U.S. patent number 3,827,247 [Application Number 05/330,577] was granted by the patent office on 1974-08-06 for process of complete cryogenic vaporization of liquefied natural gas.
This patent grant is currently assigned to Showa Denko K.K.. Invention is credited to Kazuo Akiyoshi, Kenji Kawada, Yukiyasu Kojima.
United States Patent |
3,827,247 |
Kojima , et al. |
August 6, 1974 |
**Please see images for:
( Certificate of Correction ) ** |
PROCESS OF COMPLETE CRYOGENIC VAPORIZATION OF LIQUEFIED NATURAL
GAS
Abstract
Liquefied natural gas is cryogenically vaporized completely
while being utilized as a cryogen for cryogenic heat-exchange
process by vaporizing the liquefied natural gas by a first
vaporization step at a temperature lower than -110.degree.C until
the non-vaporized residue of the liquefied natural gas becomes a
predetermined amount which is in a range between a critical
percentage at which higher hydrocarbons in the residual liquefied
natural gas are frozen out therefrom and a percentage higher by 8%
than the critical percentage, separating the residual liquefied
natural gas from the vaporized natural gas, conditioning the first
vaporized natural gas to a temperature from -110.degree. to
-40.degree.C and then, vaporizing the residual liquefied natural
gas by a second vaporization step by introducing it into the
conditioned first vaporized natural gas.
Inventors: |
Kojima; Yukiyasu (Yokohama,
JA), Akiyoshi; Kazuo (Tokyo, JA), Kawada;
Kenji (Yokohama, JA) |
Assignee: |
Showa Denko K.K. (Tokyo,
JA)
|
Family
ID: |
11858719 |
Appl.
No.: |
05/330,577 |
Filed: |
February 8, 1973 |
Foreign Application Priority Data
|
|
|
|
|
Feb 12, 1972 [JA] |
|
|
47-14354 |
|
Current U.S.
Class: |
62/50.2;
48/127.1; 48/190 |
Current CPC
Class: |
F25J
1/0221 (20130101); F25J 1/0015 (20130101); F17C
9/02 (20130101); F25J 2210/62 (20130101); F25J
2205/02 (20130101); F17C 2201/0109 (20130101); F17C
2227/0393 (20130101); F17C 2223/0161 (20130101); F17C
2221/033 (20130101); F17C 2265/015 (20130101); F17C
2250/0408 (20130101); F25J 2280/40 (20130101); F17C
2221/032 (20130101) |
Current International
Class: |
F17C
9/00 (20060101); F17C 9/02 (20060101); F25J
1/00 (20060101); F25J 1/02 (20060101); F17c
007/02 () |
Field of
Search: |
;48/190,196
;62/52,53,514 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Perlin; Meyer
Assistant Examiner: Capossela; Ronald C.
Attorney, Agent or Firm: Paul & Paul
Claims
What we claim is:
1. A process of completely vaporizing at a low temperature
liquefied natural gas by a first vaporization step at a temperature
lower than -110.degree.C until the non-vaporized residue of the
liquefied natural gas becomes a predetermined amount higher than a
critical percentage with respect to the initial weight of the
liquefied natural gas at which critical percentage higher
hydrocarbons in the residual liquefied natural gas are frozen-out
therefrom, but not higher than a percentage of 8 percent above the
critical percentage;
separating the residual liquefied natural gas from the first
vaporized natural gas;
heating the first vaporized natural gas to a temperature from
-110.degree. to -40.degree.C; and
vaporizing the residual liquefied natural gas by a second
vaporization step by introducing it into the conditioned first
vaporized natural gas.
2. A process as claimed in claim 1, wherein the cryogenic
vaporization is carried out under normal pressure.
3. A process as claimed in claim 1, wherein the cryogenic
vaporization is carried out under a pressurized condition.
4. A process as claimed in claim 1, wherein the conditioned
temperature of the first vaporized conditioned natural gas is from
-100.degree. to -50.degree.C.
5. A process as claimed in claim 4, wherein the conditioned
temperature of the first vaporized natural gas is from -100.degree.
to -80.degree.C.
