U.S. patent number 3,688,513 [Application Number 05/030,208] was granted by the patent office on 1972-09-05 for production of nitrogen and argon-free oxygen.
Invention is credited to Hartmut Voigt, Main-Unterliederbach, DE, Martin Streich, Urseler Weg 44, Republic of DE.
United States Patent |
3,688,513 |
|
September 5, 1972 |
PRODUCTION OF NITROGEN AND ARGON-FREE OXYGEN
Abstract
Nitrogen- and argon-free oxygen is recovered from air by a
three-stage rectification system in which the third stage is
maintained at an absolute pressure of 0.8 to 1.1 atmosphere while
the pressure of the second stage is higher by only 0.3 to 0.5
atmosphere. A side stream containing argon flows from the second
rectifying stage to the third stage which yields a head product
enriched in argon. This head product is pumped back into the upper
portion of the second stage. High-purity oxygen is recovered from
the sumps of the second and third rectifying stages.
Inventors: |
Martin Streich, Urseler Weg 44
(Nieder-Eschbach, Federal), Republic of DE (N/A), Hartmut
Voigt (Heimchenweg 82, Frankfurt am), Main-Unterliederbach,
DE (N/A) |
Family
ID: |
5733336 |
Appl.
No.: |
05/030,208 |
Filed: |
April 20, 1970 |
Foreign Application Priority Data
|
|
|
|
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May 6, 1969 [DE] |
|
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19 22 956.2 |
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Current U.S.
Class: |
62/646; 62/654;
62/924 |
Current CPC
Class: |
F25J
3/04212 (20130101); F25J 3/04303 (20130101); F25J
3/04454 (20130101); F25J 2220/50 (20130101); F25J
2215/56 (20130101); Y10S 62/924 (20130101); F25J
2245/58 (20130101); F25J 2245/42 (20130101); F25J
2200/50 (20130101); F25J 2235/42 (20130101); F25J
2200/54 (20130101); F25J 2200/90 (20130101); F25J
2200/34 (20130101); F25J 2250/20 (20130101) |
Current International
Class: |
F25J
3/04 (20060101); F25j 003/00 (); F25j 003/02 ();
F25j 003/04 () |
Field of
Search: |
;62/22,23,24,27,28,29,30,38,26,41 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Norman Yudkoff
Assistant Examiner: Arthur F. Purcell
Attorney, Agent or Firm: Paul W. Garbo
Claims
What is claimed is:
1. A process for the recovery of substantially nitrogen-and
argon-free oxygen by rectification of air in three rectifying
stages, which comprises separating air into a nitrogen fraction and
an oxygen-enriched fraction in the first rectifying stage, passing
entirely said nitrogen fraction to the top portion of the second
rectifying stage and said oxygen-enriched fraction to the middle
portion of said second stage, passing an argon-containing stream
from the bottom portion of said second stage to the middle portion
of the third rectifying stage, pumping entirely an argon-rich head
product from said third stage to said second stage at a level
between the introduction of said nitrogen fraction and said
oxygen-enriched fraction, the pressure of said third stage being
lower by 0.3 to 0.5 atmosphere than the pressure of said second
stage, discharging a nitrogen head product from said second stage,
and recovering said oxygen from the bottom portions of said second
and third stages.
2. The process of claim 1 wherein there is indirect heat exchange
between the nitrogen fraction of the first rectifying stage and the
sump liquid of the third rectifying stage and between the
oxygen-enriched fraction of said first stage and the argon-rich
head product of said third stage.
3. The process of claim 1 wherein the third rectifying stage is
maintained at an absolute pressure in the range of about 0.8 to 1.1
atmosphere.
4. The process of claim 1 wherein there is indirect heat exchange
between the nitrogen fraction of the first rectifying stage and a
recycle stream from the middle portion of the second rectifying
stage.
5. The process of claim 4 wherein the third rectifying stage is
maintained at an absolute pressure in the range of about 0.8 to 1.1
atmosphere.
Description
This invention relates to a process for the recovery of nitrogen-
and argon-free oxygen by multi-stage rectification of air. In the
first rectifying stage, compressed air cooled to the dew point is
separated into nitrogen and an oxygen-enriched fraction. The second
stage yields a sump product of oxygen which is practically free of
argon and nitrogen. A side product of the second rectifying stage,
containing argon, is separated in the third stage into an
argon-free sump product and an argon-enriched head product. The
argon-free oxygen product is withdrawn partly from the sump of the
second rectifying stage and partly from the sump of the third
rectifying stage.
