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Patent 1084421 Summary

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(12) Patent: (11) CA 1084421
(21) Application Number: 234075
(54) English Title: RECOVERY OF GASES FROM GASEOUS MIXTURES
(54) French Title: RECUPERATION DES GAZ D'UN MELANGE GAZEUX
Status: Expired
Bibliographic Data
(52) Canadian Patent Classification (CPC):
  • 183/24
(51) International Patent Classification (IPC):
  • B01D 53/04 (2006.01)
  • B01D 53/047 (2006.01)
  • C01B 21/04 (2006.01)
(72) Inventors :
  • MUNZNER, HEINRICH (Germany)
  • HORBEL, HUGO (Germany)
  • KNOBLAUCH, KARL (Germany)
  • KORBACHER, WERNER (Germany)
  • PETERS, WERNER (Germany)
  • JUNTGEN, HARALD (Germany)
(73) Owners :
  • BERGWERKSVERBAND G.M.B.H. (Not Available)
(71) Applicants :
(74) Agent: FETHERSTONHAUGH & CO.
(74) Associate agent:
(45) Issued: 1980-08-26
(22) Filed Date: 1975-08-25
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): No

(30) Application Priority Data:
Application No. Country/Territory Date
P 24 41 447.9 Germany 1974-08-29

Abstracts

English Abstract






ABSTRACT OF THE DISCLOSURE

A process and and arrangement for converting air into
a gaseous mixture enriched with nitrogen includes passing a
first stream of air through an adsorber which preferentially
adsorbs oxygen from the admitted first stream and thereby dis-
charges a second stream of a gaseous mixture having a higher pro-
portion of nitrogen as compared with the first stream. Control
means are positioned in the second stream to measure the oxygen
content of the continuously discharging second stream and termi-
nates the discharge of the same when the oxygen content thereof
exceeds a predetermined value. Residual amounts of gaseous mix-
ture are then evacuated from the adsorber. An additional adsorber
is connected with the first-mentioned adsorber to form a first stage
with each adsorber being alternately charged with air in a cyclic-
al operation. Additional stages are connected in series so that
the effluent nitrogen-enriched gaseous mixture can be further en-
riched to a final desired value.


-1-


Claims

Note: Claims are shown in the official language in which they were submitted.


The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:


1. A process for converting a gaseous mixture including
an initial proportion of nitrogen and oxygen into an enriched gaseous
mixture having an increased proportion of nitrogen, comprising the
steps of passing a first stream of the gaseous mixture through an
adsorber having a filling of a carbon-containing molecular sieve
material, the first stream being conveyed at a space velocity of
at least 0.01 and at most 0.04 volumes of gaseous mixture per
volume of molecular sieve material per second over a time period
of at least 40 and at most 80 seconds; adsorbing the oxygen prefer-
entially from the admitted first stream so that a second stream
discharges from said adsorber which contains a higher proportion
of nitrogen and at most a predetermined proportion of oxygen; con-
tinuing the discharge of said second stream from said adsorber until
the oxygen in said second stream exceeds said predetermined pro-
portion; thereupon terminating the discharge of said second stream;
and evacuating residual gaseous mixture from said adsorber.


2. A process as defined in claim 1, wherein the step of
passing said first stream through said adsorber is performed at a
pressure of at least 2 and at most 5 bar.


3. A process as defined in claim 1, wherein the step of
adsorbing is performed by utilizing molecular sieve coke as the
sieve material.




17

4. A process as defined in claim l, wherein the step
of evacuating said residual gaseous stream from said adsorber is
performed at a pressure of at most 70 and at least 20 torr.


5. A process as defined in claim 1, wherein the step of
evacuating residual gaseous mixture is performed by removing the
latter in a direction opposite to the flow of said first stream
passing through said adsorber.


6. A process as defined in claim l, wherein the step
of terminating the discharge of the second stream includes the step
of monitoring the percentage by volume of the oxygen in said sec-
ond stream.


7. A process as defined in claim l, and further compris-
ing repeating said steps with an additional adsorber, said steps of
passing said first stream, adsorbing, discharging said second stream
and terminating the discharge thereof being performed with said
first mentioned adsorber while said step of evacuating is simul-
taneously performed with said additional adsorber and vice versa.


8. A process as defined in claim 7; and further compris-
ing the step of connecting said first-mentioned and additional ad-
sorber in parallel to form a first stage, said adsorbers having a
common inlet and a common outlet.


