US3704600A - Cryogenic refrigerator - Google Patents

Cryogenic refrigerator Download PDF

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Publication number
US3704600A
US3704600A US77802A US3704600DA US3704600A US 3704600 A US3704600 A US 3704600A US 77802 A US77802 A US 77802A US 3704600D A US3704600D A US 3704600DA US 3704600 A US3704600 A US 3704600A
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weight
container
percent
containers
group
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US77802A
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English (en)
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Gijsbert Prast
Clifford Mcdonald Hargreaves
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US Philips Corp
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US Philips Corp
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B17/00—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type
    • F25B17/12—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type using desorption of hydrogen from a hydride
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • Y02A30/27—Relating to heating, ventilation or air conditioning [HVAC] technologies
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
    • Y02B30/62—Absorption based systems

Definitions

  • ABSTRACT A cryogenic refrigerator including cooling means for H 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 at low temperature and readily desorbing H at high temperature, which gas is again directed to said throttle.
  • 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.
  • Known cooling devices which do not demonstrate the above-described drawbacks are the so-called absorption refrigerators.
  • a cooling medium of higher pressure is supplied, via an inletduct 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.
  • 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 z 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.
  • 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.
  • isotherms can be drawn in a diagram in which the hydrogen gas pressure P is plotted vertically and the absorbed quantity of hydrogen C is plotted horizontally.
  • Each isotherm shows at a given pressure a horizontal variation, the so-called plateauf 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 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.
  • 0.80 g of hydrogen gas per centimeter is: taken up by LaNi 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 maybe 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.
  • the graph shown in FIG. 2 it is indicated how for LaNi 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 C and the other of which is heated to, for example, 80 C.
  • 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.
  • 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.
  • the containers comprise one of the alloys LaNi La Y Ni j La Zr ,Ni La' Ce Ni where 0.4 x 1; La*Ni where La is an alloy containing 85 percent by weight of La, percent by weight of Nd, 4 percent .by weight of Pr and 1 percent by weight of Ce.
  • these alloys have proved to have extremely good absorbing and desorbing properties for hydrogen gas.'lt is to be noted thatNi 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 onecontainer filled with an alloy of A and Bin 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 i 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.
  • FIG. I shows a graph of isotherms for LaNi
  • FIG. 2 shows a graph of the H gas outflow from LaNi, 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.
  • Reference numerals 31 and 32 in FIG. 3 denote two containers which are filled with a very fine powder of LaNi 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, ofa Joule-Kelvin cooling system.
  • the inlet duct 36 comprises acooler 38, a first counter flow heat exchanger 39, a heat exchanger 40, a
  • a throttle valve 42 which communicates with the outlet duct37 which also comprises the counter flow heat exchangers 39 and 41.
  • a cooler 44 and 45, respectively and aheating 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 C, while container 32 is heated, by means of the heating device 47, for example, an electric re sistance heating, to ya temperature of approximately 1 10 C.
  • the heating device 47 for example, an electric re sistance heating
  • a vessel containing liquid nitrogen, and via pressure in container 32 tends to drop below the plateau pressure associated with l l0 C or the pressure in the container 31 tends to rise above the plateau pressure of 20 C.
  • the operation is then switched, that isto say, the cooling water is now conducted throughcooler 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 thecontainers 31 and 32 have reached the operating temperatures of and 20 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.
  • 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.
  • the pre-cooler 50 may also be formed by a refrigerator, for example, a cold-gas refrigerator. It is alternatively possible to obtain the precoolingby causing the hydrogen gas to expand in an expansion machine while supplying external work.
  • 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 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.
  • 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 tempera ture 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 l7, 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 alternate
  • each of the containers contains one of the alloys LaNi La ,,Y Ni La Zr Ni La Ce Ni wherein 0.4 x 1; La Ni, wherein La is an alloy containing 85 percent by weight of La, percent by weight of Nd, 4 percent by weight of Pr and 1 percent by weight of Ce.
  • each of the containers comprises one of the alloys LaNi La Y Ni La Zr ,Ni,,; La Ce Ni wherein O.4 x 1; La Ni, wherein La is an alloy containing percent by weight of La, 10 percent by weight of Nd, 4 percent by weight of Pr and 1 percent by weight of Ce.
  • 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 l7, 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 an inlet duct for flowing said H to said container, an outlet duct for flowing H out of said container, means for cooling H in said outlet duct to below its inversion temperature, throttle means for expanding said cooled H 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.
  • A is a member selected from the group consisting of calcium, the rare earth elements
  • 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.
  • each of said containers contains one of the alloys in the group consisting of LaNi La ,,Y Ni La Zr Ni La,Ce, ,Ni 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 l percent by weight of Ce.
  • Apparatus according to claim 7 wherein said means for cooling H in the outlet duct comprises at least one counter-flow heat-exchanger cooled by the flow of expanded and cooled H in said inlet duct.
  • Apparatus for compressing H 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 l7, 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 an inlet duct for flowing said H to said container, an outlet duct for flowing H 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.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Sorption Type Refrigeration Machines (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
US77802A 1969-10-15 1970-10-05 Cryogenic refrigerator Expired - Lifetime US3704600A (en)

