U.S. patent number 3,702,063 [Application Number 04/873,964] was granted by the patent office on 1972-11-07 for refrigeration cycle for the aliquefaction of natural gas.
This patent grant is currently assigned to Linde Aktiengesellschaft. Invention is credited to Volker Etzbach, Wolfgang Forg.
United States Patent |
3,702,063 |
Etzbach , et al. |
November 7, 1972 |
REFRIGERATION CYCLE FOR THE ALIQUEFACTION OF NATURAL GAS
Abstract
In the liquefaction of natural gas wherein the refrigeration
cycle fluid contains natural gas components, and such components
are subjected to fractional condensation to obtain different
temperature levels of refrigeration, the system is improved by
adjusting the C.sub.3 -C.sub.6 content of cycle fluid and the
pressure of at least one intermediate pressure stage of the
circulation pressure in such a manner that condensate is formed in
the corresponding intercooler of said pressure stage. This
condensate is then separated and subjected to heat exchange to
utilize its refrigeration values and recirculated to the
circulation compressor via an expansion valve. In this way, a
substantial concentration of heavy hydrocarbons can be utilized to
increase the refrigeration capacity of the refrigeration cycle, but
said hydrocarbons do not deleteriously affect the lower temperature
levels of refrigeration.
Inventors: |
Etzbach; Volker (Munich,
DT), Forg; Wolfgang (Grunwald, DT) |
Assignee: |
Linde Aktiengesellschaft
(Hollriegelskreuth, DT)
|
Family
ID: |
5712332 |
Appl.
No.: |
04/873,964 |
Filed: |
November 4, 1969 |
Foreign Application Priority Data
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Nov 4, 1968 [DT] |
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P 18 06 879.6 |
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Current U.S.
Class: |
62/612 |
Current CPC
Class: |
F25J
1/0202 (20130101); F25J 1/004 (20130101); F25J
1/0212 (20130101); F25J 1/0045 (20130101); F25J
1/0022 (20130101); F25J 1/0055 (20130101); F25J
2230/30 (20130101); F25J 2220/62 (20130101); F25J
2245/90 (20130101); F25J 2290/62 (20130101); F25J
2220/64 (20130101) |
Current International
Class: |
F25J
1/00 (20060101); F25J 1/02 (20060101); F25j
001/00 (); F25j 005/00 (); F25j 001/02 () |
Field of
Search: |
;62/9,11,23,24,40 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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895,094 |
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May 1962 |
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GB |
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1,557,019 |
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Jan 1969 |
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FR |
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Other References
Kleemenko, A. P.; One Flow Cascade Cycle in Progress in
Refrigeration Science & Technology, Pergamon Press 1960 pp.
34-39..
|
Primary Examiner: Yudkoff; Norman
Assistant Examiner: Purcell; Arthur F.
Claims
What is claimed is:
1. In a process for the liquefaction of natural gas, said process
employing at least one refrigeration cycle, wherein the
refrigeration cycle fluid contains natural gas components and is
compressed, cooled, liquefied, expanded, vaporized and heated in
heat exchange with cycle fluid and natural gas to be liquefied, and
recycled to the circulation compressor, said process having
multiple stages of decreasing temperature,
the improvement comprising employing as said circulation
compressor, a multi-stage compressor, adjusting the concentration
of C.sub.3 - to C.sub.6 - hydrocarbons in the cycle fluid, and the
pressure of at least one intermediate stage of the circulation
compressor, with respect to each other so that a portion of the
effluent from said intermediate stage is condensible by heat
exchange with cooling water; cooling said effluent from said
intermediate stage in an intercooler between two successive
pressure stages to form a liquid phase condensate containing a
substantial concentration of heavy hydrocarbons and a vapor phase;
separating said condensate from said vapor phase; pressure-reducing
said condensate exclusively of any condensate of said vapor phase
separated therefrom; vaporizing and heating resultant
pressure-reduced condensate in heat exchange with the natural gas
to be liquefied and the cycle fluid; recycling resultant heated
vaporized condensate to the inlet side of the circulation
compressor, recompressing said vapor separated from said condensate
containing a substantial concentration of heavy hydrocarbons, and
subjecting resultant recompressed vapor to multiple stages of
partial condensation, phase separation, and expansion of resultant
condensates to produce said multiple stages of decreasing
temperature.