6. A process for completely vaporizing at a low temperature
liquefied natural gas while utilizing said natural gas, in both its
liquid and vaporous phases, as a coolant for a substance without
mixing said natural gas and said substance, comprising the steps
of:
exchanging heat between natural gas in the liquid phase and said
substance to be cooled whereby sufficient heat is removed from the
liquefied natural gas such that the natural gas is in a two-phase
liquid-vapor mixture;
flowing said two-phase liquid-vapor mixture into a separator;
separating the natural gas vapors from the natural gas liquid;
heating said natural gas vapors by heat exchange with said
substance to be cooled;
mixing said liquefied natural gas with said heated natural gas
vapors at a controlled rate;
vaporizing said liquefied natural gas by heat exchange with said
already vaporized natural gas;
and further heating said vaporized natural gas by heat exchange
with said substance to be cooled.
7. In an apparatus for completely vaporizing at a low temperature
liquefied natural gas while utilizing said natural gas, in both its
liquid and vaporous stages, as a coolant, for a substance without
mixing said natural gas with said substance, the improvement
comprising:
first heat exchange means for exchanging heat between liquefied
natural gas and a substance to be cooled;
heat conduit means for feeding said heated liquefied natural gas
into a separator means;
separator means for separating liquefied natural gas from vaporous
natural gas;
sensing means for sensing the liquid level of liquefied natural gas
in said separator means;
second heat exchange means or exchanging heat between vaporous
natural gas and a substance to be cooled;
second conduit means for feeding vaporous natural gas from said
separator to said second heat exchange means;
control means for controlling the liquid level in said separator by
discharging residual liquefied natural gas into vaporous natural
gas leaving said second heat exchange means;
third conduit means in which residual liquefied natural gas fed
into said third conduit means is vaporized by vaporous natural gas
flowing through said third conduit means such that upon leaving
said third conduit means all natural gas is in a vaporous
state;
third heat exchange means for exchanging heat between said
vaporized natural gas leaving said third conduit means and a
substance to be cooled;
and electrical sensing means for sensing the level of residual
liquefied natural gas in said separator and for diverting via
by-pass valve means said substance to be cooled around said first
heat exchange means such that the rate of vaporization of liquefied
natural gas in said first heat exchange means is controlled.
Description
The present invention relates to a process of cryogenic
vaporization of liquefied natural gas, particularly, relates to a
process of completely cryogenically vaporizing liquefied natural
gas while utilizing it as a cryogen for cryogenic heat-exchange
process.
It is well-known that the liquefied natural gas is vaporized at a
very low temperature while being utilized as a cryogen for
isolating ethylene gas from mixture gas generated in the ethylene
producing process or for separating and liquefying oxygen and
nitrogen from air. In all of the conventional processes, the
liquefied natural gas is always vaporized in a single step of
cryogenic vaporization wherein the entire amount of the liquefied
natural gas is cryogenically vaporized while heat-exchanging with
other fluid. For example, in the process of producing liquefied
oxygen and nitrogen from air, it is necessary that the liquefied
natural gas be vaporized at a temperature of about -161.degree.C
under a normal pressure condition.
When the entire amount of the liquefied natural gas is vaporized by
a single vaporization step at the very low temperature as stated
above, it can be observed that it is possible to merely carry out
the vaporization discontinuously because of the reasons detailed
hereinafter. Such discontinuity of the vaporization naturally
results in a discontinuity of the entire plant operations.
Generally, the liquefied natural gas is a mixture, the major part
of which is methane and the minor part other hydrocarbons. The
other hydrocarbons contain various higher molecular hydrocarbons
having a relatively high boiling point. For example, Alaskan
liquefied natural gas having a high content of methane, contains a
small amount of various higher hydrocarbons as detailed in Table
I.
Table I ______________________________________ Hydrocarbon Content
(mol p.p.m.) ______________________________________ Propane 100
C.sub.4 hydrocarbons 99.2 C.sub.5 do. 41.1 C.sub.6 do. 54.4 C.sub.7
do. 66.7 C.sub.8 do. 11.7 C.sub.9 do. 0.1
______________________________________
In the case where the cryogenic vaporization of the liquefied
natural gas is effected at a temperature of -161.degree.C under
normal pressure conditions in order to heat-exchange with notrogen
gas to be liquefied during the vaporization for a few days, some
portions of the higher hydrocarbons in the liquefied natural gas
are frozen out on a heat-transfer wall surface so as to obstruct
the heat-exchange between the nitrogen gas and the liquefied
natural gas. This obstruction results in a decrease in the
efficiency of the cryogenic vaporization of the liquefied natural
gas and the cryogenic liquefication of the nitrogen gas.