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NL6915564A NL6915564A (fr) 1969-10-15 1969-10-15

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US77802A Expired - Lifetime US3704600A (en) 1969-10-15 1970-10-05 Cryogenic refrigerator

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US (1) US3704600A (fr)
AT (1) AT299280B (fr)
BE (1) BE757518A (fr)
CA (1) CA919444A (fr)
CH (1) CH560364A5 (fr)
DE (1) DE2048513C3 (fr)
FR (1) FR2065387A5 (fr)
GB (1) GB1331284A (fr)
NL (1) NL6915564A (fr)
SE (1) SE361354B (fr)
SU (1) SU389667A3 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4096641A (en) * 1976-11-08 1978-06-27 The International Nickel Company, Inc. Method for storing hydrogen in nickel-calcium
US4096639A (en) * 1976-11-08 1978-06-27 The International Nickel Company, Inc. Nickel-mischmetal-calcium alloys for hydrogen storage
US4111002A (en) * 1976-02-25 1978-09-05 U.S. Philips Corporation Cyclic desorption refrigerator and heat pump, respectively
US4321799A (en) * 1980-03-28 1982-03-30 Georgia Tech Research Institute Method for utilizing gas-solid dispersions in thermodynamic cycles for power generation and refrigeration
EP0115159A2 (fr) * 1982-12-27 1984-08-08 Inco Engineered Products Limited Compresseur pour hydrogène
US5339649A (en) * 1991-12-09 1994-08-23 Kabushikikaisha Equos Research Cryogenic refrigerator
EP1000304A4 (fr) * 1997-04-23 2000-05-17 American Superconductor Corp Systeme de refroidissement pour aimant supraconducteur
US6376943B1 (en) 1998-08-26 2002-04-23 American Superconductor Corporation Superconductor rotor cooling system
US6489701B1 (en) 1999-10-12 2002-12-03 American Superconductor Corporation Superconducting rotating machines
US20120229959A1 (en) * 2011-03-11 2012-09-13 Grid Logic Incorporated Variable impedance device with integrated refrigeration
US11813672B2 (en) 2020-05-08 2023-11-14 Grid Logic Incorporated System and method for manufacturing a part

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3943719A (en) * 1975-02-26 1976-03-16 Terry Lynn E Hydride-dehydride power system and methods
NL7512833A (nl) * 1975-11-03 1977-05-05 Philips Nv Hydriden van intermetallische verbindingen en de toepassing daarvan bij de opslag van water- stof.
NL7602015A (nl) * 1976-02-27 1977-08-30 Philips Nv Geheugensysteem.
US4200144A (en) * 1977-06-02 1980-04-29 Standard Oil Company (Indiana) Hydride heat pump
DE3272819D1 (en) * 1981-03-23 1986-10-02 Seikisui Chemical Co Ltd Metal hydride reactor
WO1990008294A1 (fr) * 1989-01-12 1990-07-26 Innovatsionny Tsentr 'interlab' Refrigerateur a adsorption cryogenique utilise dans un procede de refroidissement d'un objet
SE9201768L (sv) * 1992-06-09 1993-12-10 Electrolux Ab Kylskåp med intermittent arbetande sorptionskylapparat