9. A process as defined in claim 8; and further compris-
ing the step of establishing equilibrium between said adsorbers of
said first stage after one of said adsorbers has been evacuated.




18


10. A process as defined in claim 8, wherein the step
of terminating the discharge of the second stream includes the
step of monitoring the oxygen in said second stream being dis-
charged from said common outlet, said monitoring step including
measuring at least 0.5 and at most 4% by volume of the oxygen
prior to terminating the discharge thereof.



11. A process as defined in claim 8; and further
comprising the step of connecting another pair of adsorbers
constituting a second stage in series with said first stage, said
other pair having a common inlet which is connected to said
common outlet of said first stage.



12. A process as defined in claim 11; and further
comprising the step of feeding residual gaseous mixture of said
second stage back to said common inlet of said first stage.



13. A process as defined in claim 11, wherein the step
of terminating the discharge of the second stream includes the
step of monitoring the oxygen in said second streams being re-
spectively discharged from said common outlets of said first and
second stages, said monitoring steps including measuring at least
4 and at most 10% by volume of the oxygen in said common outlet
of said first stage prior to terminating the discharge thereof
and measuring at least 0.1 and at most 5% by volume of the oxygen
in said common outlet of said second stage prior to terminating
the discharge thereof.




19




14. A process as defined in claim 11; and further
comprising the step of dimensioning said other pair of adsorbers
to contain about one half of the volumetric capacity of said
first stage.



15. An arrangement for converting a gaseous mixture
including an initial proportion of nitrogen and oxygen into an
enriched gaseous mixture having an increased proportion of
nitrogen, comprising adsorbing means including a filling of
molecular sieve material; admitting means for passing a first
stream of the gaseous mixture through said adsorbing means at a
space velocity of at least 0.01 and at most 0.04 volumes of
gaseous mixture per volume of molecular sieve material per second
over a time period of at least 40 and at most 80 seconds, said
adsorbing means adsorbing the oxygen preferentially from the
admitted first stream so that a second stream discharges from
said adsorbing means which contains a higher proportion of nit-
rogen and at most a predetermined proportion of oxygen; means for
continuing the discharge of said second stream from said ad-
sorbing means until the oxygen in said second stream exceeds said
predetermined proportion; means for thereupon terminating the
discharge of said second stream; and means for evacuating
residual gaseous mixture from said adsorbing means.



16. An arrangement as defined in claim 15, wherein
said admitting means passes said first stream through said ad-
sorbing means under a pressure of at least 2 and at most 5 bar.




17. An arrangement as defined in claim 15, wherein
said material comprises molecular sieve coke.



18. An arrangement as defined in claim 15 wherein
said evacuating means removes said residual gaseous stream from
said adsorbing means at a pressure of at most 70 and at least 20
torr.



19. An arrangement as defined in claim 15, wherein
said evacuating means removes said residual gaseous mixture in a
direction opposite to the flow of said first stream passing
through said adsorbing means.



20. An arrangement as defined in claim 15, wherein
said terminating means includes means for monitoring the per-
centage by volume of the oxygen in said second stream.



21. An arrangement as defined in claim 15, wherein
said adsorbing means comprises a pair of adsorbers; said means
for admitting, continuing the discharge of said second stream and
for terminating the discharge thereof being performed with one of
said adsorbers while said evacuating means is simultaneously
evacuating the other of said adsorbers and vice versa.




22. An arrangement as defined in claim 21; and further
comprising connecting means for connecting said adsorbers in
parallel to form a first stage, said pair of adsorbers having
a common inlet and a common outlet.




21



23. An arrangement as defined in claim 22; and further
comprising equilibrium means for establishing equilibrium between
said pair of adsorbers of said first stage after one of said
adsorbers has been evacuated.

24. An arrangement as defined in claim 22, wherein
said means for terminating the discharge of the second stream
includes means for monitoring the oxygen in said second stream
being discharged from said common outlet, said monitoring means
including means for measuring at least 0.5 and at most 4% by
volume of the oxygen prior to terminating the discharge thereof.

25. An arrangement as defined in claim 22; and further
comprising additional connecting means for connecting another
pair of adsorbers constituting a second stage in series with said
first stage, said other pair having a common inlet which is
connected to said common outlet of said first stage.

26. An arrangement as defined in claim 25; and further
comprising means for feeding residual gaseous mixture of said
second stage back to said common inlet of said first stage.

