U.S. patent number 3,797,261 [Application Number 05/142,299] was granted by the patent office on 1974-03-19 for single-stage fractionation of natural gas containing nitrogen.
This patent grant is currently assigned to Linde Aktiengesellschaft. Invention is credited to Friedrich Juncker, Johannes Kranz, Martin Streich, Heiner Tanz, Gerd Vollrath.
United States Patent |
3,797,261 |
Juncker , et al. |
March 19, 1974 |
SINGLE-STAGE FRACTIONATION OF NATURAL GAS CONTAINING NITROGEN
Abstract
Separation of natural gas containing nitrogen into a
low-nitrogen fraction and a high-nitrogen fraction is achieved in a
single distillation column in which reflux is provided by expanding
the high-nitrogen fraction with the performance of work and using
the resulting refrigeration to condense vapor in the upper section
of the column while additional reflux is provided by vaporizing a
recycle medium in heat exchange relation with vapor in the column.
Incoming natural gas is passed in heat exchange relation with
liquid in the column bottom, further cooled and expanded into the
middle section of the column. A helium-rich fraction may be
separated from the high-nitrogen fraction.
Inventors: |
Juncker; Friedrich
(Bergen-Enkheim, DT), Kranz; Johannes (Bad Vilbel,
DT), Streich; Martin (Nieder-Eschbach, DT),
Tanz; Heiner (Sprendlingen, DT), Vollrath; Gerd
(Steinheim/M, DT) |
Assignee: |
Linde Aktiengesellschaft
(Wiesbaden, DT)
|
Family
ID: |
5770782 |
Appl.
No.: |
05/142,299 |
Filed: |
May 11, 1971 |
Foreign Application Priority Data
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|
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May 12, 1970 [DT] |
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2022954 |
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Current U.S.
Class: |
62/622;
62/927 |
Current CPC
Class: |
F25J
3/029 (20130101); C07C 7/04 (20130101); F25J
3/0257 (20130101); F25J 3/0233 (20130101); F25J
3/0209 (20130101); C07C 7/04 (20130101); C07C
9/04 (20130101); F25J 2200/02 (20130101); F25J
2200/74 (20130101); F25J 2205/02 (20130101); F25J
2270/66 (20130101); Y10S 62/927 (20130101); F25J
2270/60 (20130101); F25J 2240/12 (20130101); F25J
2270/06 (20130101); F25J 2270/02 (20130101); F25J
2200/50 (20130101); F25J 2270/12 (20130101); F25J
2235/60 (20130101) |
Current International
Class: |
C07C
7/04 (20060101); C07C 7/00 (20060101); F25J
3/02 (20060101); F25j 001/02 (); F25j 003/02 () |
Field of
Search: |
;62/22,23,24,27,28,39,41,40,38 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Yudkoff; Norman
Assistant Examiner: Purcell; Arthur F.
Attorney, Agent or Firm: Garbo; Paul W.
Claims
What is claimed is:
1. A process for the separation of natural gas containing nitrogen
into a low-nitrogen fraction and a high-nitrogen fraction in a
single distillation zone which comprises expanding at least the
greater part of said high-nitrogen fraction with the performance of
work, using the resulting refrigeration to condense vapor of the
upper section of said distillation zone to provide reflux in said
distillation zone, and providing additional reflux below the
aforesaid reflux by vaporizing a closed recycle liquefied gas in
indirect heat exchange relation with vapor of said distillation
zone after said recycle gas has been passed in indirect heat
exchange relation with liquid while the said liquid is at the
bottom of said distillation zone.
2. The process of claim 1 wherein the distillation zone is
maintained at a pressure in the range of about 10 to 35 ata.
3. The process of claim 1 wherein the nitrogen content of the
natural gas is over 20 percent by volume and the expansion of
high-nitrogen fraction with the performance of work is conducted in
several stages with the resulting refrigeration of each stage being
used to condense vapor at different levels of the upper section of
the distillation zone.