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3195322A (en) * 1961-09-22 1965-07-20 Atomic Energy Authority Uk Refrigerator employing helium
US3302415A (en) * 1963-12-12 1967-02-07 Comp Generale Electricite Cryogenic refrigerating apparatus
US3397549A (en) * 1967-05-29 1968-08-20 Research Corp Cyclic desorption refrigerator

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3195322A (en) * 1961-09-22 1965-07-20 Atomic Energy Authority Uk Refrigerator employing helium
US3302415A (en) * 1963-12-12 1967-02-07 Comp Generale Electricite Cryogenic refrigerating apparatus
US3397549A (en) * 1967-05-29 1968-08-20 Research Corp Cyclic desorption refrigerator

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4111002A (en) * 1976-02-25 1978-09-05 U.S. Philips Corporation Cyclic desorption refrigerator and heat pump, respectively
US4096641A (en) * 1976-11-08 1978-06-27 The International Nickel Company, Inc. Method for storing hydrogen in nickel-calcium
US4096639A (en) * 1976-11-08 1978-06-27 The International Nickel Company, Inc. Nickel-mischmetal-calcium alloys for hydrogen storage
US4321799A (en) * 1980-03-28 1982-03-30 Georgia Tech Research Institute Method for utilizing gas-solid dispersions in thermodynamic cycles for power generation and refrigeration
EP0115159A2 (fr) * 1982-12-27 1984-08-08 Inco Engineered Products Limited Compresseur pour hydrogène
US4505120A (en) * 1982-12-27 1985-03-19 Ergenics, Inc. Hydrogen compressor
EP0115159A3 (fr) * 1982-12-27 1986-02-19 Inco Engineered Products Limited Compresseur pour hydrogène
US5339649A (en) * 1991-12-09 1994-08-23 Kabushikikaisha Equos Research Cryogenic refrigerator
EP1000304A4 (fr) * 1997-04-23 2000-05-17 American Superconductor Corp Systeme de refroidissement pour aimant supraconducteur
EP1000304A2 (fr) * 1997-04-23 2000-05-17 American Superconductor Corporation Systeme de refroidissement pour aimant supraconducteur
US6376943B1 (en) 1998-08-26 2002-04-23 American Superconductor Corporation Superconductor rotor cooling system
US6812601B2 (en) 1998-08-26 2004-11-02 American Superconductor Corporation Superconductor rotor cooling system
US6489701B1 (en) 1999-10-12 2002-12-03 American Superconductor Corporation Superconducting rotating machines
US20120229959A1 (en) * 2011-03-11 2012-09-13 Grid Logic Incorporated Variable impedance device with integrated refrigeration
US9072198B2 (en) * 2011-03-11 2015-06-30 Grid Logic Incorporated Variable impedance device with integrated refrigeration
US11813672B2 (en) 2020-05-08 2023-11-14 Grid Logic Incorporated System and method for manufacturing a part

Also Published As

Publication number Publication date
FR2065387A5 (fr) 1971-07-23
AT299280B (de) 1972-06-12
DE2048513C3 (de) 1979-10-04
CA919444A (en) 1973-01-23
NL6915564A (fr) 1971-04-19
CH560364A5 (fr) 1975-03-27
SE361354B (fr) 1973-10-29
DE2048513B2 (de) 1978-10-19
BE757518A (fr) 1971-04-14
SU389667A3 (fr) 1973-07-05
DE2048513A1 (de) 1971-04-22
GB1331284A (en) 1973-09-26

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