It is a known practice, in these and other rectifying processes, to
apply the principle of the heat pump and thus use the feed air as a
working fluid. For the recovery of technical grade oxygen and
nitrogen, modern production plants are using two-stage rectifying
processes. More than two stages are usually provided if one of the
components of the air is to be recovered at particularly high
purity, or if one of the rare gas components of air is to be
separated as an additional product.
The work expenditure for separating air into oxygen and nitrogen is
five to ten times greater than theoretically calculated with a
reversible separation process. This is due to losses during
compression, heat leak, less than perfect heat exchange, pressure
drop across pipes and valves, as well as losses in the rectifying
columns. During the last few decades, entropy studies led to
numerous improvements in the design of compressors, turbines, heat
exchangers, and rectifying columns, as well as process
improvements. For instance, Lachmann suggested blowing part of the
feed air into the second-stage rectifying column at a pressure
slightly above atmospheric, thus reducing the work expenditure. It
was also Lachmann's idea, to vent from the second-stage rectifying
column an amount of vapor equivalent to 10-15percent of the feed
air volume. This measure is taken not for conservation of energy
but for product purity since the venting removes a considerable
amount of the undesired argon, however not without loss of
product.
Already a few decades ago, the development of air separation for
the recovery of nitrogen and oxygen led, after limitation of some
of the irreversibilities, to the so-called medium pressure process
which operates with two rectifying stages: a medium pressure and a
low pressure stage. Since this process is being applied so
frequently and the corresponding plants are being built again and
again, practically without changes, they have been labelled
"classic" in the industry. The fact that these plants continue to
be copied signifies that the industry has become resigned to the
necessary energy consumption.
To recover part of the argon initially contained in the air, this
classic process, as known, was modified to a three-stage rectifying
process. In this process, the pressures maintained in the medium
and low pressure stages are the same as in the classic process. The
pressure in the argon rectifying stage corresponds approximately to
the pressure in the low pressure stage. The argon recovery is about
30 to 60 percent. A mixture of about 45 percent argon, 50 percent
oxygen, and 5 percent nitrogen leaves the head of the argon column.
The energy consumption for this process is about the same as for
the classic process which is considered a special advantage.
According to this invention, the energy consumption for air
separation can be lowered considerably by using, in the third
rectifying stage, a rectifying pressure which is lower by 0.3 to
0.5 atm (atmosphere) than the pressure in the second rectifying
stage, and by withdrawing the head product of the third rectifying
stage and pumping it into the top portion of the second rectifying
stage at a point which is already low in oxygen concentration.
Consequently, contrary to the classic two-stage process and the
conventional three stage process, the first rectifying stage also
can operate at a lower pressure. The compression pressure of the
feed air can be 1.5 atm lower than usual. The energy saving, based
on gaseous product, is approximately 10 percent and remains
significant, even after mathematical conversion to the product data
of the classic process. Compared to the conventional three-stage
process, oxygen losses are reduced considerably. It is particularly
surprising that, in spite of the reduced rectifying pressures, an
argon-free oxygen product of 99.5 percent purity is recovered.
Although, in the third rectifying stage, a mixture containing argon
is separated into an argon-free and an argon-rich fraction, --which
is in itself a known practice --this measure does not serve for the
recovery of argon but for faciliating the discharge of argon from
the second rectifying stage and is a means of lowering the pressure
level.
BRIEF DESCRIPTION OF THE DRAWING
The single FIGURE of the accompanying drawing is a schematic flow
diagram illustrating a preferred embodiment of the invention.
DESCRIPTION OF PREFERRED EMBODIMENT
The first rectifying stage is represented by column 1, the second
stage by column 2, and the third stage by column 3. The major
portion of the compressed, pre-cooled air enters rectifying column
1 through line 6 and is separated into nitrogen and an
oxygen-enriched fraction. The sump of the second rectifying column
2 yields a practically argon- and nitrogen-free oxygen product. A
side stream 9, containing argon, is withdrawn from rectifying
column 2 and separated in rectifying column 3 into an argon-free
oxygen sump product and an argon-rich head product. The argon-free
oxygen product is withdrawn partly through line 10 from the sump of
column 2 being desirably passed in heat exchange with the head
product of column 1 in heat exchanger 5, and partly through line 11
from the sump of column 3.
