U.S. patent number 3,818,714 [Application Number 05/231,984] was granted by the patent office on 1974-06-25 for process for the liquefaction and subcooling of natural gas.
This patent grant is currently assigned to Linde Aktiengesellschaft. Invention is credited to Volker Etzbach, Wolfgang Forg, Peter Grimm.
United States Patent |
3,818,714 |
Etzbach , et al. |
June 25, 1974 |
**Please see images for:
( Certificate of Correction ) ** |
PROCESS FOR THE LIQUEFACTION AND SUBCOOLING OF NATURAL GAS
Abstract
A process for the liquefaction and subcooling of natural gas
with a Claude closed refrigerating cycle comprising compressing
gaseous cycle medium; cooling resultant compressed gaseous cycle
medium; dividing cooled compressed gas into two streams;
engine-expanding one stream; and cooling the other stream with the
engine-expanded stream to such an extent that said other stream
becomes partially liquefied after a subsequent throttle expansion
thereof; the improvement comprising employing as the cycle medium,
a mixture of nitrogen and methane.
Inventors: |
Etzbach; Volker (Munich,
DT), Forg; Wolfgang (Grunwald, DT), Grimm;
Peter (Munich, DT) |
Assignee: |
Linde Aktiengesellschaft
(Wiesbaden, DT)
|
Family
ID: |
5800552 |
Appl.
No.: |
05/231,984 |
Filed: |
March 6, 1972 |
Foreign Application Priority Data
Current U.S.
Class: |
62/612 |
Current CPC
Class: |
F25J
1/0214 (20130101); F25J 1/025 (20130101); F25J
1/004 (20130101); F25J 1/0045 (20130101); F25J
1/005 (20130101); F25J 1/0249 (20130101); F25J
1/0219 (20130101); F25J 3/0257 (20130101); F25J
1/0037 (20130101); F25J 3/0209 (20130101); F25J
1/0022 (20130101); F25J 1/0055 (20130101); F25J
3/0233 (20130101); F25J 1/0288 (20130101); F25J
1/0279 (20130101); F25J 2215/04 (20130101); F25J
2205/04 (20130101); F25J 2200/02 (20130101); F25J
2245/02 (20130101); F25J 2200/74 (20130101); F25J
2220/64 (20130101); F25J 2210/06 (20130101); F25J
2290/10 (20130101) |
Current International
Class: |
F25J
1/00 (20060101); F25J 3/02 (20060101); F25J
1/02 (20060101); F25j 001/00 (); F25j 001/02 ();
F25j 003/00 () |
Field of
Search: |
;62/9,11,23,24,27,28,40,38 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Kleemenko, One Flow Cascade Cycle, Progress in Refrigeration
Science and Technology, Vol. 1 (1960)..
|
Primary Examiner: Yudkoff; Norman
Assistant Examiner: Purcell; Arthur F.
Attorney, Agent or Firm: Millen, Raptes & White
Claims
What is claimed is:
1. In a process for the liquefaction and subcooling of natural gas
with a Claude closed refrigerating cycle comprising compressing
gaseous cycle medium; dividing cooled compressed gas into two
streams; engine-expanding one stream; cooling the other stream with
the engine-expanded stream to such an extent that said other stream
becomes partially liquefied after a subsequent throttle expansion
thereof and passing resultant partially liquefied stream in
indirect heat exchange relationship with liquid natural gas to
subcool the liquid natural gas so that it remains substantially in
the liquid phase after being expanded to the pressure of a storage
tank;
the improvement comprising employing as the cycle medium, a mixture
of nitrogen and methane.
2. A process according to claim 1, wherein the nitrogen molar
concentration in the cycle medium is at least 20 percent.
3. A process according to claim 1, wherein the nitrogen molar
concentration in the cycle medium is at least 40 percent.
4. A process according to claim 1 further comprising separating the
natural gas from CO.sub.2, H.sub.2 O and heavy hydrocarbons;
separating a nitrogen enriched stream from resultant purified
natural gas, the nitrogen content of said enriched stream being at
least as large as that of said cycle medium and feeding said
nitrogen enriched stream into the Claude cycle in sufficient
amounts to provide makeup cycle medium.