Additionally, since the vaporization of the liquefied natural gas
has to be carried out at a very low temperature not exceeding
-110.degree.C, for example, of -161.degree.C, the heat-exchanger
for the cryogenic vaporization is different from the conventional
heat-exchanger for ordinary use. This difference is in the
complicated configuration of the heat-transfer wall surface and the
excellent high heat-insulation for transfer of ambious heat
thereinto. Therefore, the freeze-out of the higher hydrocarbons on
the heat-transfer wall surfaces of the heat-exchanger is a fatal
defect with regard to the continuous cryogenic vaporization process
of the liquefied natural gas.
Accordingly, in order to remove the frozen out higher hydrocarbons
from the heat-transfer wall surface, it is necessary to stop the
cryogenic vaporization of the liquefied natural gas at intervals of
time about 2 to 3 months and then, fuse away the frozen out higher
hydrocarbons by heating them.
The higher hydrocarbons frozen out on the heat-transfer wall
surface consist of various hydrocarbons having a relatively high
freezing point of -100.degree. to 6.5.degree.C.
Further, after the cryogenic vaporization, when the frozen out
hydrocarbons are fused and dissolved into the residual liquefied
natural gas at a relatively high temperature, and then the
resultant liquid is gradually cooled, it can be observed that the
higher hydrocarbons firstly freeze out at a temperature from
-80.degree. to -100.degree.C, but not at a temperature higher than
this. The freeze-out contains, for example, the higher hydrocarbons
as detailed in Table 2.
Table 2 ______________________________________ Hydrocarbon Content
(% by weight) ______________________________________ Dimethyl
cyclohexane 6.4 n-Heptane 5.6 Cyclohexane 5.1 Methyl cyclopentane
4.4 n-Hexane 4.1 Mixture of Methyl Cyclohexane and
2-2-Dimethylhexane 11.1 n-Nonane 2.3 1-tr-2-Dimethyl Cyclopentane
4.5 C.sub.9 Hydrocarbons 12.0 C.sub.10 Hydrocarbons 6.4
______________________________________
The higher hydrocarbons have a relatively low vaporization property
under normal pressure, and, therefore, are concentrated in the
residual liquefied natural gas with the lapse of time of the
cryogenic vaporization of the liquefied natural gas. When the
concentration of the higher hydrocarbons, exceeds the maximum
soluble in the liquefied natural gas under the cryogenic vaporizing
condition, the higher hydrocarbons are separated from the residual
liquefied natural gas and frozen out on the heat-transfer wall
surfaces. That is, in the case where the entire amount of the
liquefied natural gas is vaporized through a single step of
cryogenic vaporization, the higher hydrocarbons are always frozen
out on the heat-exchange wall surfaces as viscous and solid
matters. This is an inevitable disadvantage of the conventional
cryogenic heat-exchange process utilizing the cryogenic
vaporization of the liquefied natural gas.
In an attempt to eliminate the disadvantage stated above, an
improvement of the process has been provided. That is, prior to the
cryogenic vaporization, the higher hydrocarbons are removed by
flowing the liquefied natural gas through an adsorption column
containing adsorbent for the higher hydrocarbons. However, such
adsorption process has a technical disadvantage of difficulty of
process control and an economic disadvantage of high cost of the
adsorption column and process.
The object of the present invention is to provide a process of
complete cryogenic vaporization of liquefied natural gas without
freeze-out of higher hydrocarbons therein while utilizing the
liquefied natural gas as a cryogen for cryogenic heat-exchange
process at a high efficiency.
The above-stated object can be accomplished by the process of the
present invention. According to the present invention, liquefied
natural gas is vaporized by a first vaporization step at a
temperature lower than -110.degree.C until the non-vaporized
residue of the liquefied natural gas becomes a predetermined amount
higher than a critical percentage with respect to the initial
weight of the liquefied natural gas at which critical percentage
higher hydrocarbons in the residual liquefied natural gas are
frozen out therefrom, but not higher than a percentage of 8 percent
above the critical percentage; the residual liquefied natural gas
is separated from the first vaporized natural gas, the first
vaporized natural gas is conditioned to a temperature of
-100.degree. to -40.degree.C, and then, the separated residual
liquefied natural gas is vaporized by a second vaporization step by
introducing it into a flow of the conditioned first vaporized
natural gas.
