Europaisches P a t e n t a m t

0 1 1 2 6 4 0
4 European Patent Office Publication number:
B1
Office europeen des brevets

EUROPEAN PATENT SPECIFICATION

® intci.4: C 01 B 2 3 / 0 0 , C 01 B 1 3 / 0 2 ,
Date of publication of patent specification: 30.08.89
B 01 D 5 3 / 0 4
Application number: 83307013.9

Date of filing: 16.11.83

Process for obtaining high concentration argon by pressure-swing-adsorption.

Priority: 19.11.82 JP 203853/82 Proprietor: SEITETSU KAGAKU CO., LTD.

14.06.83 JP 203853/82 346-1, Miyanishi Harimacho, Kakp-gun
Hyogo-ken 673-01 (JP)

Date of publication of application:

04.07.84 Bulletin 84/27 Inventor: Hayashi, Saburo
823-144, Kanki Higashikankicho
Kakogawa-shi (JP)
Publication of the grant of the patent: Inventor: Tsuchiya, Hiroo
30.08.89 Bulletin 89/35 101, Kusunokidaira Minamibingo
Kakogawacho Kakogawa-shi (JP)
Inventor: Haruna, Kazuo
Designated Contracting States: 130-10, Kuchiri Onoecho
DEFRGB Kakogawa-shi (JP)

References cited: Representative: Marshall, Monica Anne et al

GB-A-1 591 798 GALLAFENT & CO. 8 Staple Inn
US-A-2 810454 London WC1V7QH(GB)
US-A-3102 013
US-A-3923477
US-A-4 190 424
o

CM

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may
give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall
Q. be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been
UJ paid. (Art. 99(1 ) European patent convention).
Courier Press, Leamington Spa, England.
 EP 0112 640 B1

Description

The present invention relates to a process for obtaining high concentration argon by pressure-swing-
adsorption (hereinafter abbreviated to PSA).
5 Argon is known as an inert gas and is utilized for electric appliances, welding, degassing in steel
production, etc.
Conventionally, argon has been obtained from air in a cryogenic air separation plant. In this case, crude
argon is obtained by rectifying liquid air in a main rectification column in a liquid oxygen-producing plant,
withdrawing, among the resulting oxygen fractions, a fraction having a high argon concentration, and
10 further rectifying this fraction. Further, from the crude argon, high purity argon is obtained by introducing
hydrogen gas from a hydrogen bomb into the crude argon, passing the resulting gas mixture through
oxygen-removing apparatus packed with a catalyst such as palladium or the like to remove oxygen, and
passing the oxygen-removed gas again through a rectification column.
Argon is chemically inactive and moreover very similar to oxygen in physical properties as shown in
15 Table 1. Therefore, it is difficult to separate argon from oxygen, and its rectification requires a large number
of plates.

TABLE 1
Physical constants of gas molecules
20
Physical properties Argon Nitrogen Oxygen

Density (kg m 3) 1.7834 1.2507 1.4289

25 Specific gravity 1.38 — 1.1053

(air=1)

Melting point (°C) -189.2 -209.8 -218.4

30 Boiling point (°C) -185.7 -195.8 -182.9

Molecule diameter
Length (1CT10} 3.84 4.1 3.9
Width (1(T10) 3.0 2.8
35
Van der Waals constants
a (10s m"12 mol"2) 1.35 1.39 1.36
b (m"6 rnol"1) 32.3 39.2 31.9

40 Critical constants
to (°C) -122.4 -47.0 -118.5
(kg m 496969.2 346122 513500.4
(kg m" 533 313 436

45 Processes for separating argon by use of an adsorbent have been proposed. US —A—2810454
describes a method of separating oxygen from a mixture of oxygen and argon to obtain purified argon,
which method comprises contacting the oxygen and argon mixture with a dehydrated sodium zeolite and
preferentially adsorbing oxygen from the mixture. US— A—3102013 describes a method of fractionating
mixtures of three gasses using four zones arranged in series and parallel in which two zones contain
50 adsorbent for one of the gases and two zones contain adsorbent for one of the other gases. The adsorbents
may, inter alia, include ion exchange resins, activated carbon and molecular sieves. Pressure cycling
without the transfer of external heat is used to achieve fractionation of the gaseous system.
US—A—3923477 describes an adsorption process for increasing the proportion of a desired gas in a
mixture of which it is constituent. The process is particularly suited to the separation of either oxygen or
55 nitrogen from air or another oxygen/nitrogen mixture and comprises passing the gaseous mixture through
an adsorbent bed under pressure, reducing the pressure by concurrently venting the adsorbed gas,
evacuating residual gas from the bed, restoring the gas pressure in the adsorbent bed by introducing
product quality gas, finally introducing partly enriched gas and then repeating the sequence. The choice of
appropriate adsorbents allows enrichment of either oxygen or nitrogen from an air fed. Thus for example
60- synthetic zeolite molecular sieves are considered generally suitable as preferential nitrogen adsorbents
and carbon molecular seives are generally suitable as preferential oxygen adsorbents.
Further Australian Patent 519010 (and GB—A— 1591578) describes a process for obtaining argon from
a gas mixture comprising argon, oxygen and nitrogen, which comprises introducing this gas mixture into a
column packed with two kinds of adsorbents A and B having different adsorptivities toward oxygen and
65 nitrogen and subjecting the gas mixture to repeated PSA operation therein to obtain argon having at least a
 EP 0112 640 B1