2. A process as defined by claim 1, wherein the pressure of fluid
leaving said intercooler is substantially the same as the pressure
of the natural gas to be liquefied, said natural gas being
intermixed into cycle fluid.
3. A process as defined by claim 1, wherein the required
refrigeration is produced by a single cycle, and the cycle fluid is
subjected to a multi-stage partial condensation, wherein, in each
partial condensation, the condensate is separated, expanded to the
inlet pressure of the circulation compressor, vaporized and warmed
in heat exchange with cycle fluid and natural gas, and recycled to
the circulation compressor.
4. A process as defined by claim 3, wherein the pressure of fluid
leaving said intercooler is substantially the same as the pressure
of the natural gas to be liquefied, said natural gas being
intermixed with cycle fluid.
5. Apparatus for the liquefaction of natural gas, said apparatus
comprising:
a condensate separator (4) having inlet means and gas outlet means
and liquid outlet means;
at least one intercooler (3) having inlet and outlet means; said
inlet means of said condensate separator being in communication
with said outlet means of said intercooler;
a circulation compressor having at least two serially connected
compression stages, said inlet means of said intercooler being in
communication with the outlet of an intermediate compression stage,
said gas outlet means of said condensate separator being disposed
before, and in communication with the inlet side of the last
serially connected compression stage (8);
an expansion valve (6) being in communication with the liquid
outlet means of said condensate separator and separate unbranched
conduit means for conducting liquid from said liquid outlet means
exclusively to said expansion valve;
heat exchange means including separate flow paths for expanded
condensate, natural gas to be liquefied, and cycle liquid; and
conduit means for effecting said communications and also for
recirculating resultant heated expanded condensate from said heat
exchange means and said expansion valve to the inlet of said
circulation compressor, and
means for effecting multiple stages of partial condensation, phase
separation, and expansion of resultant condensates, said mean being
in communication with the outlet side of the last serially
connected compression stage (8).
6. A process as defined by claim 1 wherein fluid entering said
intercooler is cooled to about 10.degree.-30.degree.C. in said
intercooler.
7. A process as defined by claim 6 wherein fluid entering said
intercooler is cooled to about 20.degree.-30.degree.C. in said
intercooler.
8. A process as defined by claim 2, said pressure being about 15-45
atmospheres absolute.
9. A process as defined by claim 8, the cycle gas entering the
intercooler having the following composition in per cent by
volume:
0-5 N.sub.2 ; 30-50 CH.sub.4 ; 20-50 C.sub.2 H.sub.6 ; 10-40
C.sub.3 H.sub.8 ; 0-15 C.sub.4 H.sub.10 ; 0-3 C.sub.5 H.sub.12 ;
and 0-2 C.sub.6 H.sub.14.
10. A process as defined by claim 2, said pressure being about
10-25 atmospheres absolute.
11. A process as defined by claim 10, the cycle gas entering the
intercooler having the following composition in per cent by
volume:
0.05-2 N.sub.2 ; 35-40 C.sub.4 ; 20-40 C.sub.2 H.sub.6 ; 10-30
C.sub.3 H.sub.8 ; 4-12 C.sub.4 H.sub.10 ; 1-2 C.sub.5 H.sub.12 ;
and 1-2 C.sub.6 H.sub.14.
12. A process as defined by claim 1, said refrigeration cycle being
a closed cycle, the pressure entering the intercooler being 2-20
atmospheres absolute and the gas entering the intercooler having
the following composition in per cent by volume:
0-10 N.sub.2 ; 10-40 CH.sub.4 ; 20-40 C.sub.2 H.sub.6 or C.sub.2
H.sub.4 ; 0-20 C.sub.3 H.sub.8 ; 10-20 C.sub.4 H.sub.10 ; 0-20
C.sub.5 H.sub.12 ; and 0-20 C.sub.6 H.sub.14.
