U.S. patent number 3,698,589 [Application Number 04/888,151] was granted by the patent office on 1972-10-17 for cryogenic storage apparatus.
This patent grant is currently assigned to Union Carbide Corporation. Invention is credited to James L. Perry.
United States Patent |
3,698,589 |
Perry |
October 17, 1972 |
CRYOGENIC STORAGE APPARATUS
Abstract
A double walled container having an inner vessel and an outer
shell with an intervening vacuum insulation space, including a neck
tube formed of certain gas impervious fiber reinforced plastic
compositions having certain physical properties, the neck tube
providing access to the inner vessel and also being loaded in
tension by the inner vessel as the sole suspension means
therefor.
Inventors: |
Perry; James L. (Totowa Buro,
NJ) |
Assignee: |
Union Carbide Corporation
(N/A)
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Family
ID: |
25392620 |
Appl.
No.: |
04/888,151 |
Filed: |
December 29, 1969 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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599343 |
Dec 1, 1966 |
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337696 |
Dec 26, 1963 |
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149356 |
Nov 1, 1961 |
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Current U.S.
Class: |
220/560.1;
220/560.12 |
Current CPC
Class: |
A47J
41/028 (20130101); F17C 3/08 (20130101); A47J
41/02 (20130101); F17C 2203/0629 (20130101); F17C
2203/0673 (20130101); F17C 2203/018 (20130101); F17C
2203/0391 (20130101); F17C 2203/032 (20130101); F17C
2260/033 (20130101); F17C 2205/018 (20130101); F17C
2203/0345 (20130101); F17C 2260/011 (20130101); F17C
2201/032 (20130101); F17C 2203/0643 (20130101); F17C
2201/0109 (20130101) |
Current International
Class: |
A47J
41/02 (20060101); A47J 41/00 (20060101); F17C
3/00 (20060101); F17C 3/08 (20060101); B65d
025/00 () |
Field of
Search: |
;220/9C,9LG,10,14,15 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
"Handbook of Plastics" by Simonds, Weith & Bigelow, Second
Edition, Jan. 1949, Published by D. Van Nostrand, Inc., Reprint of
Nov. 1955, Page 55..
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Primary Examiner: Leclair; Joseph R.
Assistant Examiner: Garrett; James R.
Parent Case Text
This application is a continuation of Ser. No. 599,343, filed Dec.
1, 1966, now abandoned, which latter application is a continuation
of Ser. No. 337,696, filed Dec. 26, 1963, now abandoned, said last
mentioned application being a continuation-in-part of Ser. No.
149,356 filed Nov. 1, 1961, now abandoned.
Claims
What is claimed is:
1. In a low temperature storage container having an outer shell and
an inner storage vessel each with an upper opening wherein the two
openings are vertically aligned and with said inner storage vessel
and outer shell sized to enclose an intervening vacuum insulation
space, the improvement comprising a cylindrical neck tube with
opposite ends respectively gas-tightly sealed to the edges of said
upper openings in the outer shell and inner vessel so as to provide
a relatively wide access hole from the atmosphere to the interior
of said inner vessel, said neck tube being formed of a
substantially gas impervious material with the outer wall thereof
sealing said vacuum insulation space and selected from the group
consisting of paper reinforced with a thermoset phenol-formaldehyde
resin, glass fiber reinforced with a thermoset epoxy resin, and
glass fiber reinforced with a thermoset polyester resin, said neck
tube being loaded in tension by said inner vessel as the sole
suspension means therefor and having the following physical
properties:
2. A storage container according to claim 1 in which the neck tube
is formed of paper reinforced with a thermoset phenol-formaldehyde
resin.
3. A storage container according to claim 1 in which the neck tube
is formed of glass fiber reinforced with a thermoset epoxy
resin.
4. A storage container according to claim 1 in which the neck tube
is formed of material having a specific gravity of at least
1.10.
5. In a low temperature vacuum insulated storage container having
an outer shell and an inner storage vessel each with an upper
opening wherein the two openings are vertically aligned, the
improvement comprising a cylindrical neck tube with opposite ends
respectively gas-tightly sealed to the edges of said upper openings
in the outer shell and inner vessel so as to provide a relatively
wide access hole from the atmosphere to the interior of said inner
vessel, said neck tube being formed of a substantially gas
impervious material selected from the group consisting of paper
reinforced with a thermoset phenol-formaldehyde resin, glass fiber
reinforced with a thermoset epoxy resin, and glass fiber reinforced
with a thermoset polyester resin, said neck tube being loaded in
tension by said inner vessel as the sole suspension means therefor
and wherein support rings with grooves that face each other axially
of the container are connected to the edges of said upper openings
in the outer shell and inner vessel, and the opposite ends of said
neck tube are positioned and gas-tightly sealed in said grooves.