chosen purity. In this process, it is intended that the two kinds of adsorbents adsorb oxygen and nitrogen,
respectively, whereby the argon concentration is increased. This is a process in which different adsorption
capacities of two adsorbents toward nitrogen, oxygen and argon are utilized, and nitrogen and oxygen in
air are successively adsorbed to leave argon.
s In this process, two different adsorbents are packed in a single adsorption column. Hence, it is difficult
to make the conditions inside the column optimum for the respective adsorbents, and accordingly, high
purity argon cannot be obtained. More specifically, if the conditions inside the column are made optimum
for either the adsorbent A or B, for example, optimum for oxygen-adsorption, oxygen is adsorbed but
nitrogen is not sufficiently adsorbed because the conditions are not optimum for the other adsorbent. In
10 this case, it follows that the argon obtained contains a considerable amount of nitrogen. Thus, satisfactory
operation cannot be conducted. The specification of the above Australian patent does not mention any
specific purity of argon obtained, but in such a process, the purity of argon recovered will be not more than
50%.
In view of the above situation, the present inventors have made extensive research on adsorption
w characteristics of various adsorbents. As a result, it has been found that a carbon molecular sieve whose
micro pore diameters have the highest distribution at 3x 10~10 m and a zeolite molecular sieve whose micro
characteristics at an
pore diameters have the highest distribution at 5x1 (T10 m have different adsorption
early stage of adsorption. For example, the carbon molecular sieve, when subjected to adsorption
operation for few minutes or more, loses its adsorption-selectivity. That is, it has been found that, when the
20 carbon molecular sieve and said zeolite molecular sieve are packed in one and same adsorption column or
one and same mechanism and PSA is conducted, the respective adsorption characteristics cannot be
sufficiently utilized. The carbon molecular sieve has an adsorption characteristic such that, in long term
adsorption, the molecular sieve adsorbs nitrogen and oxygen in equal volumes but, at an early stage of
adsorption, oxygen diffuses into its micro pores faster than nitrogen. Thus it is absolutely necessary for
25 adsorption of oxygen by use of the carbon molecular sieve that separation is conducted by utilizing the
above difference in adsorption rate between oxygen and nitrogen, that is, by adopting an adsorption time
as short as 1 to 2 min. or less including pressure equalization cycle.
On the other hand, the zeolite molecular sieve has the characteristic that nitrogen is preferentially
adsorbed and the nitrogen-adsorption ability thereof has no relation to the adsorption time.
30 US— A—4190424 describes an air separation process using PSA to provide high purity oxygen. Two
sections are used, one comprising beds of carbon molecular sieve and the other comprising beds of zeolite
molecular sieve. Oxygen is recovered using PSA by treating the starting air to a tower packed with carbon
molecular sieve in the first step and then further enriching the oxygen enriched gas from the first step in a
tower packed with zeolite molecular sieve in a second step. Alternatively the procedure can be reversed in
35 that the zeolite molecular sieve is used in the first step and the carbon molecular sieved in the second step
likewise to recover oxygen-rich gas. In both cases the argon is simply vented, without further treatment,
from the system.
In a preferred embodiment of the present invention, the difference in characteristics between the
above two adsorbents is effectively utilized, whereby one and same adsorption column is not packed with
40 the two adsorbents, but independent PSA apparatuses are packed with only one kind of adsorbent, and
nitrogen and oxygen are separated and removed stepwise under the optimum operating conditions for the
respective adsorbents, whereby argon is obtained.
According to the present invention, there is provided a process for selectively obtaining argon and
and at least 3%
oxygen by a PSA method from a starting gas comprising oxygen as the major component
45 of argon, which process comprises introducing the starting gas into a first adsorption apparatus containing
three carbon molecular sieve-packed columns, subjecting the starting gas to PSA therein to separate it into
a gas concentrated in oxygen and a gas concentrated in argon, compared with the starting gas,
subsequently introducing the gas concentrated in argon into a second adsorption apparatus containing
two carbon molecular sieve-packed columns, subjecting the gas concentrated in argon to PSA therein,
so recycling the desorbed gas of the second adsorption apparatus to the inlet of the first adsorption apparatus,
said PSA being conducted at an adsorption pressure of 135 to 1118 KPa and at a desorption pressure of not
more than 101 KPa in the first and second adsorption apparatuses whereby a gas more concentrated in
argon is obtained.
Preferably the said starting gas is itself obtained by subjecting air to PSA in a zeolite molecular sieve
55 packed adsorption apparatus to remove nitrogen. Thus the present invention also provides a process for
selectively obtaining argon and oxygen, both at high concentration, from air. Thus air may be subjected to
PSA in a zeolite molecular sieve-packed adsorption apparatus and the gas obtained then introduced into
carbon molecular sieve apparatus in accordance with the process of the invention whereby argon and
oxygen are simultaneously obtained.
60 The present invention will be explained specifically with reference to the accompanying drawings.
Fig. 1 shows a diagrammatic representation of apparatus for carrying out one PSA step of the process
of the present invention.
Fig. 2 shows the sequence and time cycle in the apparatus of Fig. 1. Fig. 3 shows a diagrammatic
representation of apparatus for carrying out a process according to the present invention. Figs. 4 to 7 show
65 the sequences and time cycles in the apparatus of Fig. 3. In Figs. 1 and 3,
 EP 0 112 640 B1
A'— Compressor I—Vacuum pump
A—Air blower J— Buffer tank
B' —Vacuum pump K—Secondary argon tank
B—Vacuum pump L—Hydrogen bomb
C —Primary argon tank M—Oxygen-removing Apparatus
C—Crude oxygen tank N—Cooler
D' —High concentration oxygen tank 0 —High concentration argon tank
D—Gas compressor P—Vacuum pump
E—Cooler Q—Cooler
w F—Vacuum pump R—Buffer tank
G—High concentration oxygen tank S—Recovered argon tank
H—Primary argon tank T—Vacuum pump