4. The process of claim 1 wherein the natural gas containing
nitrogen is passed in indirect heat exchange relation with liquid
at the bottom of the distillation zone, then with the expanded
high-nitrogen fraction and again with liquid at an intermediate
level of said distillation zone, is expanded to a pressure in the
range of about 10 to 35 ata and is discharged into the middle
section of said distillation zone.
5. The process of claim 1 wherein the recycle liquefied gas is
methane, the nitrogen content of the natural gas is at least 40
percent by volume, and the distillation zone is maintained at a
pressure of about 28 ata.
6. The process of claim 1 wherein the natural gas containing
nitrogen also contains helium and a helium-rich fraction is
recovered by partially condensing nitrogen in the vapor withdrawn
from the top of the distillation zone in two condensation stages,
for refrigeration for the first of said stages being provided by
evaporating at reduced high pressure liquid withdrawn from the top
of said distillation zone and the refrigeration for the second of
said stages being provided by the high-nitrogen fraction expanded
with the performance of work to nearly atmospheric pressure.
7. The process of claim 4 wherein the nitrogen content of the
natural gas is over 20 percent by volume, the expansion of
high-nitrogen fraction with the performance of work is conducted in
two stages, the discharge pressure of the second of said stages
being nearly atmospheric, and the resulting refrigeration of each
of said stages is used to condence vapor at different levels of the
upper section of the distillation zone.
8. The process of claim 7 wherein the natural gas containing
nitrogen also contains helium and a helium-rich fraction is
recovered by partially condensing nitrogen in the vapor withdrawn
from the top of the distillation zone in two condensation stages,
the refrigeration for the first of said stages being provided by
evaporating at reduced high pressure liquid withdrawn from the top
of said distillation zone and the refrigeration for the second of
said stages being provided by the high-nitrogen fraction expanded
with the performance of work to nearly atmospheric pressure.
Description
BACKGROUND OF THE INVENTION
This invention relates to a process for separating natural gas
containing nitrogen into a low-nitrogen and a high-nitrogen
fraction by low-temperature distillation in a single column.
Depending on the location of the well, natural gas contains
different percentages of nitrogen, carbon dioxide, and heavy
hydrocarbons. If the contents of non-combustible components are
substantial, it becomes necessary or expedient to separate the
non-combustible components prior to transportation or utilization.
The customary method for removal of nitrogen is the distillation of
natural gas at low temperatures. However, this method is subject to
difficulties due to the carbon dioxide in the natural gas.
Carbon dioxide has a triple point of -56.6.degree.C and a very low
solubility at low temperatures. Therefore, depending on the method,
the carbon dioxide may become solid at low temperatures. In known
processes, carbon dioxide is therefore separated before the natural
gas enters the low-temperature plant. This separation is costly
since, for instance, special carbon dioxide adsorbers with
regeneration facilities must be provided, and additional energy is
required.
The process of copending application Ser. No. 849,439, filed Aug.
12, 1969, by Martin Streich, avoids carbon dioxide removal by
separating the natural gas containing nitrogen into a high-nitrogen
and a low-nitrogen fraction prior to two-stage distillation as
such. This process is advantageous if the natural gas contains
little nitrogen, i.e. up to approximately 20 percent. However, with
this process too, the low-pressure column must remain free of
carbon dioxide and low in heavy hydrocarbons.
It is the object of this invention to provide a process for the
separation of natural gas containing nitrogen into a low-nitrogen
and a high-nitrogen fraction by single-stage distillation without
the aforesaid shortcomings and limitations regarding carbon dioxide
removal.
SUMMARY OF THE INVENTION
According to this invention, the reflux required for the
distillation is produced by work-performing expansion of at least
the greater part of the high-nitrogen fraction and using the
refrigeration produced by this expansion and by vaporization of a
recycle medium to condense vapor in the column.