Description
This invention relates to cryogenic storage apparatus and more
particularly to a double-walled, vacuum insulated cryogenic storage
container.
Heretofore, typical containers for storing cryogenic liquids such
as liquid oxygen and liquid nitrogen in relatively small quantities
of about 15-25 liters comprised an inner storage vessel, an outer
protective shell which enclosed the inner vessel thereby forming an
evacuable insulation therebetween, and a relatively long narrow
neck tube which served as the entrance to the inner vessel. The
inner vessel was usually supported entirely by suspension from the
top of the outer shell by such neck tube. These containers were
extremely fragile in that the inner vessel often ruptured at the
neck tube-inner vessel joint due to impact and acceleration forces
experienced during handling.
Another disadvantage of these containers was the relatively small
diameter of the neck tube which hampered access to the inner
vessel. Enlargement of the neck tube opening of these containers
was no solution, however, since this increased the heat leakage
into the inner vessel. Not only was a portion of an otherwise
well-insulated area replaced by a larger uninsulated opening, but
the heat leakage along the walls of the neck tube itself was
significantly increased.
In order to preserve the liquefied gas with a minimum of
evaporation due to excessive heat leakage and yet provide a
relatively sturdy container, the prior art found it necessary to
employ a neck tube constructed of a material such as stainless
steel. These strength and heat leak requirements are conflicting in
that a relatively strong material such as stainless steel is also a
relatively high conductor of heat. Furthermore, the prior art found
it necessary to employ a neck tube constructed of such material to
ensure an effective seal of the evacuated insulation space
surrounding the inner product liquid vessel. The gas imperviousness
and high strength advantage of stainless steel was only obtained at
the cost of gas loss due to the contribution to heat leakage into
the inner vessel.
It is an object of this invention to provide a low-temperature
storage container employing an improved neck tube constructed of
high strength material which has the advantages of large access
opening, strength, and vacuum tightness while substantially
reducing the heat leakage into the inner vessel. Another object is
to provide a low temperature liquefied gas storage container with
an improved neck tube that is constructed of a gas impervious and
low-heat conductive material. These and other objects of the
invention will become apparent from the following discussion and
the accompanying drawing in which:
The FIGURE is a view of a longitudinal cross-section of a
low-boiling liquefied gas container embodying principles of the
present invention.
While the invention will be described in conjunction with a
low-boiling liquefied gas storage container, it is to be understood
that it is equally well-suited for utilization in other type
low-temperature storage containers such as those used for the
preservation of materials such as biological substances where a
low-boiling liquefied gas is employed as a refrigerant to surround
such biological materials.
This invention is embodied in an improved vacuum-insulated, low
temperature storage container having an outer protective shell, an
inner product vessel, an evacuable insulation space therebetween,
and a neck tube connecting the outer shell to the inner vessel
large enough to provide access to the interior storage space of
such inner vessel.
The neck tube of the container is constructed of a substantially
gas impervious reinforced fibrous laminate impregnated with a
thermosetting synthetic resin. The gas permeation rate of the neck
tube material must be less than 1 .times. 10.sup.-.sup.10 cu.
cm./sec. of helium at a pressure of one atm. as determined by
testing a tube having a 11/2 inch inside diameter, a 1/16 inch wall
thickness and a length of 2 inches in a Model MS-9A Veeco Mass
Spectrometer Leak Detector. Hence the term "substantially gas
impervious" as employed herein means those materials having a gas
permeation rate of from zero to 1 .times. 10.sup.-.sup.10 cu.
cm./sec. of helium. Preferably the permeation rate is zero. The
laminates employed as the neck tube can be of any material or
synthetic fiber in random or orderly manner, such as is found in
paper, cloth, or the like or any reinforcing or rigidifying fiber
such as cellulosic fibers, glass fibers, synthetic fibers or the
like, and thoroughly impregnated with a cured thermosetting resin.
The degree of impregnation of the reinforced laminate should be
sufficient to produce, after curing of the resin to a thermoset
condition, a substantially gas impervious neck tube. Phenolic
resins, i.e., phenol-aldehyde condensates, and epoxy resins such as
the polyglycidyl ethers of polyhydric phenols, serve excellently as
the thermosetting resins of these laminates although other
thermosetting resins such as polyester resins providing the same or
equivalent degree of gas imperviousness can be employed. These
resins can be applied to liquid resins or solvent solutions of
solid resins to impregnate a preformed neck tube and the resin
cured in situ by heating to elevated temperatures or by curing aids
or hardeners, such as polyfunctional amines, or both to a thermoset
condition. If desired the neck tube can be fabricated from
preimpregnated and cured reinforced laminates in tubular form, or
they can be prepared from partially cured resin-impregnated paper
or cloth webs, and finally cured to a thermoset condition after
forming. It has been found that gas impervious neck tubes
constructed of thermoset resin impregnated fibrous laminates, in a
manner to be described, effectively reduce vaporization losses of
the liquefied gas due to atmospheric heat leakage into the inner
vessel as well as maintain the insulation qualities of the
evacuable insulation space surrounding the inner vessel by
preventing loss of the vacuum therethrough.