27. An arrangement as defined in claim 25, wherein said
means for terminating the discharge of the second stream includes
means for monitoring the oxygen in said second streams being respect-
tively discharged from said common outlets of said first and second
stages, said monitoring means including means for measuring at least
4 and at most 10% by volume of the oxygen in said common outlet of

22


said first stage prior to terminating the discharge thereof and
means for measuring at least 0.1 and at most 4% by volume of
the oxygen in said common outlet of said second stage prior to
terminating the discharge thereof.


28. An arrangement as defined in claim 25, wherein said
other pair of adsorbers contains about one half of the volumetric
capacity of said pair of adsorbers of said first stage.




23

Description

Note: Descriptions are shown in the official language in which they were submitted.


~ 10~421


Gaseous mixtures enriched in nitrogen are widely used in
industry for their inert propertles, and particularly as a protect-
ive gas in preventing explositions. -
The invention relates generally to the conversion of a
gaseous mixture having two components into a mixture having an in-
creased proportion of one of the components, and more particularly
the nitrogen-enrichment of air by selective adsorption of oxygen.
In the prior art, nitrogen is obtained by the fractional
distillation of liquid air. This process is very costly and is
generally undesirable. The equipment is very expensive to operate
and uses a relatively great expenditure of energy.
It has also already been proposed to recover nitrogen- ~ -
enriched air utilizing an adsorption process employing siliceous
or carbon-containing adsorption agents and involving the use of ~ -
relatively high temperature or pressure changes during adsorption
and desorption. Certain silicates, for example, zeolites, are
effective for preferably adsorbing nitrogen from its mixture with
oxygen so that, by conducting air through a zeolite-filled adsorber, ~ -
the remaining gas is effectively enriched as regards its nitrogen
content. me regeneration of the zeolite, however, requires a con-
siderable outlay for energy and apparatus. Additionally, the zeolites
are completely effective only when used with dry air since they are
hydrophilic.
Accordingly, the present invention overcomes disadvantages
of the prior art by providing an economical process and an ar~ange-
ment for converting a gaseous mixture having an initial proportion
of a first component into an enriched mixture having an increased
proportion of the first component.




,~ _ _

10~44Zl

Further the yield of nitrogen from air is hereby
increased in a si~,ple and efficient manner.
Additionally the proportion of contaminants such as
water is reduced from the enriched mixture.
In keeping with these advantages and othe~swhich will -
become apparent hereinafter, one feature of the invention is to
pass a first stream of a gaseous mixture having an initial pro-
portion of a first component through an adsorber filled with a
carbon-containing molecular sieve material such as molecular
sieve coke, hereinafter referred to as M-coke. ;
The M~coke preferentially adsorbs a second component from
the admitted first stream so that a second stream discharges from
the adsorber which contains a higher proportion of the first compon-
ent. The effluent second stream continues to discharge from the ad-
sorber while its proportion of the second component continues to
increase as the capacity of the M~coke to adsorb additional amounts
of second co~,ponent in the incoming gaseous mixture decreases. When
the second component exceeds a predetermined proportion, the dis-
charge of the second stream is terminated and the residual gaseous
mixture in the adsorber is evacuated.
In the particular case where the starting gaseous mixture
is air, which contains 79% by volume of nitrogen and 21% by volume
of oxygen, the oxygen will be preferentially adsorbed by the M-coke
and the effluent second stream will be nitrogen-enriched. me pro-
cess and the arrangement for converting a gaseous mixture into an
enriched mixture will be described with reference to the recovery
of nitrogen from air. It is to be explicitly understood, however,

that the description is not intended to limit the invention in
any nanner.
Accordingly, the present invention provides a process

for converting a gaseous mixture including an initial proportion


~ 3

~o~4~Z~ ~:

of nitrogen and oxygen into an enriched gaseous mixture having an increased `
proportion of nitrogen, comprising the steps of passing a first stream of
the gaseous mixture throu h an adsorber having a filling of a carbon-contain-
ing molecular sieve material, the first stream being conveyed at a space
velocity of at least 0.01 and at most 0.04 volumes of gaseous mixture per
volume of molecular sieve material per second over a time period of at
least 40 and at most 80 seconds; adsorbing the oxygen preferentially from
the admitted first stream so that a second stream discharges from said
adsorber which contains a higher proportion of nitrogen and at most a
predetermined proportion of oxygen; continuing the discharge of said second
stream from said adsorber until the oxygen in said second stream exceeds
said predetermined proportion; thereupon terminating the discharge of said
second stream; and evacuating residual gaseous mixture from said adsorber.
In another aspect, the present invention provides an arrangement
for converting a gaseous mixture including an initial proportion of nitrogen
and oxygen into an enriched gaseous mixture having an increased proportion
of nitrogen, comprising adsorbing means including a filling of molecular
sieve material; admitting means for passing a first stream of the gaseous
mixture through said adsorbing means at a space velocity of at least 0.01 and
at most 0.04 volumes of gaseous mixture per volume of molecular sieve
material per second over a time period of at least 40 and at most 80 seconds
said adsorbing means adsorbing the oxygen preferentially from the admitted
first stream so that a second stream discharges from said adsorbing means
which contains a hi~her proportion of nitrogen and at most a predetermined
proportion of oxygen; means for continuing the discharge of said second -
stream from said adsorbing means until the oxygen in said second stream
exceeds said predetermined proportion; means for thereupon terminating the
discharge of said second stream; and means for evacuating residual gaseous
mixture from said adsorbing means.
Thus, the air has been strongly reduced, resulting in an effluent
nitrogen-enriched gaseous mixture whose final proportion of nitrogen can be

increased if desired, as will be explained herein. The effluent:mixture
~ - 4 -
~' ~ ,

- 10844Zl

also surprisingly contains other contaminants as well, such as unadsorbed
traces of oxygen, carbon dioxide, argon and moisture. However, through
well-known fine cleaning techniques, virtually 100% pure nitrogen can be
reclaimed from the mixture.
The arrangement and process for converting the gaseous mixture
into an enriched mixture thus overcomes the prior art drawbacks and achieves
the aforementioned objects in a novel manner. The nitrogen is recovered
from the starting nitrogen-oxygen gaseous mixture with great efficiency and
economy of operation.
The M-coke, referred to above and described in our copending
Canadian application serial no. 191,472 (now Canadian Patent 1,033,342) and
in United States Patent No. 3,801,513, is capable of adsorbing oxygen
molecules even from a relatively fast flowing stream of air. It is
especially preferable if the average pore size of the M-coke be from at the
least 0.2 and at most 0.4 millimlcrons (2-4 Angstroms) and particularly
0.3 millimicrons. The stream passing throu~h the M-coke should flow at a
speed so that the air takes about one minute to travel through an adsorbing
chamber. To test the effectiveness of the coke, air flowing at a speed
of about 3 cm/sec should be passed through a one liter sample of the M-
coke. Thereupon, the residual mixture remc~ining in the test sample is
evacuated and should contain an oxygen content of at least 35% by volume.
The feature of terminating the discharge of the second stream
when the proportion of oxygen increases to a predetermined




- 4a -

4Z~

1 value is very advantageous in improving the nitrogen yield. As pre-
viously noted the oxygen content of the effluent gaseous mixture
may increase from at least 0.02% by volume to 10% or more by volume.
Therefore, limiting values of oxygen ~ by volume are preselected.
Depending upon the degree of nitrogen enrichment desired, limiting
values of 0.02, 2, 4, etc. by volume of oxygen may be selected.
Another feature of the invention is that the pressures --
required for evacuating the M-coke from an adsorption chamber are
not critical. Commercially available vacuum pumps capable of generat-
ing pressures down to 100 torr may be used. Pressures in the neigh- ~ -
borhood of 70-20 torr are easily obtainable by such pumps, and are
therefore especially recommended.
Another feature of the invention is to admit the starting
air (under overpressures of 2-5 bar) into the adsorption chamber
containing the M-coke at an inlet portion, and to evacuate the re-
sidual gases remaining therein after termination of the flow of the
effluent nitrogen-enriched mixture from the same inlet portion where
the starting air is admitted into the adsorption chamber but in the
opposite direction. It has been found that the moisture in the start-

ing air tends to congregate at the inlet portion of the chamber sothat, by evacuating the chamber so that residual gases are removed
in a direction opposite to the incoming air flow, the accumulated
moisture is for the most part eliminated. This overcomes the prior
art problem of removing the residual gases so that the moisture is
conducted all the way through the M-coke.
The feature of pressurizing the air flow to overpressures
of 2- 5 bar is also advantageous in increasing the adsorption capa-
city of the M-coke. It has been found that lower or higher pressures
decrease the effectiveness of the M-coke, although these lower or
higher pressures are not intended to be excluded from possible use.