An outline of a typical embodiment of the present invention (starting from air) will be described
15 hereunder. The first-stage PSA apparatus is packed with a zeolite molecular sieve having a function of
selectively adsorbing nitrogen. Air as the starting material is supplied thereto and subjected to a PSA
operation to obtain a gas comprising, for example, 94% of oxygen, 1% of nitrogen and 5% of argon. The
second-stage PSA apparatus is packed with a carbon molecular sieve having a function of selectively
adsorbing oxygen. The gas thus obtained is fed thereto and subjected to a PSA operation for a short time,
20 whereby oxygen is adsorbed and argon is concentrated to about 40% (nitrogen about 8%) as primary
argon. At this stage, an oxygen gas having an oxygen concentration higher than that of the fed gas,
namely, an oxygen concentration of about 97%, is obtained as a desorbed gas, and these two stages
contribute also to increasing the oxygen concentration of the starting gas. This is an effect of packing each
adsorbent in independent PSA apparatus and subjecting independently each apparatus to a different PSA
25 operation, and such a result cannot be obtained, when the above two adsorbents are together packed in
one and same apparatus and the starting gas is introduced into the above two adsorbents to be subjected
to PSA operation in the apparatus. Further, the third stage PSA apparatus is packed with the same carbon
molecular sieve, and in this apparatus, the primary argon gas is subjected to PSA operation in the same
manner as in the second-stage PSA apparatus, whereby oxygen is removed by adsorption and argon is
30 concentrated to 85% as secondary argon. During this operation, nitrogen is also concentrated with
substantially the same composition ratio to argon (8:40). Because the ratio of argon to nitrogen is not
varied, if further reduction of the nitrogen content is desired, another purification method is required.
By the two-stage PSA operation, the oxygen concentration is reduced down to several percent.
However, in order completely to remove oxygen, two moles of hydrogen per mole of oxygen should be
35 added to the secondary argon gas. Then, the hydrogen-added secondary argon gas is treated with a
palladium-supporting deoxygenating catalyst, whereby oxygen is removed in the form of water.
The aforementioned second-stage PSA apparatus is a three-column type apparatus. A flow sheet for
the second-stage PSA apparatus containing three columns is shown in Fig. 1, and the operational sequence
of the apparatus is shown in Fig. 2.
40 In Fig. 1, adsorption columns I, II, III are packed with a carbon molecular sieve of 3x10~10 m pore
diameter. Crude oxygen (oxygen: 94.5%, argon: 4.5%, nitrogen: 1%, 409 KPa) is introduced via a
compressor A' into column I, where oxygen is adsorbed. The resulting gas is stored in a primary argon tank
C. The adsorbed oxygen is desorbed and stored in a high purity oxygen tank D' via a vacuum pump B'.
This procedure is conducted by sequentially opening and shutting valves 1 to 16 as shown in Fig. 2.
45 The third-stage PSA apparatus contains two columns, and PSA operation is conducted by the
sequential five steps of adsorption pressure equalization, desorption, pressure equalization, and
pressurization by starting gas. The desorbed gas from the third-stage PSA apparatus is recycled to the feed
gas of the second-stage PSA apparatus to recover argon.
After the operation in the third-stage PSA apparatus, oxygen is removed by adding hydrogen, in the
50 same manner as explained above.
When the required argon purity is 99% or more, the product gas of the third-stage PSA apparatus is
sent to a fourth-stage PSA apparatus packed with zeolite molecular sieve to adsorb and remove nitrogen. It
is possible for the desorbed gas from the fourth-stage PSA apparatus to be sent to a fifth-stage PSA
apparatus packed with zeolite molecular sieve to adsorb nitrogen and recover argon, and for the recovered
55 argon to be recycled to the feed gas of the fourth-stage PSA apparatus. The desorbed gas from the
fifth-stage PSA apparatus is a gas comprising nitrogen as major component and argon, and is utilized as an
inert gas.
It is also possible for, in place of the above fifth-stage PSA apparatus, a cryogenic air separation plant
to be used to obtain high purity argon.
60 The above described operation can be summarized as follows:
Using air as the starting gas, crude oxygen is obtained in the first-stage PSA apparatus. In the
second-stage PSA apparatus, an oxygen product having an oxygen concentration of 95% or more and
primary argon gas are simultaneously obtained. The primary argon gas is concentrated in the third-stage
PSA apparatus to obtain a secondary argon gas containing a slight amount of oxygen. The desorbed gas
65 from the third-stage PSA apparatus is recycled to the feed gas of the second-stage PSA apparatus. The
 EP 0112 640 B1

