U.S. patent number 3,729,943 [Application Number 05/032,613] was granted by the patent office on 1973-05-01 for process for separation of ternary gaseous mixtures by rectification.
This patent grant is currently assigned to L'Air Liquide Societe Anonyme pour L'Etude et L'Exploitation des. Invention is credited to Pierre Petit.
United States Patent |
3,729,943 |
Petit |
May 1, 1973 |
PROCESS FOR SEPARATION OF TERNARY GASEOUS MIXTURES BY
RECTIFICATION
Abstract
The present invention concerns a process in which a gaseous
fraction is withdrawn from an intermediate level of a main
rectification and subjected to a rectification in an auxiliary
zone, the liquid fraction obtained in this auxiliary zone being
returned to the said intermediate level of the main rectification.
The improvement according to the invention concerns the
condensation of the said withdrawn gaseous fraction which is
effected at the bottom and possibly simultaneously at the top of
the said auxiliary zone by the vaporization of the liquid fractions
originating from the main rectification. The process is applicable
to the separation by rectification of a mixture formed of at least
three constituents, two of which are in major proportions, the
boiling point of the constituent in small proportions being between
the boiling points of the two constituents in major proportions and
being closer to that of the less volatile of these two
constituents. For example, the invention is applicable to a
two-stage air-separation plant with an argon side column.
Inventors: |
Petit; Pierre
(Chatenay-Malabry, FR) |
Assignee: |
L'Air Liquide Societe Anonyme pour
L'Etude et L'Exploitation des (Paris, FR)
|
Family
ID: |
9033486 |
Appl.
No.: |
05/032,613 |
Filed: |
April 28, 1970 |
Foreign Application Priority Data
Current U.S.
Class: |
62/643;
62/924 |
Current CPC
Class: |
B01D
3/143 (20130101); F25J 3/04684 (20130101); F25J
3/04412 (20130101); F25J 3/04678 (20130101); F25J
3/04672 (20130101); Y10S 62/924 (20130101) |
Current International
Class: |
B01D
3/14 (20060101); F25J 3/04 (20060101); F25j
001/00 (); F25j 003/04 (); F25j 003/02 () |
Field of
Search: |
;62/22,23,24,27,28,29,31,39,41 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Yudkoff; Norman
Assistant Examiner: Purcell; Arthur F.
Claims
What I claim is :
1. In a method for the separation of a mixture of gases by
rectification in first and second vertically elongated
rectification zones, said mixture comprising at least three
components two of which are present in relatively major proportions
and a third of which is present in a relatively minor proportion,
said first zone being at a higher pressure than said second zone,
in which liquid withdrawn from said first zone is expanded and
introduced into said second zone, and in which fluid is withdrawn
from an intermediate level of said second zone and is introduced
into an auxiliary vertically elongated rectification zone and
liquid from the bottom of said auxiliary zone is returned to an
intermediate level of said second zone, and in which the top of
said auxiliary zone is cooled by indirect heat exchange with liquid
from one of said first and second zones while said minor component
is withdrawn in gaseous phase from the top of said auxiliary zone;
the improvement comprising cooling the bottom of said auxiliary
zone by passing a cooling liquid from one of said first and second
zones through the bottom of said auxiliary zone and in indirect
heat exchange with the bottom of said auxiliary zone independently
of liquid in heat exchange with the top.
2. A method as claimed in claim 1, in which said liquid for cooling
the bottom of said auxiliary zone is withdrawn from the bottom of
said second zone.
3. A method as claimed in claim 1, in which said liquid for cooling
the bottom of said auxiliary zone is withdrawn from an upper
portion of said first zone.
4. A method as claimed in claim 1, in which said mixture of gases
is air and said gaseous phase withdrawn from the top of said
auxiliary zone is enriched in argon.
Description
The present invention relates to an improved process by which a
mixture composed of at least three constituents is separated by
rectification.
The present invention is more specifically concerned with a process
which makes possible an increase in the extraction yield of a
constituent which is in small proportions in a mixture of at least
three constituents, of which two are in major proportions, the
boiling point of this constituent present in small proportions
being between the boiling points of the two constituents in major
proportions and being closer to that of the less volatile of these
two constituents.
The present invention is particularly applicable to the separation
of air by rectification and has for its object a process permitting
the rate of extraction of argon to be increased.
The present invention is also concerned with any installation for
carrying the above processes into effect.
