wide range
which the purification of argon from nitrogen and oxy- at the cost of varying the electric heater capacity. The
gen occurs. Purification may be performed in one or two flow rates and concentrations of the components in the
serially installed adsorbers. In this case a high content desorbed gas are controlled in the course of desorption.
of nitrogen and oxygen admixture in the initial mixture The plant in the purification mode operates as follows
containing argon is allowed and the separated nitrogen (see Figure I). The preconditioned initial mixture is used
and oxygen are not wasted but are withdrawn as separa- directly from cylinder 4 or is prepared by mixing gaseous
tion products or are returned to the cycle. Thus, such argon, withdrawn from the liquid argon tank 5, with pure
technology is efficient and ecologically clean. With this oxygen from cylinder 6 through rotameter 12 in the
method, separation of nitrogen from the mixture required proportion. The mixture is passed through
(argon-nitrogen-oxygen) is carried out based on the rotameter 13 and shut-off valves, entering adsorber coil
selective adsorption of nitrogen, while purification from 17 where it is cooled to the required temperature by heat
oxygen is performed based on the molecular-sieve effect exchange with liquid oxygen fed to tank 2. Liquid oxygen
of zeolite NaA at 9&108 K. Unlike the commonly vapour is removed from the tank. The cooled initial
available distillation and adsorption technology’ used mixture enters an adsorbent sample layer where argon
for the production of pure argon, when purification from is purified from the oxygen. The purified argon is re-
nitrogen is effected through distillation and purification moved through gas meter 10. The oxygen concentration
from oxygen is carried out through adsorption at in the mixture at the inlet is controlled by gas analyser
cryogenic temperatures, the cryogenic adsorption tech- 7 while at the outlet it is controlled by gas analyser 8.
nology features lower power consumption and reduced The pressure is controlled by a standard pressure gauge
capital costs. 14 while the temperature is checked by sensors Tl, T2,
This paper describes an investigation of a number of T3 and T4.
modified samples of zeolite, type NaA, used in an im-
proved cryogenic adsorption purification of argon at the
stage of oxygen separation which may be employed both Results and discussion
in distillation and adsorption technology and in a cryo- The investigation of the adsorption under dynamic con-
genic adsorption method. ditions involved several stages.
The aim of the present study is to define the dynamic In the first stage the studies were aimed at establishing
characteristics of oxygen adsorption from an argon flow a modified type of zeolite NaA which would be suitable
under the conditions of enhanced adsorbent cooling and for cryogenic adsorption purification of argon from oxy-
zeolite dehydration at a low temperature. gen. The adsorbent was cooled and desorbed in vacuum.
Table 1 lists the investigation results, Figure 2 shows the
Experimental oxygen adsorption isographs4 constructed at 90 K. The
The studies were performed in an experimental plant3, designations of the curves in Figure 2 and in the sub-
shown diagrammatically in Figure 1. The design of the sequent figures correspond to those in Table 1. As seen

138 Gas Separation & Purification 1995 Volume 9 Number 2

 Cryogenic adsorption purification of argon from oxygen: A. N. Fedorov

Table 1 Investigation results of modified zeolite samples

Zeolite sample no.

Parameter 1 2 3 4 5 6 7 8

Grain mean diameter (m x 10m3) 2.4 2.3 2.3 2.3 2.3 2.4 2
Mixture flow rate (m min-‘) 0.94 1.04 0.97 0.734 1.12 1.06 0.98
Pressure (M Pa) 0.122 0.127 0.132 0.125 0.12 0.122 0.125 -
Oxygen volumetric fraction (%) 2.5 2.92 2.99 3.06 3.17 3.29 3.9
Period of protective effect (min) 215 255 255 120 160 218 150
Saturation period (min) 540 360 420 225 315 240 -
Ultimate cleaning degree (% x 1 Om4) 1.5 1.7 1.9 1 0.6 1.4 1.2 -
Dynamic capacity before breakthrough (%) 6.26 11.9 11.4 4.75 7.48 11.85 7.96 -
Mass transfer coefficient (I min’) 26.4 30.52 28.47 21.54 31.1 28.13
Mean effective mass transfer coefficient (I min-‘) 5.5 30.42 23.44 20.47 - 20.95 28.13
Mass transfer zone length (m) 0.315 0.12 0.144 0.145 0.18 0.125 -
Equilibrium adsorption rate (cm3 g-‘) 136.5 139.1 131.4 152 149.2 168.3 91.2
Ultimate volume of adsorption space (cm3 g-‘) 0.16 0.163 0.156 0.182 0.179 0.204 0.105
Structural constant ( Km2 x 10-e) 5.2 4.72 5.69 5.16 4.05 4.84
Degree of utilization of zeolite equilibrium 36.8 68.4 69.5 31.2 41.6 61.1 36.7
capacity (%)