small amount of oxygen in the secondary argon gas is removed by hydrogen-reduction in the
PSA
oxygen-removing apparatus. The resulting argon free from oxygen is treated in the fourth-stage
apparatus to adsorb and remove nitrogen, whereby high purity argon of at least 99% concentration is
obtained. The desorbed gas from the fourth-stage PSA apparatus is introduced into the fifth-stage PSA
feed gas of the
5 apparatus to recover argon. This recovered argon is recycled to be mixed with the
fourth-stage PSA apparatus. The desorbed gas from the fifth-stage PSA apparatus is rich in nitrogen and
utilized as an inert gas. The overall yield of high purity argon is 40% or more, as more than 99% purity
argon, based on the argon in the crude oxygen product.
When, as the starting gas, the crude oxygen containing 4.5% of argon is replaced by a gas mixture
air
10 containing about 12% of argon, which is withdrawn from the rectification column of a cryogenic
PSA and the later-stage PSA apparatus can be
separation plant, operations of the second-stage apparatus
conducted more efficiently. This process is also included in the scope of the present invention.
The zeolite molecular sieve used in the present invention has preferably a micro pore diameter having
the highest distribution at 5x10"10 m. The carbon molecular sieve usedin the present invention has
diameter showing the highest distribution at 3x10 10 m. The adsorption pressure
is preferably a micro pore
is within the range of 135 to 1118 KPa, more preferably 206 to 409 KPa, from the economical viewpoint.
With respect to the desorption pressure, a lower desorption pressure gives a better efficiency. Desorption is
KPa or less.
operated at the pressure of 101 KPa or less, generally 53.3 KPa or less, preferably of 26.7
Theoretically, the efficiency is higher when adsorption is operated at a lower temperature and desorption is
20 done at a higher temperature, in view of the adsorption capacity. However, since the PSA operation is
conducted adiabatically and the heat of adsorption (exothermic) is consumed as a heat of desorption
(endothermic), the PSA operation is effectively operated at the normal temperature.
The high purity argon referred to in the present invention means argon of at least 98% concentration. It
is possible to obtain, in the present invention, high purity argon having at least 99.9% concentration such
25 as welding argon specified by JIS, but the yield of such high purity argon is low. For applications such as
degassing in steel production, argon of about 98% concentration is sufficient, and therefore, the present
In the present
process is effective for such applications, particularly from the economical standpoint.
invention, each of the second-stage PSA apparatus and the third-stage PSA apparatus may consist of one
adsorption column, but it is desirable that ordinarily each stage-PSA apparatus has a plurality of adsorption
30 columns and a sequential operation of adsorption, pressure equalization, desorption, pressure
equalization, and pressurization by starting gas (or pressurization by product gas) which is operated by
sequentially opening and shutting valves.
In the PSA operation, there is a correlation between the composition and the yield of a product gas. If
the purity of the product gas is raised, the yield is decreased. Therefore, operation conditions such as
35 adsorption pressure, desorption pressure, cycle time and the like should be selected in compliance with the
desired product purity.
Hereinafter, the present invention will be explained in more detail referring to Examples, but is not
restricted to the Examples. (Example 1 describes only a first carbon molecular sieve PSA operation of the
the first adsorption
process of the invention; the second being described in Example 2. Finally recycling to
40 apparatus is described in Example 3).

Example 1
A mixed gas composed of 4.5% of argon, 93.6% of oxygen and 1.9% of nitrogen was supplied to the
45 first carbon molecular sieve-packed PSA apparatus shown in Fig. 1 comprising three adsorption columns
each having a size of 40 mm Dx500 mm H and being packed with a carbon molecular sieve adsorbent
having a micro pore diameter of 3x10"10 m, and PSA was operated in the apparatus. The maximum
adsorption pressure was 307 KPa and the desorption pressure was 20.0 KPa. The cycle time was, as shown
in Fig. 2, 38.5 sec for adsorption, 38.5 sec for desorption, and 1.5 sec for pressure equalization (a total time
so of one cycle: 120 sec). When the product was withdrawn at a rate of 0.8 Nl./min, the argon product
consisted of 33.0% of argon, 52.3% of oxygen and 14.7% of nitrogen. The yield of argon was 69%. The
desorbed gas (oxygen product) consisted of 1.5% of argon, 97.9% of oxygen and 0.5% of nitrogen. The
yield of oxygen was 94.7%.