The object, features and advantages of the process of the present
invention will be better understood by reading the following
description and referring to the accompanying drawings, in
which:
FIG. 1 is an explanation view of a device for determining the
critical amount of the residual liquefied natural gas at which
higher hydrocarbons being to be frozen out therefrom, and;
FIG. 2 is a flow chart showing an embodiment of the process of the
present invention.
In the process of the present invention, the liquefied natural gas
is first vaporized at a temperature lower than -110.degree.C until
the non-vaporized residue of the liquefied natural gas becomes an
amount higher than a critical percentage, with respect to the
initial weight of the liquefied natural gas, at which higher
hydrocarbons in the residual liquefied natural gas are frozen-out
therefrom, but not higher than a percentage of 8 percent,
preferably 3 percent, above the critical percentage.
The first vaporization of the process of the present invention is
carried out at a temperature lower than -110.degree.C. The
vaporization at a temperature higher than -110.degree.C results in
a low merit of the liquefied natural gas when used as the cryogen
for the cryogenic heat-exchange process.
When the residual liquefied natural gas becomes an amount as
specified above, the first cryogenic vaporization of the liquefied
natural gas has to be released. If the first cryogenic vaporization
is released at an amount of the residual liquefied natural gas
higher than a percentage of 8 percentage above the critical
percentage, the first cryogenic vaporization results in a very low
efficiency of the utilization of the liquefied natural gas as a
cryogen for the cryogenic heat-exchange process. This is
undesirable from the point of view of economy. Also, if the first
cryogenic vaporization of the liquefied natural gas is contained
until the residual liquefied natural gas becomes an amount lower
than the critical percentage, the higher hydrocarbons are frozen
out from the residual liquefied natural gas and deposited on the
heat-transfer plate surface of the heat-exchanger. This causes the
disadvantages detailed hereinbefore.
The critical percentage of the residual liquefied natural gas can
be determined by using a device as shown in FIG. 1. Referring to
FIG. 1, a gas tight Dewar vessel 7 for receiving liquefied natural
gas is covered with a heat-insulating material 7a and contains
therein a coiled tube 8 for flowing a heating medium therethrough.
An end of the coiled tube 8 is joined to a tube 8a for feeding the
heating medium from a heating medium supply source (not shown in
the drawing), and the other end of the coiled tube 8 is joined to a
tube 8b for discharging the heating medium. The Dewar vessel 7 is
provided with a tube 9 for discharging the vaporized natural gas
therethrough and a thermometer 10, a sensitive end 10a of the
thermometer 10 being present in the Dewar vessel 7. A transparent
window 11, for example, made of glass, is formed on the side wall
of the Dewar vessel 7 to allow observation of the inside of the
Dewar vessel 7.
The critical percentage of the residual liquefied natural gas is
determined by the following procedure. The Dewar vessel 7 is
charged with a predetermined weight of the liquefied natural gas
and hermetically closed. A heating medium, for example, dry air at
room temperature, is flowed through the feed tube 8a, the coiled
tube 8 and the discharge tube 8b to vaporize the liquefied natural
gas in the Dewar vessel 7, under predetermined temperature and
pressure conditions. The vaporized natural gas is discharged
through the tube 9. The amount of the liquefied natural gas
remaining in the Dewar vessel 7 decreases with the lapse of time of
the vaporization. When it is observed, through the transparent
window 11, that the residual liquefied natural gas in the Dewar
vessel 7 has become muddy and, at the same time, the thermometer 10
indicates an elevation of boiling point of the residual liquefied
natural gas, the vaporization is stopped and the weight of the
residual liquefied natural gas is measured. The critical percentage
is a ratio of the measured weight of the residual liquefied natural
gas to the initial weight of the liquefied natural gas, in percent.
The critical percentage of the liquefied natural gas depends on the
composition of the natural gas and the vaporization temperature and
pressure.
FIG. 2 of the accompanying drawings is a flow sheet showing an
embodiment of the process of the present invention in which the
liquefied natural gas is cryogenically vaporized and at the same
time, utilized as a cryogen of a cryogenic heat-exchange process.