from Figure 2, a small-size front of an adsorption wave Table 1 lists the results of the calculations and
is generated at a specified flow rate. The initial portions graphical plottings.
of the isographs are linear and characterize the distribu- Figure 3 shows plots of the adsorption graphs P,,
tion of the oxygen volumetric fraction by the layer length and Paz and definition of the heat exchange zone length
within the small breakthrough concentration range. It is L,,; Lo2 for the zeolite samples 1 and 2 which have
evident from these linear portions that external diffusion the maximum and minimum length of the heat exchange
prevails at the steady-state stage of the process within zone length, respectively.
the range of small relative concentrations. The statics of oxygen adsorption on NaA zeolite mod-
The end portions of the adsorption isographs define ified samples has been investigated concurrently with a
the equilibrium onset in the adsorbate-adsorbent sys- dynamic study of oxygen adsorption to reveal a most
tem: at c/c0 > 0.7 the internal differential resistance promising sample of the adsorbenP. The investigations
starts to have an effect on the adsorption process. were performed using a volumetric method at 90 K with
The dynamic capacity adyn of the adsorbent samples precooling of the adsorbent in vacuum.
and the mean effective mass transfer coefficient fi, were
found from the calculation of the flow material balances. -r(h)
The external mass transfer coefficient & for the experi- 0 1 2 3 4 5 6 7 8
mental conditions was determined from Equation (1)
using a similar theory for the conditions of purifying
argon from oxygen on synthetic NaA zeolites, when
governed by the effect of external diffusion kinetics:
Breakthrough
p. = 0.04Dcop~ - ‘d- l (1)

The heat exchange zone length L, is defined on the basis

of plotting the experimental isographs (Figure 3) with the
coordinates log(c/c,) and r and on the basis of the
adsorption poles Pd which correspond to the ordinate
log(cpreads/co 1.

1.0

0.8

o 0.6

-s 0.4

0.2

0
100 200 300 400 500 0.1 0.2 0.3 0.4 0.5

T (min) L Cm)
Figure 2 lsographs of oxygen adsorption Figure 3 lsographs and poles of oxygen adsorption

Gas Separation & Purification 1995 Volume 9 Number 2 139

Cryogenic adsorption purification of argon from oxygen: A. N. Fedorov

180

7 + +-+- 0.8
160 - -+------+

7- 140
(51 0.6
mE 120

t 100

80

60 0.2
0 10 20 30 40 50 60 70 80 90 100

P(kPa)
I I I I 1 I
Figure 4 Isotherms of oxygen adsorption 0 1 2 3 4 5 6

[log (P,lPl12
1.0
Figure 6 Isotherms of oxygen adsorption in the coordinates of
Equation (2)
0.8