5. A process according to claim 1 further comprising precooling
said one stream prior to engine expanding thereof with a
refrigeration precooling cycle based on a cycle medium comprising a
mixture of methane and propane ethane.
6. A process according to claim 5, wherein said precooling
refrigeration cycle is conducted in a single stage.
7. A process according to claim 5, said precooling refrigeration
cycle comprising a precooling compressor and a cooler downstream of
the precooling compressor, and further comprising with drawing a
mixture of gas and liquid from said cooler, said liquid containing
predominantly higher-boiling hydrocarbons and said gas being rich
in lower-boiling components; separating the gas and the liquid;
said separated gas and liquid streams in heat exchange with liquid
evaporating at the suction pressure of the compressor, totally
condensing said gas rich in lower-boiling components, the resultant
liquid being expanded to the suction pressure of the compressor,
whereby the total condensation is effected by the evaporation of
the thus-formed, expanded liquid.
8. A process according to claim 6, said precooling refrigeration
cycle comprising a precooling compressor and a cooler downstream of
the precooling compressor, and further comprising with drawing a
mixture of gas and liquid from said cooler, said liquid containing
predominantly higher-boiling hydrocarbons and said gas being rich
in lower-boiling components; separating the gas and the liquid;
said separated gas and liquid streams in heat exchange with liquid
evaporating at the suction pressure of the compressor, totally
condensing said gas rich in lower-boiling components, the resultant
liquid being expanded to the suction pressure of the compressor,
whereby the total condensation is effected by the evaporation of
the thus-formed, expanded liquid.
9. A process as defined by claim 5 wherein said precooling cycle
medium further comprises ethane.
10. A process as defined by claim 2 wherein the maximum molar
concentration in the cycle medium is 80% nitrogen.
11. A process as defined by claim 2 wherein the maximum molar
concentration in the medium is 60 percent nitrogen.
12. A process as defined in claim 3 wherein the maximum molar
concentration in the cycle medium is 80 percent nitrogen.
13. A process as defined by claim 3 wherein the maximum molar
concentration in the medium is 60 percent nitrogen.
Description
BACKGROUND OF THE INVENTION
This invention relates to a process for liquefaction and subcooling
of natural gas by a Claude cycle. This cycle comprises compressing
cycle gas; cooling same; dividing cooled compressed gas into two
streams; engine-expanding one stream; and cooling the other stream
with the engine-expanded stream to such an extent that said other
stream becomes partially liquefied after a subsequent throttle
expansion thereof. By the evaporation of this resultant liquid,
peak cold is made available, namely that amount of refrigeration
required for subcooling the natural gas. Before subcooling, the
natural gas has already been liquefied under a higher pressure by
heat exchange with the cycle gas, but the subcooling ensures that
the natural gas remains practically entirely in the liquid phase
even after expansion to the pressure of the storage tank. If it is
desired to avoid operation of the Claude cycle under a negative
pressure, it is essential to employ as the cycle medium a gas
having a lower boiling point than methane, nitrogen being
conventionally employed.
One disadvantage of the above-described process is that the liquid
cycle nitrogen is evaporated isothermally, i.e., yields cold at a
constant temperature, but the liquid natural gas to be subcooled
can absorb this refrigeration only at a decreasing temperature.
Consequently, because of this temperature gradient, the
refrigeration is transferred at a temperature level lower than that
necessary for cooling purposes. Thus, in the peak-cold generator,
the occurrence of large heat transfer temperature differences
.DELTA.T is unavoidable, increasing the thermodynamic
irreversibility and energy requirements of the process.
Another disadvantage is to be seen from the fact that the enthalpy
gradient in the expansion turbine, as well as the Joule-Thomson
effect in the peak-cold generator are relatively small in case of
nitrogen, so that a large amount of gas must bypass the turbine and
enter through the throttle valve, and therefore cannot be utilized
for the production of cold by engine expansion. For this reason, in
addition to the fact that the isothermal Joule-Thomson effect of
the nitrogen is also small at the warm end, the specific
refrigeration capacity of the cycle per Nm.sup.3 of circulated gas
is relatively low.