~()8~42~

1 To further improve the adsorption effectiveness of the
M-coke, the velocity of the air stream must be controlled. We have
found it especially advantageous if the gaseous mixture has a space
velocity of 0.01-0.04 volumes of gas per volume of M-coke per second
over a time period of at least 40 and at most 80 seconds. The velo-
city may be controlled by adjustable nozzles in conventional manner.
It is further advantageous to partially or entirely pre-
fill a previously partially or entirely evacuated adsorber with a
gas having a nitrogen component so as to prevent an excessively
turbulent reaction when the air first passes through the adsorber.
The gas may come from an external source, or preferably the residual~` -
gases remaining in the pores or interstices of the M-coke after
termination of the discharging of the second nitrogen-enriched
stream of an additional adsorber may be used.
To achieve this object, equilibrium valves located be-
tween the adsorbers and a vacuum pump which creates an underpress-
ure are used to conduct the residual gases having a nitrogen com-
ponent from one of the adsorbers into a freshly evacuated adsorber.
The two adsorbers are connected in parallel and operate
in alternating fashion to produce a continuous effluent stream. Of
course, other pairs of adsorbers can be connected in parallel like
the first-mentioned pair to improve the nitrogen yield and the
continuity of operation.
Still another feature of the invention is to connect two
pairs of adsorbers in series so that the effluent nitrogen-enriched
stream of the first pair or stage is used as the starting gas for
the second pair or stage. Thus, the proportion of nitrogen component
by volume in the final end product will increase.
In addition, residual gases from the second stage in their
entirety may be fed back to initially load the adsorbers of the first

~08~f~


l stage, since the residual gases have been surprisingly found to
have less oxygen than the residual gases remaining in the inter-
stices of the respective adsorbers of the first stage. Typically,
: 10%-20% of the residual gases remaining in the interstices of the
adsorber are replaced by the residual gases of the second stage.
The novel features which are considered as characteristic
for the invention are set forth in particular in the appended claims.
The invention itself, however, both as to its construction and its
method of operation, together with additional objects and advantages
thereof, will be best understood from the following description of
specific embodiments when read in connection with the accompanying
j drawing.
FIG. 1 is a diagrammatic view of a pair of adsorbers ac-
cording to the present invention; and
FIG. 2 is a diagrammatic view of two pairs of adsorbers
according to the present invention.
Inasmuch as the recovery of nitrogen from air is of such
great technical importance, the invention will be described with
reference to such enrichment. However, it is to be explicitly under-

stood that this is not intended to limit the invention in any mannerand that the invention is generally applicable to the conversion of
a gaseous mixture having at least two components so as to obtain an
enriched gaseous mixture having an increased proportion of one of
the components.
Discussing jointly the method and the apparatus illustrat-
ed in FIG. l for obtaining an enriched gaseous mixture having an in-
creased proportion of one of the components, it will be seen that
reference numeral l identifies an adsorber which is at least partial- -
ly filled with a carbon-containing molecular sieve, and particularly
molecular sieve coke, hereinafter referred to as M-coke.

10844Zl

1 Such a sieve is capable of preferentially adsorbing
that component of a gaseous mixture which has the smaller mole-
cular size. With reference to air, the oxygen molecules will be
preferentially adsorbed since they have a smaller molecular size
than nitrogen molecules. Details of a process for the production of
a carbon-containing molecular sieve capable of separating different
gases, particularly nitrogen and oxygen, are known in the art.
Admitting means is provided for passing a first stream
of the gaseous mixture (e.g. air) through adsorber 1. The admitting
10 means comprises a blower 3 and an inlet valve 7.
Discharging means is provided for issuing a second stream
from the adsorber 1. The first stream has already undergone adsorp-
tion, and the thereby resulting second stream has a higher proportion
of one of the components (nitrogen). The discha-ging means comprises
an outlet valve 9.
Control means 12a is provided in the path of the dis-
charging second stream. The control means 12a measures the propor-
tion of the adsorbed component (oxygen) therein. As will be explained
herein, the control means is operative to terminate the discharge of
20 the second stream whenever the quantity of adsorbed component (oxygen)
exceeds a predetermined value.
Reference numeral 2 identifies an analogous additional
adsorber containing M-coke and~ together with adsorber 1, comprises
a first stage. The interiors of adsorbers 1 and 2 are in communica-
tion at their respective upper portions by equilibrium valve 12 and
at their respective lower portions by equilibrium valve 11.
~ he admittlng means communicates w1th adsorber 2 by means




-8-



.: . ............................. :
,
,

10844Zl ~ :