Referring to FIG. 2, a first heat-exchanger 21 for the cryogenic
vaporization of liquefied natural gas is provided with a path 21a
for the liquefied natural gas and a path 21b for the substance to
be cooled. The entrance end of the path 21a is connected to a
supply source of the liquefied natural gas (not shown in the
drawing) through a conduit 20. An exit end of the path 21a is
connected to a separator 22 through a conduit 23. An entrance end
of the path 21b is connected to a conduit 24 for supplying the
substance to be cooled, and an exit end of the path 21b is
connected to a conduit 25 for discharging the cooled substance
therethrough. A second heat-exchanger 26, for preliminarily cooling
the substance to be cooled, is provided with a path 26a for the
vaporized natural gas and a path 26b for the substance to be
cooled. The entrance of the path 26a is connected to an upper
portion 22a of the separator 22 through a conduit 27 so as to flow
a gas in the upper portion 22a into the path 26a, and the entrance
of the path 26b is joined with the conduit 24. A third
heat-exchanger 28, for preliminarily cooling the substance to be
cooled, is provided with a path 28a for the vaporized natural gas
and a path 28b for the substance to be cooled. The entrances of the
paths 28a and 28b are connected to the paths 26a, 26b, of the
second heat-exchanger 26 through conduits 29 and 30, respectively,
the exit of the path 28a is connected to a receiver of the
vaporized natural gas (not shown in the drawing) through a conduit
31. The exitof the path 28b is connected to a supply source (not
shown in the drawing) of the substance to be cooled through a
conduit 32, a flow rate meter 33 and compressor 34. A lower portion
22b of the separator 22 is connected to a middle portion of the
conduit 30 through a conduit 35 and a valve 38. The conduit 24 is
communicated to the discharge conduit 25 through a conduit 36 and a
three-way valve 37.
The separator 22 is provided with a device 40 for controlling a
level of liquid contained in the lower portion 22b of the separator
22, which device 40 is electrically connected to the three-way
valve 37 through an electric circuit 41 so as to automatically
actuate the three-way valve 37. A device 42 for controlling a flow
rate of liquid flowing through the conduit 35 is located on the
conduit 35. The device 42 is electrically connected to the valve 38
through an electric circuit 43.
According to the process of the present invention, the liquefied
natural gas is fed into the first heat-exchanger 21 through the
conduit 20 and first cryogenically vaporized in the path 21a until
the non-vaporized residue of the liquefied natural gas becomes a
predetermined amount which is higher than a critical percentage of
the liquefied natural gas but not higher than a percentage of 8
percent above the critical percentage. During the first cryogenic
vaporization, the liquefied natural gas absorbs latent heat for
vaporization from the substance flowing through the path 21b,
through heat-transfer wall disposed between the paths 21a and 21b
so as to cool the substance to a desired very low temperature.
A mixture of the first vaporized natural gas and the non-vaporized
residue of the liquefied natural gas flows into the separator 22
through the conduit 23, and the two types of natural gases are
separated from each other in the separator 22. The separated
residual liquefied natural gas is contained in a lower portion 22b
of the separator 22, and the separated first vaporized natural gas
is received in an upper space 22a. The separated first vaporized
natural gas flows into the path 26a of the second heat-exchanger
26. While flowing through the path 26a, the first vaporized natural
gas is conditioned to a temperature of -110.degree. to -40.degree.C
by heat-exchanging with the substance flowing through the path 26b,
which preliminarily cools the substance. The first vaporized
natural gas flows from the path 26a towards the path 28a of the
third exchanger 28 through the conduit 30. The residual liquefied
natural gas in the lower portion 22b of the separator 22 is
introduced into the middle portion of the conduit 30 through the
conduit 35 and ejected into the flow of the first vaporized natural
gas which has been conditioned at a temperature of -110.degree. to
-40.degree.C. The flow rate of the residual liquefied natural gas
through the conduit 35 is controlled by actuation of the valve 38
by the control device 42. The ejected residual liquefied natural
gas is vaporized completely by a second vaporization step in the
flow of the first vaporized natural gas while absorbing latent heat
for the vaporization from the first vaporized natural gas. This
heat absorption causes a lowering of the temperature of the first
vaporized natural gas. Therefore, the mixture of the first and
second vaporized natural gases has a temperature lower than that of
the first vaporized natural gas, which has been conditioned at a
temperature of -110.degree. to -40.degree.C. The vaporized natural
gas thus prepared is introduced into the path 28a of the third
heat-exchanger 28 so as to preliminarily cool the substance flowing
through the path 28b. After passing through the third
heat-exchanger 28, the vaporized natural gas is discharged into a
receiver (not shown in the drawing) through the conduit 31.