high mass transfer coefficient and high degree of equilib-

0
0.6
B
0.4
0.2
t I I I
0 10 20 30
T (min)
Figure 5 Kinetic curves of oxygen adsorption
Figures 4 and 5 illustrate the isotherms and the kinetic
curves of oxygen adsorption on zeolite samples. All the
zeolite modifications under study have convex isotherms
and kinetic curves. Almost complete filling of the zeolite
adsorption volume occurs at about 15 kPa.
The analysis of the kinetic curves shows that the
velocity of internal diffusion of the oxygen molecules
within the crystal cavity of the modified zeolite under
study is high and the majority of oxygen is adsorbed
within l&15 min.
In compliance with the theory of volumetric filling of
micropores, the equation for the adsorption isotherm at
a temperature of T < T, has the form
Figure 6 illustrates the oxygen adsorption isotherms
of a zeolite sample with the coordinates log a and
[log(pJp)]’ of Equation (2). The constants IV, and B
and the oxygen ultimate adsorption rate were determined
from the results of the static investigations (see Tubk I).
A comparison of the results of the dynamic and static
investigations, when cooling the adsorbent in vacuum,
made it possible to establish that the modified zeolite
samples 2, 3, 6 and 7 had a high adsorption capacity,
rium capacity utilization (see Table I).
Thus, in the first stage of the investigations, the tech-
nology was studied which would allow for almost com-
plete removal of the adsorbed mixtures and prevention
of their adsorption when cooling. However, the process
of heating and cooling the adsorbent in a vacuum takes
a long time since the heat transfer over a layer of
granular, low-heat-conductive material is of low effi-
I I ciency. Enhancement of the heat exchange efficiency is
40 50 60 possible when the adsorbent is cooled by an argon how.
However, as reported in ref. 1, a decrease in the adsorbent
dynamic capacity may occur due to argon preadsorption.
In the second stage the argon adsorption was studied
when cooling the adsorbent7 on the zeolite samples of
high oxygen adsorption capacity which were revealed in
the first stage of the investigations.
It may be assumed that when cooling the adsorbent
in an argon medium, argon adsorption (a,,) would take
place on the surface of the crystals and on their defects
up to the temperature at which the molecular sieve
becomes effective in r zeolite micropore spaces (spreads);
it is also possible that argon capillary condensation (a,,,)
takes place in the secondary porosity of the zeolite grains.
Thus, the total amount of the adsorbed argon is given by
%I + %I + apreads + %sp (3)
It seem likely that the argon preadsorbed in the zeolite
micropores upon reaching the temperature when a
(2)
molecular sieve becomes effective will be blocked within
them since the dimensions of the inlet windows in the c1
spaces become smaller than the critical diameters of the
argon molecules. It may be assumed that this pre-
adsorbed argon will influence the intradiffusion kinetics
of oxygen adsorption in the purification process. The
extradiffusion kinetics of oxygen adsorption may be
influenced by the capillary condensation in the secondary
porosity of the adsorbent grains formed by the zeolite
crystals and the binder. The capillary condensation is
preceded by polymolecular adsorption on the mesopore

140 Gas Separation & Purification 1995 Volume 9 Number 2

 Cryogenic adsorption purification of argon from oxygen: A. N. Fedorov

0.6 could result in the pore dimensions being smaller than

those actually calculated and the capillary condensation
occurring at a lower partial pressure. The adsorption
layer t, may be estimated from the De Boure formula
derived for nitrogen at 77 K:

0.4584
m (5)
td = [log(p,~p)]“”
% 0.3
a
The calculations on the basis of Equation (5) show
that f, = I .28 nm. The results agree well with Aulton’s
0.2
data (t, = 1.3 nm) obtained under similar conditions’.
Thus, any possible decrease in the mesopore dimensions
0.1 due to argon adsorption is insignificant and has no effect
on the development of capillary condensation.
With regard to the above-mentioned considerations,
0 Equation (3) may be presented in the form
85 90 95 100 105 110

T(K) %t = %I + spreads (6)

Figure 7 Argon saturated vapour pressure p, as a function of
(1) temperature T and (2) the adsorption pressure p, defined by When cooling the adsorbent in vacuum and on its
Equation (4)
subsequent saturation with argon at a fixed adsorption
pressure and temperature, Equation (3) has the form
surface. Thus, before the capillary condensation develops
in the mesopores, the polymolecular adsorption rate will
be characterized by u,~ in Equation (3). The capillary
condensation takes place after the adsorbent forms a Hence, having determined a,, from the adsorbent pre-
concave meniscus in a capillary, and the pressure above cooling in vacuum, and having defined atot when cooling
it is lower than that of the saturated vapour above a flat in the argon medium, we can find the value for argon
surface. and condensation occurs at p/ps < I. At p/p, = 1 preadsorption from Equation (6).
the mesopores are filled with adsorbate. Figure 7 shows The studies were carried out in the experimental plant
the dependence (Curve 1) of argon saturated vapour (Figure I) using the volumetric method under the condi-
pressure on temperature within the period of the tions of cooling the adsorbent in an argon medium, in
molecular sieving effect of the NaA zeolite. an argon flow and in vacuum followed by its saturation
The effect of the capillary condensation is best de- with argon at 0.12 MPa’.
scribed by the Kelvin equation Figure 8 shows the plots of argon adsorption versus
cooling time when cooling the adsorbents in an argon
P 2av flow. The plots are linear, showing an increase in the
~PS = exp ( rRT 1 adsorption rate with cooling time. Samples 2, 3, and 6
would be preferable for the conditions of cooling with
Solving this equation for p makes it possible to
define the pressure at which capillary condensation may
occur. In commercial zeolite samples the effective radii
of mesopores are characterized by a peak at 230 nm8. As
an example, Figure 7 illustrates the results of defining p
from Equation (4) at Y = 230 nm (Curve 2).

