U.S. patent number 3,704,600 [Application Number 05/077,802] was granted by the patent office on 1972-12-05 for cryogenic refrigerator.
This patent grant is currently assigned to U.S. Phillips Corporation. Invention is credited to Clifford McDonald Hargreaves, Gijsbert Prast.
United States Patent |
3,704,600 |
Prast , et al. |
December 5, 1972 |
CRYOGENIC REFRIGERATOR
Abstract
A cryogenic refrigerator including cooling means for H.sub.2
before it is expanded in a throttle valve and flows back to one of
two containers which are filled with an alloy of A and B in powder
form, in which the ratio A : B can vary from 1 : 3 to 2 : 17,
wherein A is Ca or one or more of the rare earths, if desired
combined with Th and/or Zr and/or Hf, and wherein B is mainly Ni
and/or Co, this alloy having the property of readily absorbing
H.sub.2 at low temperature and readily desorbing H.sub.2 at high
temperature, which gas is again directed to said throttle.
Inventors: |
Prast; Gijsbert (Emmasingel,
Eindhoven, NL), Hargreaves; Clifford McDonald
(Emmasingel, Eindhoven, NL) |
Assignee: |
U.S. Phillips Corporation (New
York, NY)
|
Family
ID: |
19808126 |
Appl.
No.: |
05/077,802 |
Filed: |
October 5, 1970 |
Foreign Application Priority Data
|
|
|
|
|
Oct 15, 1969 [NL] |
|
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6915564 |
|
Current U.S.
Class: |
62/457.9; 62/56;
62/79 |
Current CPC
Class: |
F25B
17/12 (20130101); Y02B 30/62 (20130101); Y02A
30/277 (20180101); Y02A 30/27 (20180101) |
Current International
Class: |
F25B
17/12 (20060101); F25B 17/00 (20060101); F25d
003/08 () |
Field of
Search: |
;62/56,457,514,79 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Wye; William J.
Claims
What is claimed is:
1. A device for producing cold at low temperatures having a system
of inlet ducts which comprises one or more counter flow heat
exchangers and one or more precoolers in which a high-pressure
medium supplied to said system is cooled to below its inversion
temperature associated with said pressure and communicates with a
throttle device in which the medium expands, as well as a system of
outlet ducts which communicates with the throttle device and along
which low-pressure medium can flow away via the said counter flow
heat exchangers, characterized in that the medium is hydrogen and
the device furthermore comprises at least one container which is
filled with an alloy of A and B in powder form, in which the ratio
A : B can vary from 1 : 3 to 2 : 17, wherein A is Ca or one or more
of the elements of the rare earths, if desirable combined with Th
and/or Zr and/or Hf, and wherein B is mainly Ni and/or Co, each of
the containers being communicable with the system of inlet or
outlet ducts, each of the containers furthermore comprising a
heater and a cooler which can be switched alternately.
2. A device as claimed in claim 1, characterized in that at least
three of the said containers are present.
3. A device as claimed in claim 1, characterized in that each of
the containers contains one of the alloys LaNi.sub.5 ; La.sub.0.8
Y.sub.0.2 Ni.sub.5 ; La.sub.0.9 Zr.sub.0.1 Ni.sub.5 ; La.sub.x
Ce.sub.1.sub.-x Ni.sub.5 wherein 0.4< x <1; La Ni, wherein La
is an alloy containing 85 percent by weight of La, 10 percent by
weight of Nd, 4 percent by weight of Pr and 1 percent by weight of
Ce.
4. A device for compressing hydrogen gas particularly suitable for
use in a device as claimed in claim 1, characterized in that said
device comprises at least one container which is filled with an
alloy of A and B in powder form, in which the ratio A : B can vary
from 1 : 3 to 2 : 17, wherein A IS Ca or one or more of the
elements of the rare earths, if desirable, combined with Th and/or
Zr and/or Hf, and wherein B is mainly Ni and/or Co, in which each
of the containers can be made to communicate with an outlet for
high-pressure hydrogen gas and an inlet for low-pressure hydrogen
gas, each of the containers furthermore comprising a heater and a
cooler which can be switched alternately.