55
Example 2 . .
The starting gas which had the same composition as the product gas obtained in Example 1 was
introduced into the second carbon molecular sieve-packed PSA apparatus. The PSA apparatus had two
adsorption columns each having a size of 40 mm Dx500 mm H and being packed with a carbon molecular
The consisted of 35.5% of argon, 50% of oxygen and 14.5% of nitrogen. The maximum
so sieve. starting gas
adsorption pressure was 206 KPa and the desorption pressure was 13.3 KPa. The cycle time was 45 sec for
adsorption, 48.5 sec for desorption, 1.5 sec for pressure equalization and 3.5 sec for pressurization by
starting gas (a total time of one cycle: 100 sec). When the product was withdrawn at a rate of 1.0 Nl./min,
that consisted of 71.1% of argon, 2.67% of oxygen and 26.2% of nitrogen. The argon yield was 53%. The
and 10.6% of nitrogen.
6s desorbed gas consisted of 22.7% of argon, 66.7% of oxygen
 EP 0112 640 B1

Example 3
The desorbed gas obtained by the PSA operation in Example 2 was recycled into the starting gas of the
first carbon molecular sieve-packed PSA apparatus of Example 1. The first carbon molecular sieve-packed
PSA apparatus in Example 1 was composed of three adsorption columns, and the second carbon molecular
5 sieve-packed PSA apparatus in Example 2 was composed of two adsorption columns. The maximum
adsorption pressure was 307 KPa. The desorption pressure of the first carbon molecular sieve-packed
adsorption apparatus was 20 KPa and that of the second carbon molecular sieve-packed adsorption
apparatus was 13.3 KPa. The starting gas was a product gas consisting of 4.35% of argon, 93.5% of oxygen
and 2.15% of nitrogen from a zeolite molecular sieve-packed PSA apparatus. The product gas from the
io second carbon molecular sieve-packed PSA apparatus consisted of 71.8% of argon, 2.5% of oxygen and
25.6% of nitrogen. The argon yield was 56%. The desorbed gas (oxygen product) from the first carbon
molecular sieve-packed PSA apparatus consisted of 2.0% of argon, 96.6% of oxygen and 1.3% of nitrogen.
The oxygen yield was 99.9%.

is Example 4
The product gas from the second carbon molecular sieve-packed PSA apparatus in Example 3 was
subjected to deoxygenation in an oxygen-removing apparatus and then to PSA operation in a first zeolite
molecular sieve-packed PSA apparatus in order to remove nitrogen, and to obtain argon. The desorbed gas
from the first zeolite molecular sieve-packed PSA apparatus was subjected to PSA operation in a second
20 zeolite molecular sieve-packed PSA apparatus to further remove nitrogen and recover argon by removing
nitrogen. The desorbed gas from the second zeolite molecular sieve-packed PSA apparatus was recycled to
the feed line of the first zeolite molecular sieve-packed PSA apparatus. Each of the first zeolite molecular
sieve-packed PSA apparatus and the second zeolite molecular sieve-packed PSA apparatus was composed
of three adsorption columns. The desorption step was followed by a pressurization by the product gas,
25 namely, a step of charging these columns with a product gas. The same cycle time was used for the first
PSA apparatus and the second PSA apparatus, and it was 60 sec for adsorption, 50 sec for desorption, 10
sec for pressure equalization and 50 sec for pressure restoration by product gas. The adsorption pressure
of the first zeolite molecular sieve-packed PSA apparatus was 155.3 KPa and the desorption pressure was
6.7 KPa. The mixture of the inlet gas of the first zeolite molecular sieve-packed PSA apparatus and the
30 product gas (recycle gas) from the second zeolite molecular sieve-packed PSA apparatus consisted of
78.1% of argon and 21.9% of nitrogen. The product argon had a purity of 99%. The argon yield of the first
zeolite molecular sieve-packed PSA apparatus was 55% and the argon yield obtained when the first zeolite
molecular sieve-packed PSA apparatus was combined with the second carbon molecular sieve-packed PSA
apparatus was 79.8%. The desorbed gas from the second zeolite molecular sieve-packed PSA apparatus
35 consisted of 36.4% of argon and 63.6% of nitrogen. Incidentally, the adsorption pressure of the second
zeolite molecular sieve-packed PSA apparatus, was 226 KPa and the desorption pressure was 6.7 KPa.

Example 5
The first-stage to fifth-stage PSA apparatus were actually connected as shown in Fig. 3. PSA operation
40 was conducted by adopting the sequences and time cycles as shown in Figs. 4 to 7 which were different
from those of Examples 1 to 4, whereby high concentration argon was continuously obtained from air.
Particularly, a known sequence and a known time cycle were applied to the first-stage PSA apparatus. Each
gadget in PSA apparatus is shown in Fig. 3. The dimensions of adsorption columns of each PSA apparatus
are as shown in Table 3.
45
TABLE 3

First-stage PSA apparatus Three columns of 800 mm Dx1100 mm H

so Second-stage PSA apparatus Three columns of 200 mm Dx1100 mm H

Third-stage PSA apparatus Two columns of 130 mm Dx1100 mm H

Fourth-stage PSA apparatus Three columns of 80 mm Dx1100 mm H

55
Fifth-stage PSA apparatus Three columns of 70 mm Dx1100 mm H

The pressure, gas component and flow rate at each point are as shown in Table 4.