Finally, another disadvantage is that it is necessary, in order to
provide makeup nitrogen due to cycle losses, either to keep pure
nitrogen in readiness or to separate same continuously from the
natural gas. The latter expedient involves a substantial plant
investment, however, in case the natural gas is low in
nitrogen.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a process for
the liquefaction of natural gas by the use of a Claude closed
refrigerating cycle wherein one or more of the following advantages
are obtained: a lower energy requirement, a higher refrigerating
capacity per unit quantity of the cycle gas, and easier
availability and lower cost of makeup fluid required to effect
leakage losses.
Upon further study of the specification and appended claims, other
objects and advantages of the present invention will become
apparent.
These objects are attained, according to this invention, by using a
mixture of nitrogen and methane as the cycle medium.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a boiling point-composition diagram for N.sub.2
--CH.sub.4 at various pressures; and
FIGS. 2 and 3 are schematic views of preferred embodiments of the
process.
DETAILED DISCUSSION
One advantage of this process is that the evaporation of the liquid
methane-nitrogen mixture does not take place at a constant
temperature, but rather at a sliding temperature in accordance with
the boiling point diagram of nitrogenmethane at the evaporation
pressure under consideration, each evaporation temperature being
associated with a specific mixture (compare FIG. 1). Therefore, by
a selection of the evaporation pressure and the composition of the
cycle gas, the temperature range of the evaporation can be very
well adapted to the temperature range of the subcooling. Thus, the
temperature differences in the peak cooler are small and the energy
losses caused thereby are minor. Since the methane, in mixture with
the nitrogen, is vaporized at its partial pressure, i.e., a
pressure lower than the ambient evaporation pressure, it is
possible to obtain, with methane, a specific low temperature at a
relatively high pressure level.
The refrigerating capacity of the Claude cycle is likewise improved
by the addition of methane to the nitrogen. For the methane, as a
less than ideal gas, increases the Joule-Thomson effect in the peak
cooler, so that the amount of cycle gas to be fed to the J-T valve
can be smaller, and a larger proportion of the cycle gas can be fed
to the engine expansion. Additionally, the enthalpy gradient in the
turbine and thus the specific refrigerating capacity of the cycle,
based on the unit quantity of circulated gas, is larger in the case
of methane than in the case of nitrogen. The same holds true for
the isothermal Joule-Thomson effect at the warm end. Therefore, in
total, the amount of cycle gas required to produce a specific
amount of cold is reduced.
Finally, the use of a methane-nitrogen mixture as the cycle gas
affords the further advantage that the leakage losses of the cycle
medium can be compensated for at less cost by utilizing natural gas
therefor. This is so because the separation of a gas rich in
nitrogen prior to the liquefaction is in most cases absolutely
necessary, even in case of gases of low nitrogen content, since too
great a drop in the liquefaction temperature of the natural gas
must be avoided. The above-described advantage is especially
noticeable in the processing of natural gases having a low nitrogen
content, for otherwise rectification devices would have to be
provided in this procedure wherein the nitrogen is separated from
the natural gas not only in a high purity, but also in good yields.
The process according to the present invention offers advantages
even if the natural gas contains no nitrogen at all, since only
that proportion of the leakage losses associated with the nitrogen
need be made up from a source externally of the plant, whereas the
lost methane can readily be taken from the natural gas.
In the determination of the specific quantitative ratio of
nitrogen: methane to be employed, the following criteria must be
observed: As set forth hereinabove, the addition of methane to the
nitrogen results in an improvement of the specific refrigerating
capacity of the cycle gas; therefore, as high a methane content as
possible would be desirable, all other things being equal. However,
it can be seen from FIG. 1 that, at a constant pressure, the
boiling point temperature of a mixture in the region of high
nitrogen concentrations (down to a concentration of about 30-40
percent of nitrogen equal to 60-70 mol percent CH.sub.4) is
elevated to a relatively minor extent by the addition of a specific
quantity of methane, e.g., a 10 mol percent, increment in the
liquid, but that the addition of the same quantity of methane in a
zone of lower nitrogen concentrations (e.g. below 30 mol percent
nitrogen equal to above 70% CH.sub.4) causes a substantial
elevation in the boiling temperature. These relationships have a
significant effect on the suction intake pressure of the compressor
as will now be explained with reference to numerical values derived
from FIG. 1.