13. A process as defined by claim 1, said refrigeration cycle being
a closed cycle, the pressure entering the intercooler being 10-25
atmospheres absolute and the gas entering the intercooler having
the following composition in per cent by volume:
2-6 N.sub.2 ; 30-40 CH.sub.4 ; 35-45 C.sub.2 H.sub.6 or C.sub.2
H.sub.4 ; 0-3 C.sub.3 H.sub.8 ; 10-15 C.sub.4 H.sub.10 ; 5-10
C.sub.5 H.sub.12 ; and 5-10 C.sub.6 H.sub.14.
14. A process as defined by claim 1, said liquid phase condensate
having a substantial concentration of heavy hydrocarbons having a
molecular weight of about 40-70 and said vapor phase separated
therefrom having a molecular weight of about 20-40.
15. A process as defined by claim 1, said liquid phase condensate
having a substantial concentration of heavy hydrocarbons having a
molecular weight of about 50-60 and said vapor phase separated
therefrom having a molecular weight of about 20-30.
16. A process as defined b claim 2 comprising the steps of passing
said vapor separated from said condensate having a substantial
concentration of heavy hydrocarbons to a final compression stage of
said multi-stage compressor; cooling resultant compressed vapor to
form a liquid phase and a vapor phase; passing the just-mentioned
liquid phase through a heat exchanger, and expanding a portion of
resultant heat exchanged fluid and discharging the latter from said
liquefaction cycle, said portion being of sufficient amount and of
a composition to remove C.sub.3 and higher hydrocarbons from the
natural gas intermixed with said cycle fluid.
17. A process as defined by claim 1, said condensate from said
intercooler being employed as a cooling medium only in the higher
temperature stages of said multiple stages of decreasing
temperature.
Description
BACKGROUND OF THE INVENTION
This invention relates to a process and an apparatus for the
liquefaction of natural gas with the use of at least one
refrigeration cycle, and in particular to such a process wherein
the heat exchange fluid in the refrigeration cycle is a mixture of
natural gas components. This cycle fluid is compressed, cooled,
liquefied, expanded, evaporated and warmed in heat exchange with
itself and with the natural gas to be liquefied. It is then
recycled to the inlet of the circulation compressor.
The function of the refrigeration cycle is to produce the
refrigeration required for liquefying natural gas [depending on
climatic conditions having an ambient temperature (generally about
-20.degree. - +40.degree.C.)]. Because the natural gas contains
components having different liquefaction temperatures, a
refrigeration cycle fluid is advantageously employed which is
composed of components also having differing boiling points, as
disclosed, for example, by A. P. Kleemenko (Comptes rendus du
Congres du Froid de Copenhague 1959, pp. 34-39).
The cycle fluid is then partially condensed in multiple stages,
each liquid fraction being separated from the gaseous phase,
expanded, vaporized, heated and recycled to the compressor. The
components having low boiling points, such as methane and nitrogen,
yield the refrigeration required at the lowest temperature level
whereas the fraction containing ethane and propane yields
refrigeration values at an intermediate temperature level. The
refrigeration required for the precooling step, i.e. for cooling to
a temperature corresponding approximately to the boiling point of
ammonia at atmospheric pressure (-33.degree.C.), is produced by the
vaporization of a mixture of higher hydrocarbons, such as propane,
butane, and higher-boiling compounds.
From the standpoint of refrigeration it is desirable that the
higher hydrocarbons are present in the cycle fluid in large
quantities. This is the case because they exhibit a higher latent
heat of vaporization than the lower-boiling cycle fluid components,
so that, with an increase in their concentration, the refrigerating
capacity of the cycle, based on 1 Nm.sup.3 of circulated cycle gas,
likewise increases. However, serious problems ordinarily result
from the use of a high concentration of higher hydrocarbons.
Specifically, during the subsequent partial condensation steps, an
unacceptable amount of higher hydrocarbon remains in the gaseous
phase, passes with the low-boiling cycle gas components into the
final expansion stages, and in such final stages elevates the
vaporization temperature above the desired refrigeration level and,
in certain cases, gives rise to solid deposits in the refrigeration
cycle, causing eventual damage or shut-down of the process.