It is known to be possible to separate air into its constituent
elements by means of two successive rectification zones, for
example, at medium pressure and low pressure. Thus, the air,
purified beforehand from traces of CO.sub.2 and water which it
contains, is brought to its dew point for the pressure in question
in a first rectification zone, called the medium pressure zone. A
liquid fraction rich in oxygen is collected at the bottom of this
zone and a liquid fraction poor in oxygen is collected at the top
thereof. At least a part of each of these two collected liquid
fractions is sent into a second zone, called the low pressure zone.
The fraction with low oxygen content is introduced into the top of
this second zone, while the rich fraction is introduced
approximately at the middle of this second zone.
In the conventional processes, some of the coldness which is
necessary for keeping the installation cold can be obtained by
expanding a part of the supply air stream and by blowing this into
the second rectification zone at an intermediate level of the said
zone.
The amount blown in is generally between 5 and 15 percent by
volume, relatively to the volume of supply air. If the amount blown
in is too high, however, this causes firstly an appreciable
decrease in yield of oxygen in the separating operation and
secondly an almost total impossibility of separating the argon.
Different processes for improving the extraction yield have been
proposed.
It is thus possible to utilize the cold units liberated by the
vaporization of a part of the liquid oxygen collected at the bottom
of the said second zone for condensing, in a condenser at the top
of an auxiliary column, a part of a fraction withdrawn from an
intermediate level of the said second zone, this condensed part
being reintroduced into the said second zone at the same
intermediate level. This process is relatively satisfactory but
nevertheless it involves a high energy expenditure. In effect, to
condense a mixture containing essentially argon in the auxiliary
condenser, it is necessary for the vaporization pressure of the
oxygen to be lower than that of the mixture undergoing
condensation, and this has the disadvantage of requiring, for
example, the presence of an extraction blower, with the dangers of
leakages and of introducing air, due to working under vacuum, or of
noticeably increasing all the pressures in the said two zones of
the main rectification.
The present invention consists in an improvement in existing
processes and installations, which permits the aforesaid
inconveniences to be obviated and the cost price and also the
energy consumption to be reduced to the greatest possible degree.
The improvement forming the subject of the present invention makes
possible an improvement in the extraction yield of a constituent
which is in small proportions in a mixture; it is possible to
operate without any special installation being required.
The present invention has for its object an improved separation
process by rectification, making possible an increase in the
extraction yield of a constituent which is in small proportions in
a mixture of at least three constituents, two of which are in major
proportions, the boiling point of this constituent in small
proportions being between the boiling points of the two
constituents in major proportions and being closer to that of the
less volatile of these two constituents, in which a gaseous
fraction is withdrawn from an intermediate level of a main
rectification and subjected to a rectification in an auxiliary
zone, the liquid fraction obtained in this auxiliary zone being
returned to the said intermediate level of the main rectification,
and in which the condensation of the said withdrawn gaseous
fraction is effected at the bottom and simultaneously at the top of
the said auxiliary zone by the vaporization of liquid fractions
originating from the main rectification.
According to one embodiment of the present invention, the said
withdrawn gaseous fraction is at least partly condensed at the
bottom of the said auxiliary zone by the vaporization of at least a
part of the liquid fraction collected at the bottom of the second
zone of the said main rectification.
According to another embodiment of the present invention, the said
withdrawn gaseous fraction is at least partly condensed at the
bottom of the said auxiliary zone by the vaporization of at least a
part of the liquid fraction collected at the top of the first zone
of the said main rectification.
According to another embodiment of the present invention, the
withdrawn gaseous fraction is at least partly condensed at the top
of the said auxiliary zone by the vaporization of at least a part
of the liquid fraction collected at the top of the first zone of
the said main rectification.
According to yet another embodiment of the present invention, the
said withdrawn gaseous fraction is at least partly condensed at the
top of the said auxiliary zone by the vaporization of at least a
part of the liquid fraction collected at the top of the first zone
of the said main rectification, and simultaneously by the
vaporization of at least a part of the liquid fraction collected at
the bottom of the first zone of the said rectification.
According to one embodiment of the present invention, the
concentration in the withdrawn gaseous fraction of the said
constituent in small proportions, relatively to the least volatile
constituent, is the highest possible, and the concentration of the
most volatile constituent is the lowest possible.
According to one embodiment of the present invention, the liquid
fractions originating from the said zones of the main rectification
are, after at least partial vaporization in the auxiliary
rectification zone, preferably returned into the second zone of the
said main rectification.