5. A device as claimed in claim 4, characterized in that each of
the containers comprises one of the alloys LaNi.sub.5 ; La.sub.0.8
Y.sub.0.2 Ni.sub.5 ; La.sub.0.9 Zr.sub.0.1 Ni.sub.5 ; La.sub.x
Ce.sub.1.sub.-x Ni.sub.5 ; wherein 0.4< x <1; La Ni, wherein
La is an alloy containing 85 percent by weight of La, 10 percent by
weight of Nd, 4 percent by weight of Pr and 1 percent by weight of
Ce.
6. Apparatus for producing cold comprising at least one container
having therein an alloy of members A and B in powder form in which
the ratio of A : B by weight is from 1 : 3 to 2 : 17, and wherein A
is a member selected from the group consisting of calcium, the rare
earth elements, mixtures of calcium and at least one element
selected from the group consisting of Th, Zr, and Hf, and mixtures
of a rare earth element and at least one element selected from the
group consisting of Th, Zr, and Hf, and where B is a member
selected from the group consisting of Ni, Co, and mixtures thereof,
a source of high pressure H.sub.2, an inlet duct for flowing said
H.sub.2 to said container, an outlet duct for flowing H.sub.2 out
of said container, means for cooling H.sub.2 in said outlet duct to
below its inversion temperature, throttle means for expanding said
cooled H.sub.2 to provide said cold, first means for cooling said
container, second means for heating said container, and third means
for selectively activating said first and second means.
7. Apparatus according to claim 6 comprising at least two
containers as described and switch means for selectively operating
said first means for heating one of said containers while operating
said second means for cooling the other container.
8. Apparatus according to claim 6 wherein each of said containers
contains one of the alloys in the group consisting of LaNi.sub.5,
La.sub.0.8 Y.sub.0.2 Ni.sub.5, La.sub.0.9 Zr.sub.0.1 Ni.sub.5,
La.sub.x Ce.sub.1.sub.-x Ni.sub.5 wherein 0.4< x <1, and La
Ni, wherein La is an alloy containing 85 percent by weight of La,
10 percent by weight of Nd, 4 percent by weight of Pr and 1 percent
by weight of Ce.
9. Apparatus according to claim 7 wherein said means for cooling
H.sub.2 in the outlet duct comprises at least one counter-flow
heat-exchanger cooled by the flow of expanded and cooled H.sub.2 in
said inlet duct.
10. Apparatus for compressing H.sub.2 comprising at least one
container having therein an alloy of members A and B in powder form
in which the ratio of A : B by weight is from 1 : 3 to 2 : 17, and
wherein A is a member selected from the group consisting of
calcium, the rare earth elements, mixtures of calcium and at least
one element selected from the group consisting of Th, Zr, and Hf,
and mixtures of a rare earth element and at least one element
selected from the group consisting of Th, Zr, and Hf, and where B
is a member selected from the group consisting of Ni, Co, and
mixtures thereof, a source of low pressure H.sub.2, an inlet duct
for flowing said H.sub.2 to said container, an outlet duct for
flowing H.sub.2 out of said container, first means for cooling said
container, second means for heating said container and third means
for selectively activating said first and second means.
11. Apparatus according to claim 10 wherein each of said containers
contains one of the alloys in the group consisting of LaNi.sub.5,
La.sub.0.8 Y.sub.0.2 Ni.sub.5, La.sub.0.9 Zr.sub.0.1 Ni.sub.5,
La.sub.x Ce.sub.1.sub.-x Ni.sub.5 wherein 0.4<x<1, and La Ni,
wherein La is an alloy containing 85 percent by weight of La, 10
percent by weight of Nd, 4 percent by weight of Pr and 1 percent by
weight of Ce.
Description
BACKGROUND OF THE INVENTION
The invention relates to a device for producing cold at low
temperatures having a system of inlet ducts which comprises one or
more counter flow heat exchangers and one or more precoolers in
which a high-pressure medium supplied to the system of ducts is
cooled to below its inversion temperature associated with said
pressure and communicates with a throttle device in which the
medium expands; also there is a system of outlet ducts which
communicates with the throttle device and along which low-pressure
medium can flow away via the counter flow heat exchangers.