;0
Thus, the working pressure in the process of purifying
argon from oxygen under the experimental conditions
concerned (90 K) must not exceed 0.12 MPa. Specific
pressure values (see Figure 7) correspond to different m,Ej 60 t
temperatures of the purification process. The absence of
capillary condensation in the samples under study, mod- 40
ified at high partial argon pressures, was confirmed by
the static investigations of oxygen and argon adsorption.
The adsorption isotherms are of a rectangular nature and
the capacity, close to equilibrium, is achieved at low I I I 1 I I I I

partial pressures when the conditions for capillary con- 0 IO 20 30 40 50 60 70 80

densation are absent. r(min)

Equation (4) was derived without considering that the Figure 8 Argon adsorption when cooling zeolite specimens in an
layer of molecules adsorbed on the mesopore surface argon flow

Gas Separation & Purification 1995 Volume 9 Number 2 141

 Cryogenic adsorption purification of argon from oxygen: A. N. Fedorov

Table 2 Calculation results of argon adsorption when cooling in argon medium and in vacuum

Cooling in argon medium Cooling in vacuum for 3 h

Zeolite Cooling period Capacity for argon Capacity for argon

sample no. (min) (N m3 g-l) (N m3g-‘)

7 84 119.5 59.6
6 40 38 22.3
2 35 36.2 23
3 35 31.3 24.3

argon. With a decrease in the cooling period the differ- conditions, cooling the adsorbents in an argon medium
ence in the argon adsorption rate for these samples using the experimental plant shown in Figure 1. Table 4
decreases to a minimum. presents the results of the defined adsorption values for
Table 2 presents the values of argon adsorption when oxygen and argon. The value for argon preadsorption is
cooling the adsorbent in an argon medium and when defined by Equation (6).
cooling it in vacuum with its subsequent saturation with The comparison of the values obtained for the oxygen
argon for 1 h. capacitance of the zeolite specimens with the test results,
It follows from Table 2 that cooling the adsorbent in when cooling the adsorbents in vacuum (see Table I),
vacuum would be preferential from the point of view of shows some decrease in the dynamic capacitance when
ensuring a minimum rate of argon adsorption. In this cooling the adsorbents in the argon medium.
case the adsorbent cooling period amounts to about 3 h, The argon capacitance and the argon preadsorption
whereas when cooling the adsorbent in an argon medium values obtained are in agreement with the data given in
it is shorter by a factor of 4.5. However, when cooling Table 3, when cooling the adsorbents in the argon
the adsorbent by an argon flow, the cooling period may medium. Thus, the adsorption values presented in Table
be reduced significantly (see Figure 8) although this 2 may be considered as constant under evaluation of the
would require a large amount of pure argon, or provision argon preadsorption value, when cooling the argon
should be made for a special circulation system. It is medium for the appropriate zeolite specimens.
possible, however, to cool the adsorbent in an argon The data on the argon adsorption values for the zeolite
medium quite rapidly for which purpose no additional specimens, Figure 8, may be used for a graphical
equipment is needed and the argon flow rate is a determination of the argon preadsorption value as a
minimum. Hence, this cooling method would be function of cooling time’, as shown in Figure 10. The
preferable provided the argon-from-oxygen purification construction reduces to the determination of the
process is not influenced by preadsorbed argon. preadsorption pole position PPreads,at the point of
Figure 9 shows the characteristic curves obtained when intersection of the straight line CD, characterizing the
cooling the modified zeolite samples by different argon adsorption value as a function of time, and the
methods. straight line parallel to the time axis, intersecting the
Table 3 lists the argon preadsorption rates found from coordinate axis at the level of a,,. Then, for instance, the
Equation (6).
For the determination of the preadsorption argon
Table 3 Argon preadsorption rates for zeolite samples when
influence on the process of purification from oxygen, the cooling in argon flow or argon medium
tests on zeolite specimens were performed under dynamic
Argon preadsorption rate (cm3 g-‘)
Zeolite
300 sample no. Cooling in argon flow Cooling in argon medium

7 51.7
6 22.3 15.7
250 2 15.5 13.2
3 8.2 7

2- 200
L Table 4 The results of the defined adsorption values for oxygen
and argon using zeolite specimens under dynamic conditions