The substance to be cooled flows from a source thereof (not shown
in the drawing) through the conduit 32 and is compressed to a
desired pressure by the compressor 34. It is then fed into the path
28b of the third heat-exchanger 28 at a predetermined flow rate,
which is detected by the flow rate meter 33. The substance thusly
fed is preliminarily first cooled by heat-changing with the
vaporized natural gas flowing through the path 28a. The first
cooled substance is introduced into the path 26b of the second
heat-exchanger 26 through the conduit 29, and then, preliminarily
second cooled by heat-exchanging with the first vaporized natural
gas flowing through the path 26a. The substance thusly second
cooled is introduced into the path 21b of the first heat-exchanger
21 through the conduit 24, and then finally cooled to the desired
temperature by heat-exchanging with the liquefied natural gas
flowing through the path 21a.
The substance thusly finally cooled is discharged into a receiver
(not shown in the drawing) through the three-way valve 37 and the
conduit 25.
According to the process of the present invention, the separated
residual liquefied natural gas in the separator 22 is introduced
into a flow of the first vaporized natural gas in order to vaporize
it by a second vaporization step. In this second vaporization, it
is important that the first vaporized natural gas has been
conditioned at a temperature of -110.degree. to -40.degree.C,
preferably, -100.degree. to -50.degree.C, and more preferably,
-100.degree. to -80.degree.C. If the temperature of the conditioned
first vaporized natural gas is lower than -110.degree.C, it is
difficult to completely vaporize the residual liquefied natural gas
in the second vaporization step. Also, if the temperature of the
conditioned first vaporized natural gas is higher than
-40.degree.C, the resultant mixture of the first and second
vaporized natural gases has a low merit when used as a cryogen for
the cryogenic heat-exchange due to its relatively high
temperature.
Referring to FIG. 2, the level control device 40 is to prevent the
freeze-out of the higher hydrocarbons from the residual liquefied
natural gas in the first heat-exchanger. In the case where the feed
rates of the liquefied natural gas and/or the substance to be
cooled are varied, and thus, the level of the residual liquefied
natural gas in the separator 22 is varied, the variation of the
liquid level is detected by the level control device 40 and the
three-way valve 37 is opened or closed in response to the type of
variation detected. That is, the flow rate of the substance
introduced into the path 21b is controlled by discharging a portion
of the substance flowing through the conduit 24, through the
conduit 36, the three-way valve 37 and the conduit 25.
Particularly, in the case where the liquid level in the separator
22 becomes lower than the predetermined height, that is, the
liquefied natural gas is vaporized over the predetermined amount,
the three-way valve is actuated by the level control device 40 so
as to discharge a portion of the substance flowing through the
conduit 24. The cryogenic vaporization of the present invention may
be carried out under normal pressure or a pressurized condition,
preferably, lower than 20 atmospehres.
Preferable modes of the process of the present invention will be
better understood from the following examples.
EXAMPLE 1
The cryogenic vaporization of the present invention was applied to
a process of preparing liquefied nitrogen gas.
Referring to FIG. 2, recycled nitrogen gas was introduced into a
conduit 32 at a flow rate of 20,000 Nm.sup.3 /hr at room
temperature and under a middle pressure, and then compressed to a
pressure of 28 atmospheres by the compressor 34. The nitrogen gas
thus compressed flowed through the path 28b of the third
heat-exchanger 28 and was preliminarily first cooled to a
temperature of -50.degree.C by heat-exchanging with the vaporized
natural gas flowing through the path 28a. The nitrogen gas thus
first cooled flowed through the path 26b of the second
heat-exchanger 26 and was preliminarily second cooled to a
temperature of -90.degree.C by heat-exchanging with the first
vaporized natural gas flowing through the path 26a. Thereafter, the
nitrogen gas thus second cooled flowed through the path 21b of the
first heat-exchanger 21 and was finally cooled to a temperature of
-151.degree.C so as to be liquefied by heat-exchanging with the
liquefied natural gas flowing through the path 21a. The liquefied
nitrogen gas was discharged through the conduit 25 into the
receiver (not shown in the drawing). The liquefied natural gas was
fed into the first heat-exchanger 21 at a flow rate of 12,750
Nm.sup.3 /hr under normal pressure. While flowing through the path
21a, the liquefied natural gas was first vaporized to a vapor of a
temperature of -161.degree.C in a percentage by weight of 98
percent based on the initial weight thereof. The remaining 2
percent by weight of the liquefied natural gas remained in the
liquid state. The critical percentage of the liquefied natural gas
used, was 1.5 percent. The mixture of the first vaporized natural
gas and the residual liquefied natural gas was introduced into the
separator 22 and the two gases were separated from each other. The
separated first vaporized natural gas of a temperature of
-161.degree.C was introduced into the second heat-exchanger 26.