Advantageously, the pressure for this process is between 10 and 35
ata (atmospheres absolute) and a pressure of approximately 28 ata
is preferred. Methane is a preferred recycle medium. The process
becomes particularly favorable if the high-nitrogen fraction is
expanded in several stages with inter-stage heating. In the known
manner, the natural gas entering the plant at high pressure is
utilized to heat the column sump before it is expanded into the
middle section of the distillation column. In an advantageous form
of this process, the natural gas is also brought into heat exchange
relation with vapor in the lower section of the column before being
expanded into the column; thus, the reflux conditions in the column
are improved.
The process of the invention is very well suited for recovering a
helium-rich fraction from natural gas containing a worthwhile
percentage, say over 0.1 percent, of helium. For this purpose, the
head product of the distillation, which contains helium, is
enriched in two nitrogen condensing stages; in the first stage
fractional condensation is carried out by heat exchange with
high-nitrogen fraction boiling at high pressure, and in the second
stage with cold gaseous high-nitrogen fraction at approximately
atmospheric pressure from the work-performing expansion of the
high-nitrogen fraction. Refrigeration for the second stage can also
be supplied by nitrogen evaporating at low pressure. If necessary,
the low-nitrogen liquid fraction from the sump of the distillation
column may be pumped to higher pressure before being vaporized and
heated to ambient temperature.
BRIEF DESCRIPTION OF THE DRAWINGS
Further advantages of the invention will become apparent from the
description of the accompanying drawings of which:
FIG. 1 is a flow diagram of an embodiment of the invention
utilizing two-stage expansion of the high-nitrogen fraction;
and
FIG. 2 is similar to FIG. 1 with additional features for helium
recovery.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the process shown in FIG. 1, natural gas enters the
low-temperature plant through line 1 after removal of moisture in a
drier (not shown). The natural gas contains about 43% by volume of
nitrogen and 56% by volume of methane, the remainder consisting of
heavy hydrocarbons 0.4%m helium 0.4% and carbon dioxide 0.2%. The
gas pressure is 55 ata.
In heat exchanger 2, the natural gas is cooled by counter-current
flow to the separation fractions. Then it flows through vaporizer 3
in the bottom of distillation column 4 and thus it provides part of
the vapor upflow required in column 4.
The natural gas is then further cooled by flowing through subcooler
5 and coil 6 in the lower section of column 4 where it produces
more vapor upflow and thus improves the rectification conditions.
Finally, the subcooled natural gas is expanded through expansion
valve 7 into the middle section of column 4 to a pressure of 28
ata.
In distillation column 4, the natural gas is separated into a
high-nitrogen mixture at the head of column 4 and a low-nitrogen
mixture at the bottom of column 4. At the head of column 4, the
high-nitrogen mixture is withdrawn in gaseous state through line 8,
somewhat heated in heat exchanger 9, and expanded in
work-performing turbine 10 to a medium pressure of about 6 ata.
Then it is reheated in heat exchanger 11 against condensing vapors
of the high-nitrogen mixture, further expanded in turbine 12 to
about atmospheric pressure and once again heated in heat exchanger
13 against condensing vapors of the high-nitrogen mixture. After
further heating in heat exchangers 9, 5, and 2, the high-nitrogen
fraction is finally available at the plant outlet at ambient
temperature.
Liquid high-nitrogen mixture from the column head can be expanded
through line 14 into storage vessel 15 where it is separated into a
liquid and a gaseous phase. The gaseous phase is withdrawn through
line 18 and fed through valve 19 into the discharge line of turbine
10. The liquid phase is withdrawn through line 16 and expanded
through expansion valve 17 into the discharge line of turbine 12.
This is necessary only in case of a sudden need for refrigeration
in column 4, for instance in case of a sudden rise in pressure in
column 4. The liquid from storage vessel 15 will then supply the
necessary additional refrigeration.