To achieve these results, a gas impervious neck tube is preferably
constructed of resin impregnated fibrous laminates having the
following physical properties:
Specific Gravity between about 1.10-1.55 Compressive Strength at
least 10,000 psi. Tensile Strength at least 8,500 psi. Specific
Heat between about 0.26-0.40 Thermal Conductivity between about
0.0007-0.0012
cal/sec/cm.sup.2 /deg C/ cm. These thermoset resin impregnated
laminates reduce liquified gas vaporization induced by heat leakage
to less than about 70 percent of the loss attained by employing a
stainless steel neck tube. For example a material known
commercially as Synthane Grade X manufactured by the Synthane Corp.
of Oaks, Penn., which comprised a paper tube of 11/2 inch inside
diameter with a wall thickness of 1/16 inch, reinforced with a
thermoset phenol-formaldehyde resin having the above physical
characteristics and a zero gas transmission rate as hereinbefore
described was subjected to a 3-month test as a neck tube in a
double-walled vacuum insulated storage container during which it
was found that the loss of liquefied gas through vaporization
induced by heat leak was 1.4 lbs/day as compared to 2 lbs/day
employing a stainless steel neck tube in the same type of container
under similar conditions. Further, it was found that there was no
gas leak to the evacuable insulation space surrounding the inner
vessel. Similar tests were preformed employing materials known
commercially as Synthane Grade G-10 and G-11 manufactured by the
Synthane Corp. which comprised neck tubes of a glass fiber fabric
reinforced with a thermoset epoxy resin. The insulation space was
evacuated to an absolute pressure of below about 30 microns of
mercury and, after 3 months of continuous testing, the vacuum
therein was substantially identical to that at the beginning of the
test. The gas imperviousness of neck tubes constructed from these
resin impregnated fibrous laminates has been further proven by mass
spectographic tests.
The preferred embodiment of this invention employs opacified
insulation wherein such insulation substantially completely fills
the evacuable insulation space between the outer shell and the
inner vessel. However, lower quality insulating systems such as the
powder-in-vacuum insulators or straight vacuum with highly polished
outer shell inner and inner vessel outer surfaces may be
alternately employed.
The term "opacified insulation" as used herein refers to a
two-component insulating system comprising a low heat conductive,
radiation permeable material and a radiant heat impervious material
which is capable of reducing the passage of infrared rays without
significantly increasing the thermal conductivity of the insulating
system. Such opacified insulation is more fully described in U.S.
Pat. No. 2,967,152 issued Jan. 3, 1961, and copending U.S.
application Ser. No. 597,947, filed July 16, 1956, now U.S. Pat.
No. 3,007,596 both in the name of L. C. Matsch.
The opacified insulation of the former incorporates the radiation
impervious barrier directly into the low heat conductive material.
For example, equal parts by weight of copper flakes and finely
divided silica might be mixed. The latter material has a very low
solid conductivity value but is quite transparent to radiation. The
copper flakes serve to markedly reduce the radiant heat inleak.
The latter referenced opacified insulation takes the form of low
heat conductive material separated by a multiplicity of
radiation-impervious barriers. The low heat conductive material may
be a fiber insulation produced in sheet form. Examples include a
filamentary glass material such as glass wool and fiber glass,
preferably having fiber diameters less than about 50 microns. Also,
such fibrous materials preferably have a fiber orientation
substantially perpendicular to the direction of heat flow across
the insulation space. The spaced radiation-impervious barriers may
comprise either a metal, metal oxide, or metal coated material,
such as aluminum coated plastic film, or other radiation reflective
or radiation adsorptive material or a suitable combination thereof.
Radiation reflective material, comprising thin metal foils are
particularly suited in the practice of the present invention, for
example, reflective sheets of aluminum foil having a thickness
between 0.2 millimeters and 0.002 millimeters. When fiber sheets
are used as the low conductive material, they may additionally
serve as a support means for the relatively fragile radiant heat
impervious sheets. For example, it is preferred that an aluminum
foil-fiber insulation be spirally wrapped around the inner vessel
with one end of the insulation wrapping in contact with the inner
vessel, and the other end nearest the outer shell, or in actual
contact therewith.