60

65
 EP 0112 640 B1
Note: 1. ND is an abbreviation for Not Determined and refers to a concentration which cannot be
detected by a zirconia type oxygen analyzer.
2. All the other data of the gas component are analytical values obtained by gas
chromatography.
5
As shown in Table 4, argon in the outlet gas (2) of the first-stage PSA apparatus was enriched to 99%
concentration, and was recovered with a 40% yield at the outlet (10) of the fourth-stage PSA apparatus.
Oxygen of 90% concentration in the outlet gas (2) of the first-stage PSA apparatus was enriched to 94.8%
concentration in line (5) and desorbed at the pressure of 20.0 KPa in the second-stage PSA apparatus.
10 Further, a nitrogen gas of 86.6% concentration free from oxygen was obtained as the desorbed gas (13)
from the fifth-stage PSA apparatus.

Claims

is 1. A process for selectively obtaining argon and oxygen by a pressure-swing-adsorption method from
a starting gas comprising oxygen as the major component and at least 3% of argon, which process
comprises introducing the starting gas into a first adsorption apparatus containing three carbon molecular
sieve-packed columns, subjecting the starting gas to pressure-swing-adsorption therein to separate it into a
gas concentrated in oxygen and a gas concentrated in argon, compared with the starting gas, subsequently
20 introducing the gas concentrated in argon into a second adsorption apparatus containing two carbon
molecular sieve-packed columns, subjecting the gas concentrated in argon to pressure-swing-adsorption
therein, recycling the desorbed gas of the second adsorption apparatus to the inlet of the first adsorption
apparatus, said pressure-swing-adsorption being conducted at an adsorption pressure of 135 to 1118 KPa
and at a desorption pressure of not more than 101 KPa in the first and second adsorption apparatuses
25 whereby a gas more concentrated in argon is obtained.
2. A process according to claim 1, wherein the said gas more concentrated in argon obtained from the
said second adsorption apparatus is further subjected to pressure-swing-adsorption in a zeolite molecular
sieve-packed adsorption apparatus to separate out nitrogen to obtain gas further concentrated in argon.
3. A process according to claim 2, wherein the said gas more concentrated in argon obtained from the
30 said second adsorption apparatus, prior to being passed to the zeolite molecular sieve-packed adsorption
apparatus, is passed through a deoxygenation apparatus, in which hydrogen is added, whereby there is
obtained argon rich gas substantially free from oxygen.
4. A process according to claim 2 or 3, wherein desorbed gas from the said zeolite molecular
sieve-packed adsorption apparatuses further subjected to pressure-swing-adsorption in a second zeolite
35 molecular sieve-packed adsorption apparatus to recover argon, and the argon recovered is introduced into
the starting gas at the inlet of the first zeolite molecular sieve-packed adsorption apparatus.
5. A process according to claim 4 wherein each of the said first and second zeolite molecular
sieve-packed adsorption apparatus consist of three columns.
6. A process according to claim 1, wherein the said gas more concentrated in argon obtained from the
40 said second adsorption apparatus is passed through a deoxygenation apparatus in which hydrogen is
added, thereby obtaining argon rich gas substantially free from oxygen, and this is sent to a low
temperature liquefaction apparatus in which argon is liquefied to separate out nitrogen, thereby obtaining
further purified argon.
7. A process according to any one of the preceding claims, wherein the starting gas is obtained by
45 subjecting air to pressure-swing-adsorption in a zeolite molecular sieve-packed adsorption apparatus.
8. A process according to any one of claims 1 to 7 wherein the starting gas is a side cut from the
liquefaction-rectification column of a cryogenic air separation plant, which is a mixed gas comprising
oxygen as the major component and about 12% argon.
9. A process according to any one of the preceding claims wherein the carbon molecular sieve has a
so micropore diameter of 3x1 0~10 m.
10. A process according to any one of the preceding claims wherein the adsorption pressure is 206 to
409 KPa.
11. A process according to any one of the preceding claims wherein the desorption is operated at
pressure of 53.3 KPa or less.
55 12. A process according to claim 11 wherein the desorption is operated at a pressure of 26.7 KPa or
less.
Patentanspriiche