SUMMARY OF THE INVENTION
Bearing the above problems in mind, a principal object of this
invention is to provide an improved process for the liquefaction of
natural gas so that the refrigerating capacity of the cycle fluid
is increased without deleteriously affecting the temperature level
of the lower temperature refrigerating stages.
Another object is to provide apparatus for conducting such a
process.
Upon further study of the specification and appended claims, other
objects and advantages of the invention will become apparent.
These objects are attained, according to this invention, by
adjusting both the concentration of the C.sub.3 -C.sub.6
hydrocarbons in the cycle fluid and the pressure of the
intermediate stages of the circulation (cycle) compressor in
relation to each other so that a condensate is formed after the
cooling step following the intermediate compression stage. This
condensate is then separated, expanded, vaporized, and then heated
in heat exchange with both the natural gas to be liquefied and the
cycle fluid. After the latter heat exchange step, the resultant
warmed gas is recycled to the inlet side of the circulation
compressor. It is important to note that the condensate is expanded
(pressure-reduced) exclusively of any condensate of the vapor phase
separated therefrom in the preceding step; the resultant separated
vapor is then recompressed downstream of the intermediate
compression stage, and then subjected to multiple stages of
condensation, phase separation, and expansion of resultant
condensates to produce the required multiple stages of decreasing
temperature necessary for liquefying the natural gas.
In general, the molecular weight of the condensate after the
cooling step following the intermediate compression stage is about
40 to 70, preferably 50 to 60, and that of the resultant vapor
about 20 to 40, preferably 20 to 30.
The advantage of the above described system resides in that the
refrigeration capacity of the cycle is increased, due to the
presence of larger amounts of C.sub.3 -C.sub.6 hydrocarbons, and
that simultaneously, by the partial condensation after the
intermediate cooling in the intercooler, the partial pressure of
these hydrocarbons in the refrigeration medium passing into the
lowest temperature stages is maintained at such a low level that
there is no undesired increase of the vaporization temperature in
such stages.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a schematic diagram of a preferred embodiment of this
invention wherein the natural gas is intermixed with cycle
fluid.
FIG. 2 is a schematic diagram of another preferred embodiment
wherein the natural gas is liquefied independent of any intermixing
with cycle fluid.
DETAILED DISCUSSION
In order to obtain the desired molecular weight of condensate and
vapor after the cooling step following the intermediate compression
stage, the pressure of the intermediate compression stage and the
content of C.sub.3 -C.sub.6 hydrocarbons in the cycle fluid are
adjusted. When the natural gas to be liquefied is intermixed with
cycle fluid, it is advantageous for the pressure of the
intermediate compression stage to be the same or substantially the
same as the natural gas pressure, generally about 45 to 35,
preferably 10 to 25 atmospheres absolute. Under such conditions the
cycle gas must have about the following composition:
Component General Preferred % by Volume % by Volume
__________________________________________________________________________
N.sub.2 0-5 0.05-2 CH.sub.4 30-50 35-40 C.sub.2 H.sub.6 20-50 20-40
C.sub.3 H.sub.8 10-40 10-30 C.sub.4 H.sub.10 0-15 4-12 C.sub.5
H.sub.12 0-3 1-2 C.sub.6 H.sub.14 0-2 1-2
__________________________________________________________________________
when the natural gas to be liquefied is not intermixed with the
cycle gas, the pressure of the intermediate compression can be
altered with even greater flexibility, for example, in the range of
2 to 20, preferably 10 to 15 atmospheres absolute. Under such
conditions, the cycle fluid can have the following analysis:
Component General Preferred % by Volume % by Volume
__________________________________________________________________________
N.sub.2 0-10 2-6 CH.sub.4 10-40 30-40 C.sub.2 H.sub.6 or C.sub.2
H.sub.4 20-40 35-45 C.sub.3 H.sub.8 0-20 0-3 C.sub.4 H.sub.10 10-20
10-15 C.sub.5 H.sub.12 0-20 5-10 C.sub.6 H.sub.14 0-20 5-10
__________________________________________________________________________
for optimum economics, a chemical engineer can select the precise
conditions of the process, depending on energy costs at the plant
site, etc. It is also to be noted that these minor components may
exist in the cycle gas, such as helium, CO.sub.2 and H.sub.2 S and,
if so, appropriate adjustments will again be made to optimize the
process.