1 of inlet valve 8; the discharging means also permits the second
i~ stream issuing from adsorber 2 by means of outlet valve 10 to be
measured by control means 12a.
Evacuating means comprise a vacuum pump 4 and evacuation
valves 5 and 6 associated with adsorbers 1 and 2, respectively. The
evacuating means is operative for removing or desorbing residual
gaseous mixture from the adsorbers 1 and 2.
The alternating cycle operation of adsorbers 1 and 2 will
now be described with particular reference to FIG. 1: Firstly, eva-
cuation valve 5 is opened and all remaining valves 6 - 12 are closed~.
Upon activation of pump 4, the interior of adsorber 1 is evacuated
and maintained at an underpressure. Next, equilibrium valves 11 and
12 are opened so that the residual gaseous mixture contained in the
interstices or pores of the M-coke in adsorber 2 will flow into ad-
sorber 1. The equilibrium valves are preferably kept open for a
time period of at least 2 and at most 3 seconds. After this time
period is over, equilibrium valves 11 and 12 are closed.
Next, the inlet valve 7 and other valve 9 are opened and
blower 3 is actuated to pass a first stream of air through adsorber
1 to be adsorbed therein. The resulting adsorbed second stream con- -
tains a higher proportion of nitrogen as compared with its initial
proportion in the air. The preferred time period for the first stream
to pass through adsorber 1 is about one minute, or about 1 cubic
meter air per 1 cubic meter of M-coke.
As the M-coke within adsorber 1 becomes more and more
loaded with oxygen, its effectiveness decreases. The escaping second
!
~ stream will, at first, have a very small percentage by volume of
:~
oxygen mixed with the desired nitrogen gas and, subsequently, the
percentage by volume of oxygen will increase. The control means 12a
~` 30 is an oxygen-measuring device which is located in the discharging
:'~

_9_
~,
, ............................................... .
7~

~~
10844Zl

J 1 second stream to measure when the quantity of oxygen exceeds a
predetermined value. In one application, the initial percentages
'~ of oxygen is about 0.5% by volume and the upper limit is about 4
by volume. When this upper predetermined value is reached, inlet
- valve 7 and the outlet valve 9 are closed, thus terminating the
; discharge of the second stream from adsorber 1.
During this time between the aforementioned opening and
closing of the inlet value 7 -- that is, during the loading of ad-
sorber 1 and the obtaining of a first fraction of gaseous mixture
enriched with nitrogen -- the evacuation valve 6 is opened and
pump 4 reactuated to a final pressure of about 35 torr so that the
interior of adsorber 2 is evacuated and maintained at underpressure.
Moreover, evacuation valve 6 is then closed, and equilibrium valves
11 and 12 opened so as to permit the residual gaseous mixture con-
tained in the interstices of the M-coke in adsorber 1 (after valves
7 and 9 have been closed) to flow into adsorber 2. Equlibrium
valves 11 and 12 are then closed and inlet and outlet valves 8 and
~ 10 opened so as to permit the admitting means to pass another
: stream of air through adsorber 2.
As described above for adsorber 1, adsorber 2 discharges
a second stream of nitrogen-enriched gaseous mixture towards control
means 12a. As before, when the upper predetermined value is obtained,
inlet valve 8 and outlet valve 10 are closed, thus terminating the
discharge of the second stream from adsorber 2. Thereupon, evacua-
tion valve 5 is opened, and inlet valve 7 and outlet valve 9 are
closed so that the above-described cycle will beging again.
In this manner, adsorbers 1 and 2 alternately discharge
a nitrogen-enriched gaseous mixture. They may work independently of
each other, or together in the above-described cyclical fashion, or
with other non-illustrated adsorbers so as to produce a continuous
i, . '
, -10- . -
. ' , ' . ,,


: .. .. ~ . , : :, , . .. :
~ : . :. :
.. .. . .

lV844Zl
1 effluent stream.
Turning now to FIG. 2, the first stage of adsorbers 1
and 2 is connected in series with a second stage of adsorbers 21
and 22, that is the effluent nitrogen-enriched stream is used as
the starting gas in the subsequent second stage. Except as noted
below, the second stage is exactly identical with the first in that
equilibrium valves 31 and 32 correspond to valves 11 and 12, inlet
valves 27 and 28 correspond to valves 7 and 8, outlet valves 29 and
30 correspond to valves 9 and 10, evacuation valves 25 and 26 cor-