According to yet another embodiment of the present invention, at
least one of the liquid fractions originating from the said zones
of the main rectification is, after at least partial vaporization
in the auxiliary rectification zone, preferably expanded in a
turbine so as to assure a supply of cold to the installation.
Preferably, the said mixture of at least three constituents is air,
from which it is desired to extract the argon (which is found
therein in small proportions), of which the boiling point is
between that of the nitrogen and that of the oxygen and is closer
to that of oxygen, which is the least volatile.
However, it must be understood that the present invention is
applicable to any mixture, whether it is gaseous or liquid at
ambient conditions as regards temperature and pressure.
The present invention is also concerned with any installation for
carrying out the process according to the present invention.
The invention will be best understood from reading the following
description and the accompanying drawings, which show different
embodiments of the present invention as non-limiting examples,
applicable to the case of the production of argon.
FIGS. 1 and 2 represent different embodiments of the present
invention. For the purpose of simplification the similar parts of
these figures bear the same references.
FIG. 1 represents an embodiment in which the low pressure oxygen is
at least partly vaporized at the bottom of the auxiliary column and
the liquid with high oxygen content from the medium pressure column
is possibly partly vaporized at the top of the auxiliary
column.
FIG. 2 shows an embodiment in which the medium pressure liquid
nitrogen is at least partly vaporized at the bottom of the
auxiliary column.
These embodiments are obtained by means of a double rectification
column comprising two zones, which are a medium pressure zone 1 and
a low pressure zone 2, and an auxiliary rectifier column 4. The
air, previously purified from traces of CO.sub.2 and water which it
contains, is brought in the vicinity of its dew point temperature
for the medium pressure in question into this medium pressure
column 1 through the pipe 5. The liquid fraction rich in oxygen
which is obtained at the bottom leaves this said column 1 through
the pipe 12, while the liquid fraction rich in nitrogen obtained at
the top of the column 1 leaves the latter through the pipe 13. All
or part of the liquid fractions drawn off from the column 1 are
then introduced into the low pressure column 2.
The auxiliary rectifier column 4 comprises a condenser 6 at the top
and a condenser 7 at the bottom.
The liquid oxygen is drawn off from the double rectifier column
through the pipe 14 and the gaseous nitrogen is drawn off through
the pipe 10. At an intermediate level of the column 2, a gaseous
fraction is withdrawn through the pipe 8; this fraction is supplied
to the auxiliary rectifier column 4, in which the oxygen which it
contains is condensed, and then the fraction thus condensed is
returned through the pipe 9 to the low pressure zone.
The level at which the withdrawal takes place is a function of the
operating conditions: pressure, nature of the constituents of the
mixture, etc. In the case of low pressure rectification of air, the
withdrawal takes place at the level where the argon concentration
is the highest possible and the nitrogen concentration is the
lowest possible. In a conventional installation comprising
approximately 60 plates, the withdrawal is generally effected at
the level of the 15th plate.
A much larger proportion of the argon in the air is withdrawn
through the pipe 11 than is the case with the known processes.
Instead of recovering 70 percent of the argon present in the air,
as is generally the case in the known processes, it is found, for
example, in the case of FIG. 1, that more than 78 percent of the
argon present in the air are recovered. A much better separation
between oxygen and nitrogen is also obtained.
In FIG. 1, the liquid fraction rich in oxygen and leaving the
column 1 through the pipe 12 is introduced by way of the pipe 112
into the condenser 6, in which at least a fraction of the fraction
rich in oxygen is vaporized, whereafter this fraction rich in
oxygen is conveyed through the pipe 212 into the low pressure
column 2. Another part of the cold supply necessary for the
rectification is obtained in the condenser 7 by vaporizing a part
of the liquid oxygen fraction collected in the column 2.
In FIG. 2, the fraction rich in oxygen and leaving the column 1 by
way of the pipe 12 is brought directly into the column 2, another
part being supplied through the pipe 112 to the condenser 6, in
which it is at least partly vaporized, and then by way of the pipe
212 to the column 2.
A part of the fraction rich in nitrogen, which is obtained in the
column 1, is conducted through a pipe 113 into the condenser 7,
which it leaves, ac least partly vaporized, by way of the pipe
213.
It is obvious that the invention is not limited to the embodiment
which has been illustrated and that it is capable of numerous
variations available to the person skilled in the art, depending on
the proposed applications, and without thereby departing from the
scope of the invention.
* * * * *