Devices of the above-described type are known under the name of
Joule-Kelvin systems. In such devices the supply and exhaust of
high-pressure medium and low-pressure medium, respectively, is
ensured by a compression device communicating with the system of
inlet ducts and outlet ducts, respectively. Drawbacks of this is
that the compression device produces noise and vibrations as a
result of its moving components, and its reliability and lifetime
are inadequate to satisfy stringent requirements as regards long
reliability and long lifetime. Moreover, in many places where cold
has to be produced, for example, in cooled infrared detection
systems, the produced noise and vibrations are not tolerable.
Known cooling devices which do not demonstrate the above-described
drawbacks are the so-called absorption refrigerators. In these
refrigerators a cooling medium of higher pressure is supplied, via
an inlet duct which comprises a condenser in which the medium
condenses, to a pressure-reducing valve which communicates with an
outlet duct having a vaporizer in which the cooling medium
evaporates at lower pressure. The inlet duct and outlet duct each
communicate with a container in which a substance (liquid or solid)
is present which has an absorbing power for the cooling medium, the
container with which the outlet duct communicates being cooled and
the container with which the inlet duct communicates being heated.
Due to this temperature difference, a pressure differential occurs
between the two containers, the cooling medium being absorbed in
the cold container and desorption of the cooling medium occurring
in the warm container. A drawback of these known absorption
refrigerators is that, with the known combinations of cooling
medium and absorbing substance, the achievable temperature
difference is only small so that temperatures much lower than
-70.degree. C are substantially unachievable.
SUMMARY OF THE NEW INVENTION
It is the object of the invention to provide a device for producing
cold of the type mentioned in the preamble with which temperatures
in the order of 25.degree. K can be achieved and which in addition
can operate without noise, vibration-free and for a very long
period of time in a very reliable manner due to the absence of
moving parts.
In order to reach these objectives the device according to the
invention is characterized in that the medium is hydrogen and the
device furthermore comprises at least one container filled with an
alloy of A and B in powder form, in which the ratio A : B can vary
from 1 : 3 to 2 : 17, wherein A is Ca or one or more of the
elements of the rare earths, if desirable combined with Th and/or
Zr and/or Hf, and wherein B is mainly Ni and/or Co, each of the
containers being alternately communicable with the system of inlet
or outlet ducts, each container furthermore comprising a heating
and a cooling device which are alternately switchable. It is to be
noted that the element Y is considered among the elements of the
rare earths within the scope of the present application.
The operation of the device according to the invention is mainly
based on the surprising property of the alloy AB of being capable
of absorbing very much hydrogen gas in a short period of time,
while it can also rapidly give off again said hydrogen gas.
For each of the alloys belonging to the said group AB, isotherms
can be drawn in a diagram in which the hydrogen gas pressure
P.sub.H2 is plotted vertically and the absorbed quantity of
hydrogen C.sub.H is plotted horizontally. Each isotherm shows at a
given pressure a horizontal variation, the so-called "plateau." At
the plateau pressure it is possible by means of a small pressure
variation to cause much hydrogen gas to be taken up or to be given
off in a reversible process. The graph shown in FIG. 1 denotes the
variation of the said isotherms for LaNi.sub.5.
Of great advantage in the use of said materials in the device
according to the invention, is their power of taking up large
quantities of hydrogen gas. For example, 0.80 g of hydrogen gas per
centimeter is taken up by LaNi.sub.5 powder having a packing
density of 65 percent at a hydrogen gas pressure of 5 atmospheres.
The density of the hydrogen gas in these materials may be in the
order of magnitude of that of liquid hydrogen and more.
A second advantage is that the hydrogen gas can very rapidly be
recovered again from the material. In the graph shown in FIG. 2 it
is indicated how for LaNi.sub.5, the quantity of outflowed hydrogen
gas depends upon time at different operating temperatures and at an
external pressure of 1 atmosphere.