In any case, there is no question that a chemical engineer will be
able to make the necessary adjustments of the pressure in the
intermediate circulation compressor and the content of C.sub.3 -
C.sub.6 - hydrocarbons in the cycle fluid to obtain a condensate
after the cooling step following the intermediate compression step.
For this purpose, such cooling steps will generally be conducted so
that the cycle fluid is cooled to about 10.degree. to 35.degree.,
preferably 20.degree. to 30.degree.C., dependent on the cooling
water temperature.
The invention is applied in a particularly suitable manner to a
process wherein the required refrigeration is produced by a single
cycle, and the cycle fluid is subjected to a multi-stage partial
condensation, where, in each instance, the condensate is separated,
expanded to the inlet pressure of the circulation compressor,
vaporized and warmed in heat exchange with cycle fluid and natural
gas, and recycled to the circulation compressor. By this process, a
high liquefaction efficiency is obtained with a low expenditure in
apparatus, and, furthermore, the process can be easily adapted to
various natural gas compositions and operating conditions.
The apparatus for conducting the process according to the invention
comprises as the essential novelty, a separator connected after at
least one intercooler of the circulation compressor, which
separator is in communication in the gas phase via a conduit, with
the subsequent compression stage and, in the liquid phase, via an
expansion valve, and the refrigerating cycle path of a heat
exchanger, with the inlet side of the circulation compressor, and
associated conduit.
DETAILED DESCRIPTION OF DRAWINGS
Without further elaboration, it is believed that one skilled in the
art can, using the preceding description, utilize the present
invention to its fullest extent. The following preferred specific
embodiments are, therefore, to be construed as merely illustrative,
and not limitative of the remainder of the disclosure in any way
whatsoever.
FIG. 1 shows a process with an open cycle, i.e. wherein the natural
gas to be liquefied is compressed and brought to a low temperature
together with the cycle gas. The cycle fluid has approximately the
following composition:
1-5% N.sub.2 1-6% C.sub.4 H.sub.10 35-55% CH.sub.4 0.5-2.5% C.sub.5
H.sub.12 27-38% C.sub.2 H.sub.6 0-2% C.sub.6 H.sub.14 12-25%
C.sub.3 H.sub.8
20,000 nm.sup.3 /h of the cycle gas is fed at about 6 atmospheres
absolute through conduit 1 to the inlet side of the first
compressor stage 2, compressed at that point to about 20
atmospheres absolute, and brought to the cooling water temperature
in the intercooler 3. 1,000 Nm.sup.3 /h of the cycle fluid are
liquefied during this step, separated from the gaseous phase in the
separator 4, cooled to about 280.degree.K. in the heat exchanger 5,
and expanded through valve 6 into the conduit 1 whereupon it is
then reintroduced to the first stage of the compressor. The gas
leaving the separator 4, together with 6,000 Nm.sup.3 /h of natural
gas (freed of CO.sub.2, H.sub.2 S, and H.sub.2 O), is compressed in
the second compressor stage 8 to about 35 atmospheres absolute. In
the final cooler 9, there is again obtained about 1,000 Nm.sup.3 /h
of liquid, the latter being collected in the separator 10 and
subcooled in heat exchanger 5. The major portion of the subcooled
liquid expanded by valve 11, into the conduit 1, is then vaporized
and heated in heat exchanger 5. Before the resultant cycle gas is
again returned to the first compressor stage, it passes through the
liquid trap 12, the latter protecting the compressor from liquid
impacts, for example when the plant is placed on stream, or in case
of operating errors.
A small portion of the subcooled liquid from separator 10 is
expanded, at the cold end of the heat exchanger 5, via valve 13
into the conduit 27 leading to the gasometer. In this connection,
the amount and composition of this stream are chosen so that the
C.sub.3 - and higher hydrocarbons entering the plant together with
the natural gas again are discharged from the plant by this
path.
