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137-145, 1995
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A. N. Fedorov
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- ‘)
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
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)
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
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
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
;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
Table 2 Calculation results of argon adsorption when cooling in argon medium and in vacuum
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
No. of Oxygen
100 zeolite (cm3 g-l) Argon Argon
specimen (% weight) (cm3 g-‘) (cm3 g-‘)
0 30 60 90 120 150 180
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
.-c
E
P
-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
7=~~-~[~ln(~-l)+ln~-l]j (11)
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