The device according to the invention may comprise two containers
filled with the alloy AB of which one is cooled to, for example,
20.degree. C and the other of which is heated to, for example,
80.degree. C. By communicating the heated container with the system
of inlet ducts and communicating the cooled container with the
system of outlet ducts, desorption of the hydrogen gas at higher
pressure (associated with 80.degree. C) will occur in the heated
container. This high-pressure hydrogen gas flows through the
counter flow heat exchangers and along the precooler and expands in
the throttle device while cooling further. The throttled gas then
flows along a place to be cooled and thence through the counter
flow heat exchanger to the cooled container where it is absorbed.
In this manner a refrigerator is obtained without moving components
which can supply cold at approximately 25.degree. K, is very
reliable, and produces no noise or vibrations.
When only two containers are present, the device according to the
invention cannot operate continuously since upon switching the
containers, the warm container should be cooled to the temperature
of the cold container, while the cold container should be heated to
the temperature of the warm container. In a further embodiment of
the device according to the invention, at least three containers
are therefore present. Two of these containers are always in
operation while the third is brought to the desirable temperature
in the mean time. If desirable it is also possible to use only one
container, the system of outlet ducts comprising a large buffer
volume. The desorbing hydrogen gas periodically flows from the
container through the system of inlet ducts and via the throttle
valve to the buffer volume while after cooling the container, the
hydrogen gas flows back from the buffer volume again directly to
the container.
In a further preferred embodiment of the device according to the
invention the containers comprise one of the alloys LaNi.sub.5 ;
La.sub.0.8 Y.sub.0.2 Ni.sub.5 ; La.sub.0.9 Zr.sub.0.1 Ni.sub.5 ;
La.sub.x Ce.sub.1.sub.-x Ni.sub.5, where 0.4< x <1; La Ni
where La is an alloy containing 85 percent by weight of La, 10
percent by weight of Nd, 4 percent by weight of Pr and 1 percent by
weight of Ce. Especially these alloys have proved to have extremely
good absorbing and desorbing properties for hydrogen gas. It is to
be noted that Ni and/or Co can be partly replaced by some other
elements, for example, Fe, Cu, and so on, without the properties as
regards the absorption and giving-off of hydrogen gas strongly
deteriorating.
The invention furthermore relates to a device for compressing
hydrogen gas which is characterized in that it comprises at least
one container filled with an alloy of A and B in powder form, in
which the ratio A : B can vary from 1 : 3 to 2 : 17, wherein A is
Ca or one or more of the elements of the rare earths, if desirable,
combined with Th and/or Zr and/or Hf, and wherein B is mainly Ni
and/or Co, and which each of the containers can be made to
communicate with an outlet for high-pressure hydrogen gas and an
inlet for low-pressure hydrogen gas, each of the containers being
furthermore provided with a heater and a cooler which are
switchable alternately. In this manner an extremely reliable and
noiseless operating device for compressing hydrogen gas is
obtained.
BRIEF DESCRIPTION OF THE DRAWINGS
In order that the invention may be readily carried into effect, it
will now be described in greater detail, by way of example, with
reference to FIGS. 3, 4 and 5 of the accompanying drawings.
FIG. 1 shows a graph of isotherms for LaNi.sub.5.
FIG. 2 shows a graph of the H.sub.2 gas outflow from LaNi.sub.5 as
a function of time and temperature.
FIG. 3 shows diagrammatically a refrigeration system of the present
invention.
FIG. 4 shows diagrammatically another embodiment of the invention
of FIG. 3, and
FIG. 5 shows diagrammatically a hydrogen compression device.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Reference numerals 31 and 32 in FIG. 3 denote two containers which
are filled with a very fine powder of LaNi.sub.5. Ducts 33 and 34,
respectively, communicate with each of the containers and can be
made to communicate, via a four-way valve 35, with an inlet duct 36
and an outlet 37, respectively, of a Joule-Kelvin cooling system.
The inlet duct 36 comprises a cooler 38, a first counter flow heat
exchanger 39, a heat exchanger 40, a second counter flow heat
exchanger 41, a throttle valve 42 which communicates with the
outlet duct 37 which also comprises the counter flow heat
exchangers 39 and 41. In each of the containers 31 and 32, a cooler
44 and 45, respectively and a heating device 46 and 47,
respectively, are accommodated which can be actuated
alternately.