respond to valves 5 and 6, pump 24 corresponds to pump 4, and con-
trol means 32a corresponds to control means 12a.
A gasometer or gas storage container 13 is located inter-
mediate the stages to collect the effluent gaseous mixture discharged
; from the adsorbers of the first stage and supply the second stage. -~
In order to further increase the yield, the residual gas of the second
stage which contains less oxygen as a rule than the residual gases
respectively remaining in the interstices of the adsorbers 1 and 2
is fed back to the first stage by means of feedback valves 14 and
15. Another gasometer 33 is used to collect the residual gases of
, 20 the second stage alternately evacuated from adsorbers 21 and 22.
The operation of the two stages is as follows: As before,
adsorber 1 is evacuated, equilibrium valves 11 and 12 are opened,
` residual gas remaining within the interstices of adsorber 2 flows
into adsorber 1, and equilibrium valves 11 and 12 are closed after
about 2 or 3 seconds. Feedback valve 14 and outlet valve 9 are then
opened, and the residual gas collected in gasometer 33 is conveyed
to and through adsorber 1 for a time period of about 4 - 6 seconds.
Feedback valve 14 is then closed, and inlet valve 7 is opened so
that the blower 3 passes an additional air stream through adsorber
1. The additional air stream pushes the already nitrogen-enriched
.
,
` -11-
., .
' : '

10844Zl
-.

1 residual gas out of the interstices of adsorber 1. The additional
air stream is discharged from adsorber 1 and is collected down-
stream in gasometer 13. As soon as the proportion of oxygen in the
- effluent stream exceeds a predetermined value, e.g., the proportion
rises from 0.5 to 4% by volume, the inlet and outlet valves 7 and
9 are closed.
As before, during this time, adsorber 2 has been evacuat-
ed so that now by opening equilibrium valves 11 and 12, any residual
gas remaining in adsorber 1 is conveyed to adsorber 2. Then, feed-

back valve 15 and outlet valve lO are opened, and the remainder of
the residual gas collected in gasometer 33 is conveyed to and through
adsorber 2. Then, feedback valve 15 is closed, and inlet valve 8 is
opened so that the blower 3 forces an additional stream of air
through adsorber 2 past control means 12a towards gasometer 13. In
this manner, adsorbers 21 and 22 are alternately loaded with a first
fraction of effluent nitrogen-enriched mixture and, in a manner
analogous to the first stage, generate a second fraction of effluent
mixture even ~ore greatly enriched than the first fraction. The
control means 32a is therefore set to measure a lower proportion of
oxygen content than control means 12a. For example, the second frac-
tion may rise from 0.1 to 1% by volume of oxygen before the dis-
charging operation is terminated by closing the inlet and outlet
valves 27, 29, or 28, 30 respectively. The second fraction further
contains traces of moisture, carbon dioxide, carbon monoxide, and
argon.
The two stages operate with continuously driven gas and
vacuum pumps and valves. The actuation of the pumps and valves is
directly controlled by the control means 12a and 32a in convention-
al manner. Instead of such control means, the valves and pumps can -
be operated by a timing device which actuates the devices by a pre-

" ~

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.

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1 selected time sequence program.
Since both stages have gasometers which have a variable
volume capacity, both stages may be operated independently of each
other. Since the effluent gas of the first stage is already nitro-
gen-enriched, the required volume of M-coke in the second stage is
considerably less. As diagrammatically shown in FIG. 2, adsorbers
21 and 22 are smaller than adsorbers 1 and 2 in order to illustrate
that the entire volume of M-coke required in the second stage is ~-
about 2/3 to 1/2 of the volume required in the first stage (e.g.
10 10 cubic meters of M-coke). The primary supply source upstream of
the first stage should have a capacity which corresponds at least
to the full capacity of the adsorbers of the first stage.
The following Examples are given in order to more fully
illustrate the invention but are in no manner to be considered as
limiting the scope thereof.
Example 1
Two adsorbers filled with M-coke, and each having a capa-
s city of 0.5 m3, are alternately charged with air(21% by volume of
oxygen, 450 ppm carbon dioxide, dew point 16C) in a cyclic opera-
20 tion. Each adsorber is in turn evacuated and the time to achieve
equilibrium between the adsorbers is 2.5 seconds. Pressure is built
up in 4 seconds, and the time for the air to alternately pass through
each adsorber is 53.5 seconds. Each adsorber is evacuated or desorb-
ed in 57.5 seconds, and the adsorption pressure at the end of the
adsorption phase is 770 torr. The effluent gaseous mixture at the
end of the adsorption phase has an oxygen content of 3% by volume.
At the end of the evacuation of the adsorbers, a vacuum of 35 torr
is obtained. For loading the adsorbers, 57.5 m of air at NTP is
required. Flowing out of each adsorber, 25 m3 of nitrogen-enriched
30 mixture at NTP having an average content of 1.6% by volume of oxygen,

. . .