Even though the previously described preferred opacified insulation
is more effective than straight vacuum insulation at higher
internal pressures (poorer vacuum), its effective thermal
insulation life is extended if the vacuum pressure can be
maintained at or below a desired level. A gas-removing material
such as an adsorbent may be used in the insulation space to remove
by adsorption any gas entering through the joints of the outer
shell. In particular, crystalline zeolitic molecular sieves having
pores of at least about 5 Angstrom units in size, as disclosed and
claimed in U.S. Pat. No. 2,900,800 issued in the name of P. E.
Loveday, are preferred as the adsorbent. They have extremely high
adsorptive capacity at the temperature and pressure conditions
existing in the insulation space and are chemically inert toward
any gases which might leak into the insulation space.
In the preferred embodiment depicted in the FIGURE of the drawing,
neck tube 10 is constructed of a paper or fabric tube impregnated
with a thermoset epoxy or phenolic resin in a manner such that neck
tube 10 has the aforementioned physical properties. Neck tube 10 is
preferably joined to the outer shell 12 of container 14 and to the
inner storage vessel 16 by means of rigid annular support rings 18
and 20 respectively. As shown, neck tube 10 is preferably
positioned by annular grooves 17 and 19 in rings 18 and 20, and
bonded therein. Rings 18 and 20 are employed to simplify joining
the neck tube to the inner vessel and the outer shell inasmuch as
it has been found that stronger joints may be constructed by
bonding the neck tube in grooves. In this manner, the shear
strength of the bonding resin is more fully utilized and a more
leak tight joint is achieved. If a relatively weaker joint can be
tolerated, the neck tube joints can be formed without the use of
grooves. It has been found that "A-12" epoxy resin manufactured by
Armstrong Products Co. of Warsaw, Ind., is a suitable bonding
agent.
Inner vessel 16 is preferably supported in tension by neck tube 10
at one end, the tensile strength of said tube being sufficient to
support the entire weight of said vessel and its contents.
Insulation space 24 between outer shell 12 and inner vessel 16 is
preferably substantially completely filled with an opacified
insulation material. Such insulating material affords lateral
support for inner vessel 16 but no appreciable vertical
support.
Insulation space 24 is preferably evacuated to a low positive
pressure of less than about 25 microns of mercury and preferably
less than about 0.5 microns by a vacuum pump capable of being
connected to pinch-off tube 25. Absorbent material 26 such as
silica gel or sodium zeolite A is located within enclosure 28
attached to the bottom of inner vessel 16 to assist in preserving
the low vacuum pressure within insulation space 24.
The access opening formed by neck tube 10 is substantially occupied
by an annular low heat conductive plug 30 such that liquid
vaporized by unavoidable heat leakage will flow out through the
annular space between plug 30 and neck tube 10. The vaporized gas
will absorb a substantial part of the heat which would otherwise be
conducted into inner vessel 16 by neck tube 10. Low heat conductive
plug 30 may be constructed of a material such as foam plastic or
cork.
A neck tube constructed of a reinforced thermoset phenol-aldehyde
or epoxy resin laminate will not creep or change its shape under
varying the temperature conditions. In the preferred embodiment
support rings 18 and 20 and neck tube 10 are designed to bear the
vertical loads that are imposed upon the inner vessel and, since
rigidity and dimensional stability are important, the properties
exhibited, and mentioned above, by these reinforced thermoset resin
laminates are desirable.
The bonded joints, between neck tube 10 and annular rings 18 and 20
are preferably formed by curing an application of epoxy resin, such
as the previously noted A-12 brand resin, at a temperature of about
150.degree. F. In this respect, it should be noted that outer shell
12 and inner vessel 16 should be connected, by means such as
welding to annular rings 18 and 20 prior to their assembly with
neck tube 10 so that the heat necessary to form the weld joining
rings 18 and 20 to outer shell 12 and inner vessel 16 will not
damage the bonded joints in the annular grooves of rings 18 and 20.
Therefore, to assemble this arrangement, inner vessel 16 with its
welded ring 20 is first attached to the support member 22 within
the lower section of outer shell 12. Neck tube 10 is then placed in
the annular groove of ring 20 and an upper section of outer shell
12, with annular ring 18 attached, is placed into position,
elastically elongated and preferably girth welded at 11 to its
first lower segment. The resulting joints in the annular grooves 17
and 19 of rings 18 and 20 are then cured, employing the epoxy resin
as the neck tube joint bonding agent. Insulation space 24 is
preferably evacuated simultaneously with the curing process.
It has been found that the ends of the neck tube and the annular
grooves should be sandblasted prior to bonding to provide
sufficiently roughened surfaces for proper bonding thereof. The
sandblasting may be accomplished by projecting 120-mesh aluminum
oxide particles against the surfaces of the grooves at a velocity
of about 500 fps.
* * * * *