In order to maintain a boiling temperature of 110.degree. K, a
pressure of 16 ata. (atmospheres absolute) is required in the case
of pure nitrogen (point A), and in the case of a mixture containing
55 percent of methane, a boiling pressure of 8 ata. is necessary
(point B). Thus, the addition of 55 percent of methane only effects
a lowering of the boiling pressure to one-half the value. In
contrast thereto, in the region of high methane concentrations, the
boiling point pressure is lowered by the factor of one-half already
with a substantially lower quantity of added methane. For example,
if the methane concentration is increased only 10 percent from 85
percent (point C) to 95 percent (point D), the boiling point
pressure at 110.degree. K is lowered from about 4 ata. to about 2
ata. Therefore, in the zone of high methane concentrations, an
increase in the refrigeration capacity of the cycle by the further
addition of methane can be obtained only at the cost of a
considerable percentage-wise drop in the suction pressure;
consequently, in this region of high methane concentration, the
number of required compressor stages increases sharply.
In accordance with a preferred embodiment of the invention,
therefore, the nitrogen concentration of the cycle gas is, on a
molar basis, at least 20 percent, preferably at least 40 percent,
conversely, the maximum preferred nitrogen concentration is 80
percent, particularly 60 percent.
To provide makeup for leakage losses according to this invention, a
nitrogen separation unit is incorporated in the natural gas
liquefaction process. From the head of this unit there is withdrawn
a fraction having a nitrogen concentration of at least the same
level as that of the cycle gas, and this fraction is then fed into
the cycle as makeup gas. If this fraction contains more nitrogen
than the cycle gas, then supplemental methane from the purified
natural gas (freed of CO.sub.2, H.sub.2 O, and heavy hydrocarbons)
can be added thereto.
One negative feature of the cycle of this invention is that the
cycle gas must be precooled to a very low temperature prior to
entering the expansion engine so that it can be cooled to a
sufficiently low temperature during the expansion. This precooling
can be conducted conventionally with a multistage refrigerating
machine operating with freon, ammonia, or propane, also including,
in many cases, an essential third stage of vacuum. These
refrigerating machines exhibit the same disadvantage described
above in connection with the Claude cycle, namely that the
refrigeration is transferred at a constant temperature, to a stream
having a sliding temperature. Thus, unnecessarily large temperature
differences inherently must occur in the heat exchangers associated
with the individual pressure stages. To avoid these disadvantages,
according to a further embodiment of this invention, there is
employed a mixture of methane, propane, and optionally ethane as
the cycle medium for the precooling cycle.
A main advantage of this latter feature is that the refrigeration
liberated during the evaporation is transferred at a decreasing
temperature so that small temperature differences (.DELTA.T's) can
be employed in the heat exchangers, resalting in a
thermodynamically more efficient process. Since the propane and any
ethane present evaporate under a partial pressure lower than the
total pressure ambient during the evaporation, the desired low
temperature is obtained at a higher total pressure than would be
the case when evaporating pure ethane or propane. In other words,
because the transfer of peak cold involves a smaller pressure drop,
the number of compressor stages and thus the number of evaporators
is decreased, and the cost of control elements is also reduced.
Finally, it is to be noted that leakage losses amounting to about 1
- 5 parts per thousand of the quantity of cycle medium can
frequently be covered, in the case of methane and ethane, merely by
simple separation from the natural gas proper, i.e., they need not
be stored in additional tanks. Propane is always available in any
case so that the BTU value of the gas can be adjusted or desired.
The proportion of each of methane, propane and optionally ethane in
the total of the cycle gas is about 20-50 molar percent,
respectively. If a very low precooling temperature is to be
reached, e.g., 200.degree. to 215 .degree.K, there is employed a
cycle gas having a composition, of in moles percent 40 and 60
methane; 25 and 60 percent propane; and 0 and 15 ethane.