-13-
'' .
.
.. . .

i0844Zl
:

1 10 ppm carbon dioxide, and a dew point of - 35C is generated.
From the desorption or evacuation phase of operation, 32.5 m3 of
gaseous mixture having an average oxygen content of 36.4% is re-
moved. This evacuated mixture also contains traces of carbon di-
oxide and moisture.
Example 2
Two adsorbers filled with M-coke, and each having a ca-
pacity of 0.5 m , are alternately loaded and unloaded with air
; under an adsorption pressure of 2 bar. At the end of the evacua-
tion or desorption phase, an end vacuum pressure of 57 torr is
realized. For loading purposes, 112.6 m3 of air at NTP are required.
The predetermined end limting value of the effluent nitrogen-en-
riched mixture is 1.5% by volume of oxygen. The capacity of the
effluent mixture is 42.3 m3 at NTP with an average oxygen content
of 0.9% by volume of oxygen, 13 ppm carbon dioxide, dew point
- 36C. The capacity of the evacuated mixture is 76.8 m3 at NTP
with an average oxygen content of 32.9% by volume.
Example 3
; Four adsorbers filled with M-coke, and each having a
capacity of 0.25 m3 comprise two pairs of adsorber stages. The
i first pair of adsorbers is alternately loaded and unloaded with
; air; the second pair is connected in series with the first pair so
that the adsorbers of the second pair are alternately loaded and
unloaded with the effluent nitrogen-enriched gaseous mixture of
the first pair by means of a gasometer placed between the two pairs
and serving as a storage place. Both pairs or stages are controlled
in synchronism. Equilibrium time between adsorbers is 2.5 seconds.
Pressure is built up in 4 seconds, and the time that the adsorbers
are loaded with gas is 53.5 seconds. Evacuation time is 57.5 seconds.
;` 30 The adsorption pressure at the end of the adsorption phase in the

.' '~. .
:~ .,

-14-
. .: .:
.. - . ,. . . . ~ ~ .

. 10~44Z~ :
. ~.,.
l first stage is 780 torr; the final adsorption pressure in the
second stage is 765 torr. In both stages, a 34 torr vacuum is
created at the end of the evacuation phase. The end limiting value
for the oxygen content in the effluent gas of the first stage is

., .
; 7% by volume; the end value for the oxygen content of the effluent
gas of the second stage is 0.4% by volume. For loading the first
stage, 24.2 m of air at NTP are required. The residual gaseous
mixture of the first stage amounts to 13.7 m at NTP with an oxygen
,~
content of 37.1%. The effluent enriched gaseous mixture of the
second stage, that is the end product, has an oxygen content of
0.1% by volume and an overall volume of 10.5 m at NTP.
Example 4
Two adsorbers filled with M-coke, and each having a ca-
pacity of 0.5 m3, are alternately charged and unloaded with an
~,~ oxygen-nitrogen mixture. For purposes of loading 50 m3 of boiler
exhaust gases which contains 93% by volume of nitrogen and 7% by
volume of oxygen are used. The effluent nitrogen-enriched gaseous
~, mixture has a capacity of 14 m at NTP with an average oxygen con-
tent of 0.7% by volume. From the desorption step, 36 m3 of residual
gases at NTP are removed with an oxygen content of 8.8% by volume.
The end limiting value of oxygen is 1.2% by volume. ;~
It will be understood that each of the elements described
:,.~, . .
.~ above, or two or more together, may also find a useful application

in other types of processes and arrangements differing from the

;~ types des~ribed above.

~ While the invention has been illustrated and described as

,r.;
embodied in a process and an arrangement for the conversion of a
gaseous mixture, it is not intended to be limited to the details
shown, since various modifications and structural changes may be
made without departing in any way from the spirit of the present




-15-


, , . - ~ ,

-`` 1084421


invention .




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3 0


-16-

Representative Drawing

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Administrative Status

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Administrative Status

Title Date
Forecasted Issue Date 1980-08-26
(22) Filed 1975-08-25
(45) Issued 1980-08-26
Expired 1997-08-26

Abandonment History

There is no abandonment history.

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $0.00 1975-08-25
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
BERGWERKSVERBAND G.M.B.H.
Past Owners on Record
None
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Drawings 1994-04-07 2 34
Claims 1994-04-07 7 253
Abstract 1994-04-07 1 31
Cover Page 1994-04-07 1 20
Description 1994-04-07 16 737