While flowing through the path 26a, the first vaporized natural gas
was conditioned to a temperature of -100.degree.C while
preliminarily second cooling the nitrogen gas flowing through the
path 26b. The first vaporized natural gas of a temperature of
-100.degree.C flowed through the conduit 30 at a flow rate of
12,495 Nm.sup.3 /hr. The residual liquefied natural gas was
vaporized completely by a second vaporization step by introducing
it into the flow rate of the first vaporized natural gas in the
conduit 30 at a flow rate of 255 Nm.sup.3 /hr. By this second
vaporization, the mixture of the first and second vaporized natural
gas was adjusted to a temperature of -107.degree.C.
The vaporized natural gas of a temperature of -107.degree.C flowed
through the path 28a of the third heat-exchanger 28 at a flow rate
of 12,750 Nm.sup.3 /hr so as to preliminarily first cool the
nitrogen gas flowing through the path 28b. After passing through
the path 28a, the vaporized natural gas had a temperature of
20.degree.C, and was discharged into the receiver (not shown in the
drawing) through the conduit 31.
Throughout the above-stated cryogenic vaporization, no freeze-out
of the higher hydrocarbons was observed, and the cryogenic
vaporization could be continuously carried out for a period longer
than 12 months.
EXAMPLE 2
The procedure of Example 2 was repeated using liquefied natural gas
of a temperature of -132.degree.C under a pressure of 7 atmospheres
and air containing no moisture or carbon dioxide. The air was
compressed to a pressure of 6 atmospheres by the compressor 34, and
fed into the third heat-exchanger 28 at a flow rate of 10,000
Nm.sup.3 /hr. After passing through the path 28b, the compressed
air was preliminarily first cooled to a temperature of
-19.degree.C. The compressed air thus first cooled was
preliminarily second cooled to a temperature of -37.degree.C by
flowing through the path 26b of the second heat-exchanger 26.
Thereafter, the compressed air thusly second cooled was fed into
the path 21b of the first heat-exchanger 21 and finally cooled to a
temperature of -130.degree.C. The cooled air was discharged through
the conduit 25 into the receiver (not shown in the drawing).
The liquefied natural gas having a temperature of -132.degree.C
under a pressure of 7 atmospheres was fed into the path 21a of the
first heat-exchanger 21 at a flow rate of 4,132 Nm.sup.3 /hr. After
passing through the path 21a, 98 percent by weight of the liquefied
natural gas was first vaporized, and 2 percent by weight of the
liquefied natural gas remained in liquid phase. The critical
percentage of the liquefied natural gas was 1.5 percent at a
temperature of -132.degree.C under a pressure of 7 atmospheres. The
first vaporized natural gas was separated from the residual
liquefied natural gas in the separator 22. The separated first
vaporized natural gas flowed through the path 26a of the second
heat-exchanger 26 in order to second cool the air flowing through
the path 26b. While passing through the path 26a, the first
vaporized natural gas was conditioned to a temperature of
-100.degree.C. The conditioned first vaporized natural gas flowed
through the conduit 30 at a flow rate of 4,049 Nm.sup.3 /hr and was
mixed with the residual liquefied natural gas ejected through the
conduit 35 at a flow rate of 83 Nm.sup.3 /hr. The residual
liquefied natural gas thus ejected was vaporized completely by a
second vaporization step. By this second vaporization, the mixture
of the vaporized natural gases from the first and second
vaporization steps was adjusted to a temperature of -105.degree.C.
The vaporized natural gas flowed through the path 28a of the third
heat-exchanger 28 while preliminarily first cooling the air flowing
through the path 28b. After passing through the path 28, the
vaporized natural gas having a temperature of 10.degree.C was
discharged into the receiver (not shown in the drawing).
The cooling of the compressed air and the cryogenic vaporization of
the liquefied natural gas could be continuously carried out without
difficulty for a period longer than 12 months. After operating for
a period of 12 months, no-freeze-out of the higher hydrocarbons was
observed in any of the paths of the natural gas.
* * * * *