60 1. Verfahren zum selektiven Gewinnen von Argon und Sauerstoff durch eine Schaukeldruck-
Adsorptionsmethode aus einem Ausgangsgas, welches Sauerstoff als Hauptkomponente und weniger als
3% Argon enthalt, wobei das Verfahren umfasst: das Einfiihren des Ausgangsgases in eine erste
Adsorptionsvorrichtung, enthaltend drei mit einem Kohlenstoff-Molekularsieb gepackte Kolonnen,
Unterwerfen des Ausgangsgases einer Schauckeidruck-Adsorption unter Auftrennung in ein Gas, das im
65 Vergleich zu dem Ausgangsgas an Sauerstoff und ein Gas, das im Vergleich zum Ausgangsgas an Argon
 EP 0112 640 B1

konzentriert ist, anschliessendes Einfuhren des an Argon konzentrierten Gases in eine zweite
Unterwerfen
Adsorptionsvorrichtung, die zwei mit Kohlenstoff-Molekularsieb gepackte Kolonnen enthalt,
des an Argon konzentrierten Gases einer Schauckeldruck-Adsorption darin, Zuruckfiihren des desorbierten
Gases von der zweiten Adsorptionsvorrichtung in den Einlass der ersten Adsorptionsvorrichtung, wobei
5 die Schauckeldruck-Adsorption bei einem Adsorptionsdruck von 135 bis 1118 KPa und einem Desorptions-
druck von nicht mehr als 101 KPa in den ersten und zweiten Adsorptionsvorrichtungen vorgenommen
wird, wodurch man ein Gas, das starker an Argon konzentriert ist, erhalt.
2. Verfahren gemass Anspruch 1, bei dem das aus der zweiten Adsorptionsvorrichtung an Argon
starker konzentrierte Gas einer weiteren Schauckeldruck-Adsorption in einer mit einem Zeolithmolekular-
starker
10 sieb gepackten Adsorptionsvorrichtung unterworfen wird, urn Stickstoff abzutrennen und ein noch
an Argon konzentriertes Gas zu erhalten.
3. Verfahren gemass Anspruch 2, bei dem das noch starker an Argon konzentrierte Gas, welches aus
der zweiten Adsorptionsvorrichtung erhalten wurde, vor dem Einfuhren in die mit einem Zeolithmolekular-
sieb gepackte Adsorptionsvorrichtung durch eine Desoxidationsvorrichtung geleitet wird, in welcher
15 Wasserstoff zugegeben wird und wodurch man ein im wesentlichen von Sauerstoff freies, argonreiches
Gas e r h a l t . .
4. Verfahren gemass Anspruch 2 oder 3, bei dem das desorbierte Gas aus der mit einem
Zeolithmolekularsieb gepackten Adsorptionsvorrichtung weiterhin einer Schauckeldruck-Adsorption in
einer zweiten mit einem Zeolithmolekularsieb gepackten Adsorptionsvorrichtung unterworfen wird, unter
der ersten mit einem
20 Gewinnung von Argon, und das gewonnene Argon in das Ausgangsgas am Einlass
Zeolithmolekularsieb gepackten Adsorptionsvorrichtung eingefuhrt wird.
5. Verfahren gemass Anspruch 4, bei dem jede der ersten und zweiten, mit einem Zeolithmolekularsieb
gepackten Adsorptionsvorrichtungen aus drei Saulen besteht.
6. Verfahren gemass Anspruch 1, bei dem das starker an Argon konzentrierte Gas, das aus der zweiten
Wasserstoff
25 Adsorptionsvorrichtung erhalten wurde, durch eine Desoxidationsvorrichtung, in welcher
wird, geleitet wird, wodurch man ein argonreiches Gas erhalt, das im wesentlichen von
zugegeben
Sauerstoff frei ist, und dass man dieses zu einer Niedrigtemperatur-Verflussigungsvorrichtung leitet, in
welcher das Argon verflussigt und Stickstoff abgetrennt wird und wodurch man ein weiter gereinigtes
Argon erhalt.
30 7. Verfahren gemass einem der vorhergehenden Anspruche, bei dem das Ausgangsgas erhalten
wurde, indem man Luft einer Schauckeldruck-Adsorption in einer mit Zeolithmolekularsieb gepackten
Adsorptionsvorrichtung unterwirft.
8. Verfahren gemass einem der Anspruche 1 bis 7, bei dem das Ausgangsgas em Schnitt aus der
Verfliissigungs-Rektifikationskolonne einer kryogenen Lufttrennanlage ist, welches ein Mischgas darstellt
35 aus Sauerstoff als Hauptkomponente und etwa 12% Argon.
9. Verfahren gemass einem der vorhergehenden Anspruche, bei dem das Kohlenstoff-Molekuiarsieb
einen Mikroporendurchmesser von 3x10"10 m hat.
10. Verfahren gemass einem der vorhergehenden Anspruche, bei dem die Adsorptionsdrucke 206 bis
409 KPa betragen.
40 11. Verfahren gemass einem der vorhergehenden Anspruche, bei dem die Desorption bei einem Druck
von 53,3 KPa oder weniger vorgenommen wird.
12. Verfahren gemass Anspruch 11, bei dem die Desorption bei einem Druck von 26,7 KPa oder
weniger vorgenommen wird.