The rectifying pressure in column 3 is lower by 0.3 to 0.5 atm than
the pressure in column 2. The head product of column 3 is withdrawn
through line 4 and introduced by pump 12 into the top portion of
column 2 at an upper level which is already low in oxygen
concentration.
The drawing also shows how the heat input and heat withdrawal at
column 3, and the heat input to column 2 can be achieved in an
advantageous manner. There is indirect heat exchange between the
sump liquid of column 3 and the head product from column 1 in heat
exchanger 5A, and between the head product of column 3 and the sump
product of column 1 in heat exchanger 5B, as well as between the
sump liquid of column 2 and the air feed in heat exchanger 5C. It
is expedient to operate heat exchanger 5C at the sump of column 2
by means of a control device so that the sump product just remains
free of nitrogen. This results in increased argon concentration in
side stream 9.
It is furthermore advantageous to operate column 3 at an absolute
pressure between 0.8 and 1.1 atm.
ILLUSTRATIVE EXAMPLE
In a system conforming to the drawing and designed to process air
fed at the rate of 100 nm.sup.3 /hr (cubic meters per hour measured
at normal conditions), an absolute pressure of 1 atm is maintained
in column 3, while the absolute pressure in column 2 is 1.5 atm and
4.2 atm in column 1. The pressure is determined directly above the
sump liquid in each column.
Feed air, cooled to a temperature of -176.degree. C and at an
absolute pressure of 4.24 atm, is supplied to the process via line
6. A partial air stream of 13 nm.sup.3 /hr is passed via line 7
through a conventional reheater R and heat exchanger 5G to
expansion engine 8 and fed to column 2 at a temperature of
-168.degree. C. After passing through heat exchanger 5C at the sump
of column 2, the main air stream enters column 1 at -178.degree. C.
From the head of column 1, 32.8 nm.sup.3 /hr of overhead vapor,
after heat exchange with the head product of column 2 in heat
exchanger 5D, flows into the upper portion of column 2. The inlet
temperature is -189.degree. C. From the sump of column 1, liquid at
a rate equivalent to 54.2 nm.sup.3 /hr, after heat exchange with
the head product of column 2 in heat exchanger 5E, flows to column
2; a part of this stream equivalent to 32 NM.sup.3 /hr flows
through condenser 5B of column 3 before entering column 2 at
approximately the center, whereas the remainder of the stream
equivalent to 22.2 nm.sup.3 /hr enters a column 2 at a higher
level. At the head of column 1, a temperature of -181.degree. C is
maintained. This is accomplished by heat exchange of the head
product with the sump liquid of column 3 in heat exchanger 5A and
by heating a partial head product recycle stream of 4.8 nm.sup.3
/hr with liquid from column 2 in heat exchanger 5F.
From column 2, a side stream of 14.2 nm.sup.3 /hr, containing
argon, is fed via line 9 to column 3. In column 3, a head
temperature of -185.5.degree. C and a sump temperature of
-183.degree. C are maintained. A head product of 2 nm.sup.3 /hr
from column 3 is pumped into the upper portion of column 2 by way
of line 4 and pump 12. Liquid product is withdrawn at a rate
equivalent to 7.8 nm.sup.3 /hr from the sump of column 2 by line
10, and at a rate of 12.2 nm.sup.3 /hr as 99.5 percent pure oxygen
from column 3 by line 11. The argon-contaminated nitrogen leaves
overhead of column 2 at a rate of 80 nm.sup.3 /hr. The oxygen
product is recovered by way of lines 10 and 11 at -183.degree. C
and atmospheric pressure, and the nitrogen at -178.degree. C and at
an absolute pressure of 1.2 atm after leaving heat exchanger
5G.
The pressures of the process may be varied within the given limits.
This process however is also suitable for application of the method
of balancing refrigeration losses in the classic process by
work-performing nitrogen expansion. The recovery of pure nitrogen
is not shown in the flow diagram or described in the process
example but could be done in the conventional manner without
essentially changing the pressure conditions.
* * * * *