The above-described advantages are of special importance when the
precooling cycle is operated, according to a further preferred
embodiment of the invention, in a single stage, i.e., when the
evaporation of the compressed, cooled, and throttle-expanded
refrigerant takes place at a uniform pressure level set by the
compressor suction pressure. In this way, for example, a precooling
temperature of -60.degree. C. can be attained in a single stage
with a mixture consisting of approximately equal parts of methane
and propane, whereas, in contrast, a three-stage plant would be
required for this purpose if freon were employed as the
refrigerant. The precooling temperature attainable in this manner
is generally sufficient, even in case of low natural gas pressures,
to result in the condensation of the heavy hydrocarbons which,
otherwise, could lead to obstructions in the low-temperature
sections. Thus, the plant can be rapidly brought to the required
cold operating condition.
By utilizing the above-described single-stage precooling cycle, an
even lower precooling temperature, e.g. 160.degree. to 200.degree.
K, according to a still further preferred embodiment of this
invention, as follows: a fraction of the cycle medium remains in
the gaseous phase downstream of the final cooler of the compressor,
and the fraction containing lower boiling components is separated
from the liquid fraction containing predominantly the
higher-boiling hydrocarbons. Both separated gas and liquid are then
cooled by heat exchange with the liquid evaporating at the suction
pressure of the compressor. The gas rich in lower-boiling
components is thus totally condensed, and is then in the liquid
phase expanded (pressurereduced) to the suction pressure of the
compressor. The resultant liquid is then evaporated to effect said
total condensation.
DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to FIGS. 2 and 3, the natural gas to be processed
(0.6,780 Nm.sup.3 /hr.), after having been freed of water, carbon
dioxide, and hydrogen sulfide, and having approximately the
following composition: 2 percent nitrogen, 94 percent methane, 3
percent ethane, 1 percent propane and higher hydrocarbons, is fed
to the plant, via conduit 1, at 298.degree. K and under 39 ata. and
is then cooled in the heat exchanger 2.degree. to 216.degree. K.
During this step, the C.sub.5 - and higher hydrocarbons are
substantially condensed, which would otherwise cause clogging in
subsequent sections of the plant. The liquid is thus separated from
the gaseous phase in phase separator 3, evaporated and warmed in
heat exchanger 2, and discharged from the plant via conduit 4. The
portion remaining in the gaseous phase is further cooled in heat
exchanger 5.degree. to about 190.degree. K; during this step, a
liquid is obtained consisting of about 85 percent methane, 10
percent ethane, and 5 percent propane. This liquid after being
passed in separator-collector 6, is branched into two streams, and
the amount necessary to make up for leakage losses of the
precooling cycle is introduced into the latter via conduit 7. The
remainder is evaporated and warmed in heat exchangers 5 and 2, and
then discharged from the plant via conduit 4.
A portion of the gas withdrawn from the separator 6 overhead is now
further cooled in the heat exchanger 8 to 163.degree. K and
expanded into the nitrogen separation column 9 operating at 22 ata.
The remaining gas is conducted through a heating coil located in
the sump of the column 9 and is then expanded into the midsection
of column 9. At the head of the column 9, a temperature of about
150 K is maintained; the gaseous head product consists of 50
percent of a methane and 50% of nitrogen. This head product is
discharged from the plant via conduit 4, except for that amount of
gas required for providing makeup due to the leakage losses of the
Claude refrigerating cycle and which is fed into said cycle via
conduit 10. From the sump of the column 9, 5,820 Nm.sup.3 /h. of
liquid natural gas is withdrawn having a temperature of 167.degree.
K and approximately the following composition: 97 percent methane,
1 percent nitrogen, and 2 percent ethane. This liquid is passed to
the heat exchangers 11 and 12 and cooled therein to 111.degree. K
so that, during the subsequent expansion in the valve 13 to the
pressure of the storage tank (slightly above 1 ata.), only a
minimum amount of liquid is evaporated (about 40 Nm.sup.3 /h).