45
Revendications

1. Procede destine a I'obtention de fagon selective d'argon et d'oxygene par une methode d'adsorption
a oscillation de pression a partir d'un gaz de depart comprenant de I'oxygene en tant que constituant
so principal et au moins 3% d'argon, lequel procede consiste a introduire le gaz de depart dans un premier
appareil d'adsorption contenant trois colonnes garnies de tamis moleculaires de carbone, a soumettre le
le un gaz
gaz de depart a une adsorption a oscillation de pression a I'interieur de celles-ci pour separer en
concentre en oxygene et en un gaz concentre en argon, par rapport au gaz de depart, subsequemment a
introduire le gaz concentre en argon dans un second appareil d'adsorption contenant deux colonnes
adsorption a
55 garnies de tamis moleculaires de carbone, a soumettre le gaz concentre en argon a une
oscillation de pression a I'interieur de celles-ci, a recycler le gaz desorbe du second appareil d'adsorption
jusqu'a I'entree du premier appareil d'adsorption, cette adsorption a oscillation de pression etant conduite
KPa
a une pression d'adsorption de 135 a 1118 KPa et a une pression de desorption non superieure a 101
dans les premier et second appareils d'adsorption, un gaz plus concentre en argon etant ainsi obtenu.
6o 2. Procede selon la revendication 1, dans lequel le gaz plus concentre en argon obtenu a partir du
second appareil d'adsorption est de plus soumis a une adsorption a oscillation de pression dans un
appareil d'adsorption garni de tamis moleculaires de zeolite pour extraire par separation I'azote afin
d'obtenir un gaz davantage concentre en argon.
3. Procede selon la revendication 2, caracterise en ce que I'on fait passer le gaz davantage concentre en
son passage sur I'appareil
65 argon obtenu a partir du second appareil d'adsorption, prealablement a
 EP 0112 640 B1

d'adsorption garni de tamis moleculaires de zeolite, a travers un appareii de desoxygenation, dans lequel
on ajoute de I'hydrogene, un gaz riche en argon sensiblement exempt d'oxygene, etant ainsi obtenu.
4. Procede selon la revendication 2 ou 3, dans lequel le gaz desorbe a partir de I'appareil d'adsorption
garni de tamis moleculaires de zeolite est soumis de plus a une adsorption a oscillation de pression dans
s un second appareii d'adsorption garni de tamis moleculaires de zeolite pour recuperer I'argon, et I'argon
recupere est introduit dans le gaz de depart a I'entree du premier appareii d'adsorption garni de tamis
moleculaires de zeolite.
5. Procede selon la revendication 4, dans lequel chacun des premier et second appareils d'adsorption
garni de tamis moleculaires de zeolite est constitue par trois colonnes.
10 6. Procede selon la revendication 1, dans lequel on fait passer le gaz davantage concentre en argon,
obtenu, a partir du second appareii d'adsorption, a travers un appareii de desoxygenation dans lequel on
ajoute de I'hydrogene, permettant ainsi d'obtenir un gaz riche en argon sensiblement exempt d'oxygene, et
celui-ci est envoye a un appareii de liquefaction a basse temperature dans lequel I'argon est liquefie pour
en separer I'azote, permettant ainsi d'obtenir de I'argon davantage purifie.
15 7. Procede selon I'une quelconque des revendications precedentes, dans lequei le gaz de depart est
obtenu en soumettant de I'air a une adsorption a oscillation de pression dans un appareii d'adsorption
garni de tamis moleculaires de zeolite.
8. Appareii selon I'une quelconque des revendications 1 a 7, dans lequel le gaz de depart est une coupe
ou fraction laterale provenant de la colonne de liquefaction-rectification d'une installation de separation
20 d'air cryogenique, qui est un gaz melange comprenant de I'oxygene en tant que constituant principal et
environ 12% d'argon.
9. Procede selon I'une quelconque des revendications precedentes, dans lequel le tamis moleculaire de
carbone presente un diametre de micropores de 3X1O~10 m.
10. Procede selon I'une quelconque des revendications precedentes, dans lequel la pression
25 d'adsorption est de 206 a 409 KPa.
11. Procede selon I'une quelconque des revendications precedentes, dans lequel la desorption est
effectuee a une pression de 53,3 KPa ou inferieure.
12. Procede selon la revendication 11, dans lequel la desorption est effectuee a une pression de 26,7
KPa ou inferieure.
30

35

40

45

50

55

60

65

10
 EP 0112 640 B1

FIG. I

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 EP 0112 640 B1

FIG. 2

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FIG. 4

FIRST STAGE PSA SEQUENCE

60 SEC. 60 SEC 60 SEC.

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 EP 0112 640 B1

FIG. 5

SECOND STAGE PSA SEQUENCE

I.5 SEC. L5 .SEC I.5 SEC.

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 EP 0112 640 B1

FIG. 6

THRIRD STAGE PSA SEQUENCE

2 SEC. 3 SEC. 2 SEC 3 SEC.
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 EP 0 112 640 B1

FIG. 7

FOURTH AND FIFTH STAGE PSA SEQUENCE

5 SEC. 5 SEC 5, SEC

VALVE NQ 55 SEC. 55 SEC. 55 SEC.

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