The low-nitrogen mixture is withdrawn from the sump of column 4
through line 20, pressurized by pump 21 to the inlet pressure of 55
ata of the natural gas and heated in heat exchanger 2 to ambient
temperature.
If the average nitrogen content of the natural gas is about 40 to
50percent by volume, the refrigeration supplied by expansion of the
gas in turbines 10, 12 is not enough to produce sufficient reflux
for the complete fractionation of the natural gas. Therefore, a
recycle medium is provided to improve the reflux conditions. The
preferred recycle medium or gas is methane; however a mixture of
nitrogen and light hydrocarbons may also be used. In compressor 22,
the recycle gas is compressed from a pressure of about 2 ata to a
pressure which is higher than the pressure of distillation column
4.
Since, in the present example, the recycle medium is also to take
refrigeration from the returning low-nitrogen fraction in line 20,
it is compressed to 55 ata. After flowing through after-cooler 23,
it is cooled in heat exchanger 2 against itself and the returning
fractions. Then, in heat exchanger 24, the recycle gas heats the
liquid in the column sump, and in heat exchangers 5 and 9 it is
subcooled. After expansion to 2 ata in expansion valve 25, it
evaporates in heat exchanger 236, at least to a great extent.
Consequently, with heat exchanger 26, the recycle medium also
produces reflux in column 4. In heat exchangers 9, 5 and 2, the
recycle gas is reheated to approximately ambient temperature. Since
expansion of the high-nitrogen fraction in work-performing turbines
10 and 12 supplies a lot of refrigeration, the recycle gas may be
discharged from the low-temperature plant at a relatively low
temperature. In compressor 22, the recycle gas may then be
compressed cold, i.e., with less energy consumption. Preferably,
the recycle gas is fed into compressor 22 at a temperature of about
-35.degree.C since, at that temperature, it is not necessary to use
special materials for compressor 22.
FIG. 2 illustrates the process with the additional recovery of
helium. Identical plant components have been marked with identical
reference numerals from FIG. 1 and the process will be described
only insofar as it differs from the process shown in FIG. 1. As
compared to FIG. 1, the head of distillation column 4 is provided
with an additional condenser 27 where the high-nitrogen vapor
mixture rising from heat exchanger 11 is extensively liquefied. The
gas withdrawn above condenser 27 through line 28 already contains 5
to 10 percent by volume of helium. In heat exchanger 29, this vapor
mixture is further concentrated by partial condensation to 80 to 90
percent by volume of helium. The helium vapor concentrate is
withdrawn through line 30, while the nitrogen condensate is
returned to column 4 by line 32.
The concentration of helium is accomplished in two stages. The
refrigeration for first-stage condenser 27 is supplied by
evaporating the high-nitrogen liquid mixture which is withdrawn
from column 4 through line 14, expanded to 24 ata in expansion
valve 31 and discharged into condenser 27. The resulting
high-nitrogen vapor mixture is then conducted through turbines 10
and 12 as already described for FIG. 1. The refrigeration for the
concentration second-stage heat exchanger 29 is supplied by the
cold high-nitrogen vapor mixture from turbine 12, which is
subsequently heated to ambient temperature as described for FIG. 1.
The refrigeration for the second concentration stage may also be
supplied by high-nitrogen liquid mixture evaporating at low
pressure.
Heat exchangers 24, 3, 6, 26, 13 and 11 may also be located outside
column 4 as plate heat exchangers.
The process of this invention avoids very low temperatures for the
natural gas and for the low-nitrogen product fraction. Furthermore,
the natural gas evaporates at high pressure. Thus, it is possible
to tolerate higher percentages of heavy hydrocarbons in the natural
gas without entailing deposits and plugging. Conditions are similar
where carbon dioxide is concerned. The carbon dioxide passes
through the plant without being deposited anywhere. The costly
pre-purification of the natural gas is thus avoided.
* * * * *