The gas from the separator 10 is cooled, in heat exchanger 5, to
about 280.degree.K. and is partially condensed during this step. In
the separator 14, the liquid, about 4,200 Nm.sup.3 /h, is separated
from the vapor. Both fractions are cooled in heat exchanger 15 to
about 245.degree.K. The subcooled liquid is expanded, admixed to
the returning cycle gas, and vaporized in heat exchanger 15. The
gas is once again partially condensed and separated, in separator
16, into a liquid and a gaseous phase. The amount of the
thus-formed liquid is about 6,000 Nm.sup.3 /h.
Both phases are now cooled in heat exchanger 17 to about
195.degree.K. The subcooled liquid is expanded, in the manner
described above, into the recycling cycle gas, and vaporized in
head exhanger 17. The partially condensed vapor is again separated,
in separator 18, into the two phases which are cooled, in heat
exchanger 19, to about 185.degree.K. The liquids from the
separators 18 (7,300 Nm.sup.3 /h) and 20 (500 Nm.sup.3 /h) are
combined, subcooled together in heat exchanger 21, and thereafter
expanded in the valve 22. During this process, a temperature of
about 140.degree.K. is reached. The liquid is now vaporized and
warmed in heat exchangers 21 and 19, then mixed with the liquid
from separator 16, which liquid was subcooled in heat exchanger 17,
and recycled in the manner described above to the circulation
compressor.
The vapor separated in separator 20 is cooled, liquefied, and
subcooled in heat exchangers 21 and 23. The liquid passes at a
temperature of about 115.degree. K. into the storage tank 25 by way
of expansion valve 24. The temperature at the cold end of the heat
exchanger 23 is obtained by expansion and vaporization of a portion
of the liquid leaving the heat exchanger 23; this liquid is
expanded via valve 26 into the conduit 27 leading to the gasometer,
and is discharged from the plant via the heat exchangers 23, 21,
19, 17, 15, and 5. The gas vaporized in the storage tank 25 by the
effect of heat is withdrawn via conduit 28 and conveyed, through
the cold gas blower 29, and via conduit 27 to the gasometer.
In the following table, the pressure and temperature conditions
ambient in the individual separators are set forth (P in
atmospheres absolute, T in .degree.K.), as well as the total amount
fed to each separator (F in Nm.sup.3 /h), the amount of liquid
separated therein (L in Nm.sup.3 /h), and also the approximate
molecular weight of the respective gaseous or liquid phase, M.sub.G
and M.sub.L :
separator P T F L M.sub.G M.sub.L
__________________________________________________________________________
4 20 303 20,000 1,000 30 51 10 35 303 25,000 1,000 27 43 14 35 281
24,000 4,200 24 38 16 35 245 19,800 6,000 21 32 18 35 195 13,800
7,300 18 23 20 35 187 6,500 500 18 20
__________________________________________________________________________
it can be seen from the above table that in the separator 4,
propane (molecular weight 44) and the higher hydrocarbons are
obtained in the liquid phase. The liquid in separator 10 consists
essentially of propane; in separators 14 and 16, the proportion of
ethane (molecular weight 30) increases in the liquid. In separators
18 and 20, a mixture of ethane and methane (molecular weight 16) is
separated. The gas leaving the separator 20 is mostly methane. In a
similar manner, the molecular weight of the gaseous phase decreases
from separator to separator.
Referring now to FIG. 2, there is disclosed another important
embodiment of this invention wherein a closed cycle is employed,
i.e. when natural gas and cycle medium are always conducted
separately from each other. Identical structural components bear
identical reference numerals. The cycle fluid has the following
compositions:
1-5% N.sub.2 8-20% C.sub.4 H.sub.10 20-35% CH.sub.4 2-7% C.sub.5
H.sub.12 35-50% C.sub.2 H.sub.6 1-4% C.sub.6 H.sub.14
the essential difference as compared to FIG. 1 resides in that the
natural gas is not fed via conduit 7 to the second compressor stage
8, but rather via conduit 40 to the heat exchanger 5 and then to
the low-temperature plant disposed thereafter as in FIG. 1. This
embodiment obviates the need for a device for the removal of the
high boiling hydrocarbons introduced into the cycle by the natural
gas, as would correspond to the valve 13 of FIG. 1.
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.
* * * * *