The refrigeration required for the liquefaction is provided by a
Claude cycle with precooling by a one-stage cycle based on a
mixture of gases. This mixture comprises 50 percent methane and 50
percent nitrogen and is employed as the cycle medium. This gas
(37,900 Nm.sup.3 /hr) is compressed, in compressor 14, to 25.5
ata., and after being cooled, is further compressed to 35.5 ata. in
compressor 15. The gas enters the heat exchanger 2 at a temperature
of 298.degree. K and is precooled therein and also in the heat
exchanger 5.degree. to 197.degree. K. 35,600 Nm.sup.3 /h. of cycle
gas is then expanded in the expansion turbine 16 to 8 ata. and,
during this step, is cooled to 138.degree. K. A portion of this gas
is branched off via conduit 17 and serves for cooling the head of
column 9; the main quantity is fed, via conduit 18, to the cold end
of the heat exchanger 11, heated therein and in heat exchangers 8,
5, and 2, to ambient temperature and thereafter recompressed in the
compressor 14.
The proportion of the cycle medium not subjected to engine
expansion, i.e., 2,300 Nm.sup.3 /h., is cooled in conduit 19 under
its pressure of 35.5 ata. in heat exchangers 8, 11, and 12, to
111.degree. K. During the subsequent throttle expansion to 8 ata.
in valve 20, the temperature drops to 109.degree. K, so that the
liquid natural gas can be subcooled to 111.degree. K by heat
exchange with the boiling cycle liquid, before it is expanded in
valve 13. At 21, the throttle-expanded cycle medium is combined
with the engine-expanded cycle medium, and is warmed and
recompressed together therewith.
The cycle medium of the precooling cycle consists of 45 percent
methane, 5 percent ethane, and 50 percent propane. 4,200 Nm.sup.3
/h. of this gas is compressed in compressor 22 from 10 ata. to 50
ata., cooled and simultaneously liquefied in heat exchanger 2, and
then expanded to 10 ata. in valve 23. The precooling temperature
attainable in this manner, i.e., the temperature at which the
gaseous streams to be cooled leave the cold end of the heat
exchanger 2, is 216.degree. K. The evaporated and warmed cycle
medium is then recompressed in the compressor 22. The leakage
losses of the cycle, as mentioned above, are, in part, compensated
for by the liquid withdrawn from separator 6 via conduit 7. Since
this liquid contains less propane than the cycle medium, pure
propane or a gas more enriched therewith must be added. This can be
done by conducting the gaseous stream returning to the compressor
22 via conduit 30 through the tank 28 filled with liquid propane,
rather than via conduit 29. The dome 31 serves as an entrainment
separator for the separation of droplets of liquid propane.
If the natural gas is available at a lower pressure, then a lower
precooling temperature is required. In order to attain such lower
temperature, the precooling cycle shown in FIG. 3 is employed. The
cycle medium consists of about 70 percent methane, 5 percent
ethane, and 25 propane. The liquid formed in the secondary cooler
of the compressor denoted by 24 is separated from the gaseous phase
in the separator 25, cooled in heat exchanger 2, expanded in valve
23' from 35 to 8 ata., and reevaporated and warmed in heat
exchanger 2. The gaseous phase enriched in the lower-boiling
components of the cycle medium, is withdrawn from separator 25,
conducted, via conduit 26, through the heat exchangers 2 and 5,
being cooled and liquefied during this step, and then expanded in
valve 27 from 35 to 8 ata. By the evaporation of the resultant
pressure-reduced liquid, a precooling temperature of about
165.degree. K is attacined at the cold end of the heat exchanger 5.
The cycle medium evaporated and warmed in heat exchanger 5 is
recombined with the cycle medium expanded in valve 23', and the
combined stream is then recycled to the suction side of compressor
22.
For the sake of clarity, B in FIG. 3 denotes the sum total of the
remaining gaseous streams to be cooled, i.e., the natural gas to be
liquefied and the compressed cycle medium of the Claude cycle; and
C denotes the sum total of the other gaseous streams to be warmed,
i.e., the fractions obtained during the natural gas liquefaction
and to be discharged from the plant in the gaseous phase, and the
expanded cycle medium of the Claude cycle.
From the foregoing description, one skilled in the art can easily
ascertain the essential characteristics of this invention, and
without departing from the spirit and scope thereof, can make
various changes and modifications of the invention to adapt it to
various usages and conditions. Consequently, such changes and
modifications are properly, equitably, and intended to be within
the full range of equivalence of the following claims.
* * * * *