Capacitance value under Amount of

150 dynamic conditions preadsorbed argon

No. of Oxygen
100 zeolite (cm3 g-l) Argon Argon
specimen (% weight) (cm3 g-‘) (cm3 g-‘)
0 30 60 90 120 150 180

T (min) 7 59.1 (7.83) 110.2 60

6 81.4 (10.77) 39.7 17.4
Figure 9 Characteristic curves for cooling zeolite specimens: 1, 2,
2 85.9 (11.37) 38.5 15.5
4, argon flow cooling (T = 15, 30. 60 min); 3, argon medium
3 85.1 (11.42) 33.7 9.4
cooling; 5, vacuum cooling

142 Gas Separation & Purification 1995 Volume 9 Number 2

 Cryogenic adsorption purification of argon from oxygen: A. N. Fedorov

0’ 4 a purification from oxygen, but results in increased power

I consumption and metal content of the equipment.
I
I r In the third stage the work was devoted to the study

I;lplead; of the dehydration influence of zeolite specimen 3 on the

process of argon purification from oxygen at decreased
temperature. The studies were again performed at the
experimental plant shown in Figure 1.
p ~“i7ial! The dehydration was carried out by a method which
preads ? o involved heating the zeolite by gas flow to the desorption
I st *
I I I temperature of the basic mass of water (393423 K) with
b
subsequent cooling and saturation of the adsorbent with
[T1”lt T
pure oxygen at the temperature of the process of argon
Figure 10 Argon preadsorption as a function of cooling time purification from oxygen (about 90 K) and desorption of
adsorbed oxygen at the cost of heating. The desorbed
oxygen was analysed for the water content. Figure 11
argon preadsorption value at zB may be defined accord-
shows the adsorbent temperature variation (curve 1) in
ing to the following formula
the course of saturation with oxygen and desorption and
a preads =
the characteristic outlet curves for water (2) under oxygen
Kprcads TB + Aa (8)
desorption”.
Thus, it is established that zeolite dehydration is
where Kpreads
is the coefficient of preadsorption
corresponding to the tangent of the angle y. carried out at the cost of water removal with the
It may be assumed that for a particular adsorbent desorbed oxygen.
there is a maximum allowable time of adsorbent cooling When performing the dehydration, a check of the
C~lub when the preadsorption argon [alpreads will adsorption properties of zeolite specimen 3 was carried
significantly affect the process of argon purification from out under the dynamic conditions of argon purification
oxygen. from oxygen with the parameters of the previous studies.
Table 5 presents the results of the test data processing, As a result, a value of 75 cm3 g-’ for the dynamic
when cooling the adsorbents by argon flow. It follows capacitance of oxygen was obtained and the oxygen
from the Table 5 that specimen 3, which has the capacitance decreased by 12% compared with dehydra-
minimum value of argon preadsorption and a high tion at 673 K. Thus, it is shown that the adsorbent
oxygen capacitance under dynamic conditions, is the dehydration is possible according to the proposed
preferred modification of zeolite for the argon cooling method. The decrease in the dynamic capacitance of
conditions. oxygen at the cost of dehydration under decreased
Thus, the introduction of the preadsorption pole temperature may be taken into account by the decrease
concept allows one to illustrate readily the preadsorption coefficient KdeCr. Figure 12 shows the decrease coefficient
process under argon cooling. The construction of as a function of dehydration temperature on the basis of
preadsorption poles for various modifications of zeolite the obtained results, assuming the linear character of the
under specified conditions of the cooling process allows adsorption capacitance reduction under temperature
one to choose the adsorbent with the minimum decrease and assuming that Kdecr = 1 at 673 K.
preadsorption value. In the final stage of the adsorption studies the influence
Taking Equation (8) into consideration, Equation (6) of the argon flow rate on the purification process was
for defining the total adsorption value may be written in defined. The studies were performed within the range of
the following form the working rates of the industrial process.
Figure 13 shows the results of defining the dynamic
alo1= a,, + &reads Llol + Aa (9) capacitance and mass transfer coefficient. The relation

The studies performed in the first and second stages

have been carried out with zeolite specimens subject to
- 100
dehydration at 673 K, which permits the exclusion of the
influence of preadsorbed water on the process of argon
-2
k
-50 -
Table 5 The results of the test data processing under cooling 0
zeolite specimens with argon flow I”

No. of zeolite K Aa
(cm3g~ta~in-l) 90 I 0
specimen (cm3 g-‘)
0 60 120 180
7 0.296 11.5 T (min)
6 0.114 5.29
2 0.096 3.56 Figure 11 The adsorbent temperature variation in the course of
3 0.044 3.34 oxygen saturation (curve 1) and characteristic outlet curves of water
(2) under oxygen desorption