The operation of this device is as follows. The device is filled
with hydrogen in a suitable manner. One container 31 is then cooled
by means of cooler 44 by setting valve 48 in the correct position,
so that cooling water flows through it, at a temperature of
approximately 20.degree. C, while container 32 is heated, by means
of the heating device 47, for example, an electric resistance
heating, to a temperature of approximately 110.degree. C. It may be
seen from the graph shown in FIG. 1 that a pressure of
approximately 2 atmospheres will prevail in the container 31, and a
pressure of approximately 50 atmospheres will prevail in container
32.
Four-way valve 35 is now set so that container 32 communicates with
the inlet duct 36, and container 31 communicates with the outlet
duct 37. Desorped hydrogen gas from container 32 will now flow to
throttle valve 42 via cooler 38 where it is cooled, counter flow
heat exchanger 39, heat exchanger 40, where the hydrogen gas is
further cooled by a precooler 50, for example, a vessel containing
liquid nitrogen, and via counter flow heat exchanger 41. Here the
gas throttles with simultaneous cooling. After the throttle valve,
the hydrogen which may then have a temperature of approximately
23.degree. K, is contacted with a place to be cooled and then said
medium flows via outlet duct 37 and four-way valve 35 to container
31 where it is absorbed. The desorption in container 32 and the
absorption in container 31, respectively, is continued until the
pressure in container 32 tends to drop below the plateau pressure
associated with 110.degree. C or the pressure in the container 31
tends to rise above the plateau pressure of 20.degree. C. The
operation is then switched, that is to say, the cooling water is
now conducted through cooler 45 while heating device 47 is switched
off and heating device 46 is switched on. The four-way valve is set
in a closed position. As soon as the containers 31 and 32 have
reached the operating temperatures of 110.degree. and 20.degree. C,
respectively, four-way valve 35 is set in the position in which
container 31 communicates with the inlet duct and container 32
communicates with the outlet duct.
If desirable, it is possible to avoid this discontinuity in the
operation by providing buffer vessels in the inlet and outlet
ducts, or by using three or more containers of which always two are
coupled to the inlet and outlet ducts, while the non-coupled
containers are brought to the desirable operating temperature.
Instead of a four-way valve 35 for controlling the flow of hydrogen
gas, each of the containers 31 and 32 may comprise an inlet valve
52 and 54, respectively, and an outlet valve 53 and 55,
respectively, as is shown in FIG. 4.
Instead of constructing the pre-cooler 50 as a vessel with liquid
nitrogen, it may also be formed by a refrigerator, for example, a
cold-gas refrigerator. It is alternatively possible to obtain the
precooling by causing the hydrogen gas to expand in an expansion
machine while supplying external work.
It may be obvious from the above that the invention provides an
extremely reliable cooler for very low temperatures which comprises
no moving components and which operates in a noiseless and
vibration-free manner.
FIG. 5 show a device for compressing hydrogen gas which consists of
two containers 61 and 62, respectively, filled with LaNi.sub.5.
Coolers 64 and 65, respectively, and heaters 66 and 67,
respectively, are accommodated in each of the said containers. Each
of the containers comprises an inlet valve 68 and 69, respectively
and outlet valves 70 and 71, respectively. The outlet valves 70 and
71 communicate with an outlet duct 72 for high-pressure hydrogen,
while the inlet valves 68, 69 communicate with an inlet duct 73 for
low-pressure hydrogen. By alternately actuating the heaters 66, 67
and the coolers 64, 65, one of the containers is brought at a
higher temperature and the other is brought at a lower temperature,
desorption of hydrogen gas at higher pressure occurring in the
higher temperature container and absorption at lower pressure
occurring in the lower temperature container. The desorbed
high-pressure hydrogen gas is supplied to duct 72, while the
hydrogen gas to be absorbed is applied via duct 73. In this manner
an extremely simple compression device for hydrogen gas is
obtained.
* * * * *