Gas Separation & Purification 1995 Volume 9 Number 2 143

 Cryogenic adsorption purification of argon from oxygen: A. N. Fedorov

.-c
E
P

0 0.5 1 .o 1.5 2.0

-1
w(mmin )
500 600
Figure 14 The test adsorber protective action time as a function of
T(K) the rate of flow: (-) calculated by Equation (11); (0) experimental
values
Figure 12 The coefficient of zeolite dynamic capacitance
decrease as a function of dehydration temperature

is obtained for defining the adsorber protective action

time for argon purification from oxygen:

7=~~-~[~ln(~-l)+ln~-l]j (11)

wherep, = c,/y, and y1 is the mass concentration of the

adsorbing component in the gas flow equal to the half
the maximum amount, adsorbed by the zeolite at a given
temperature (kg me3).
30 - 60
Figure 14 shows the dependence of the protective
action time of the test adsorber on the flow rate, defined
- 50
by Equation (1 l), and the experimental points. As seen
20 - 40 in Figure 14, good agreement between the test data and
- 30 the calculated relation is observed.
To take account of the influence of argon and water
10 20
preadsorption, Equation (11) may be supplemented by
Equation (8) for defining the preadsorption value spreads
and the coefficient of the dynamic capacitance decrease
0 0.4 0.8 1.2 1.6 2.0 K deer, defined according to Figure 12. Then, the relation
-1 for defining the protective action time takes the following
w(m min )
form:
Figure 13 The dynamic capacitance (1) and mass transfer
coefficient (2) as a function of the rate of flow

for defining the dynamic capacitance has been obtained

on the basis of the test data processing:
The relation obtained allows one to perform the
a dyn=f(o) = a - Kc0 (10) calculations of the adsorbers of the systems for argon
purification from oxygen, taking into account the flow
Figure 13 shows the relations ad,,,, =f(w) calculated by parameters, the adsorption properties of the zeolite and
using Equation (10) and /II0 Z:(W) constructed according the conditions of the adsorbent preparation for the
to Equation (1) on the basis of calculation of the external purification process.
mass exchange coefficient. Good agreement of the The results of this work are at the stage of industrial
experimental and calculated data confirms the decisive adoption.
role of the external diffusion kinetics of the process of
argon purification from oxygen under the considered
conditions. References
Using the known equation for calculation of the
1 Golovko, G.A. Cryogenic production of inert gases Mash-
adsorption duration’, with allowance for the relation (10) inostroene (1983) 416
and the external mass exchange coefficient /IO, a formula 2 Barron, R.F. Cryogenic systems Energoizdat (1989) 408

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 Cryogenic adsorption purification of argon from oxygen: A. N. Fedorov

3 Fedorov, A.N., Davidov, I.A. and Golovko, G.A. The plant for the 7 Fedorov, A.N. The investigation of argon adsorption by modified
study of adsorbents under cryogenic dynamic conditions for the specimens of zeolite NaA under cryogenic purification of argon
process of argon purification from oxygen Khim Nsft Mnshinostr from oxygen in the shell-and-tube adsorber Cryogenic processes
(1990) 6 16 and technology: Proc NPO Cryogenmash (1990) 127-136
4 Fedorov, A.N. Golovko, G.A. and Davidov, LA. Investigation of 8 Keltsev, N.V. Fundamentals of adsorption technology Khimiya
modified zeolites for cryogenic purification of argon from oxygen (1984) 592
Khim Neft Mashinostr (1990) 11 20 9 Fedorov, A.N. The investigation of argon preadsorption on
5 Fedorov A.N. The experimental and calculated data on cryogenic cooling modified specimens of zeolite NaA Cryogenic processes
adsorption purification of argon from oxygen by modified zeolites and technology: Proc NPO Cryogenmash (1990) 1377140
Khim Neft Mushinostr (1990) 12 14 10 Fedorov, A.N. The increase of the efficiency of cryogenic
6 Chelishev, V.Yu., Golovko, G.A. and Fedorov, A.N. The adsorption purification of argon from oxygen for large-capacity
experimental and theoretical study of statics of oxygen adsorption plants Thesis: NPO Cryogenmash (1991) 135
with modified specimens of zeolite NaA Khim Ne/i Mashinostr
(1992) 9 18

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