WO2012114229A1 - Compresseur d'hydrogène à hydrure métallique - Google Patents

Compresseur d'hydrogène à hydrure métallique Download PDF

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Publication number
WO2012114229A1
WO2012114229A1 PCT/IB2012/050686 IB2012050686W WO2012114229A1 WO 2012114229 A1 WO2012114229 A1 WO 2012114229A1 IB 2012050686 W IB2012050686 W IB 2012050686W WO 2012114229 A1 WO2012114229 A1 WO 2012114229A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen
heat transfer
compressor
compression
transfer fluid
Prior art date
Application number
PCT/IB2012/050686
Other languages
English (en)
Inventor
Mykhaylo Lototskyy
Yevgeniy KLOCHKO
Vladimir Mikhailovich Linkov
Original Assignee
Eskom Holdings Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eskom Holdings Ltd filed Critical Eskom Holdings Ltd
Publication of WO2012114229A1 publication Critical patent/WO2012114229A1/fr

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
    • F04B37/00—Pumps having pertinent characteristics not provided for in, or of interest apart from, groups F04B25/00 - F04B35/00
    • F04B37/10—Pumps having pertinent characteristics not provided for in, or of interest apart from, groups F04B25/00 - F04B35/00 for special use
    • F04B37/18—Pumps having pertinent characteristics not provided for in, or of interest apart from, groups F04B25/00 - F04B35/00 for special use for specific elastic fluids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
    • F04B19/00—Machines or pumps having pertinent characteristics not provided for in, or of interest apart from, groups F04B1/00 - F04B17/00
    • F04B19/20—Other positive-displacement pumps
    • F04B19/24—Pumping by heat expansion of pumped fluid
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Definitions

  • the present invention relates to a metal hydride hydrogen compressor.
  • the present invention relates to a metal hydride hydrogen compressor which is adapted to be thermally driven.
  • MH metal hydrides
  • the hydrogen compressor comprises a plurality of hydride containers equipped with hydrogen inlet / outlet pipelines and heat exchange means, an inlet for hydrogen gas fed at a low inlet pressure and an outlet for hydrogen gas supplied at high pressure, as well as heating and cooling means providing a periodic heating / cooling of the heat exchange means associated with the corresponding hydride containers where high-pressure hydrogen desorption / low-pressure hydrogen absorption takes place.
  • the hydrogen inlet / outlet pipelines of the containers are connected through a one-way (check) valve arrangement, and the periodic heating / cooling of the heat exchange means is controlled by timing means.
  • the first, second and third containers were filled with different hydride-forming materials in the sequence of the decrease of thermal stability of the hydrogenated material disposed in the next container, as compared to the previous one.
  • the two assemblies of metal hydride containers disposed in the heat exchange jackets (let us call this assembly as a compression module) were heated / cooled in the opposite manner, i.e. when one compression module was heated up the other one was cooled down.
  • the prototype compressor according to the cited invention was characterised by a rather modest output productivity (28 L H 2 /min STP), however the productivity could be increased by using several identical containers whose gas pipelines were connected in parallel (let us call this assembly as a compression element).
  • the compressor according to the described invention used flows of hot and cold water for the heating and cooling, respectively.
  • the hot and cold water were supplied to and removed from the compressor via pipelines (separate for both input and output of each heat transfer fluid), and periodic heating and cooling of the compression modules were provided by a system of four three-way servo-valves whose common ports were connected to the inputs and outputs of the hot and cold water, and other ports - to the heat exchange jackets of the compression elements.
  • the MH containers (especially of the bigger size) must be properly pressure- temperature-rated that results (because of the increase of wall thickness) in the significant increase of their weight and, as a sequence, in a big parasitic thermal mass which has to be alternatively heated and cooled.
  • the thermal efficiency of the MH compressor decreases significantly, and special solutions for heat recovery / regeneration are necessary.
  • the compressor should provide a necessary compression ratio (usually about 20-40, or from 5-10 to 200 bar; the latter value corresponds to the pressure in standard gas cylinders) utilising the available temperature range.
  • a necessary compression ratio usually about 20-40, or from 5-10 to 200 bar; the latter value corresponds to the pressure in standard gas cylinders
  • the operation between ambient temperatures (cooling) and 150-200°C (heating) is the option available in the industry (including power engineering where steam and super-heated water having similar temperatures are available).
  • Lototsky et. al. M . Lototsky, H. Halldors, Ye. Klochko, J . Ren, V. Linkov.
  • the required total output productivity can be also increased by the increase of weight of MH material in the compression element, particularly, by the increase of the size of the MH container.
  • a metal hydride hydrogen compressor includes: (a) At least two compression modules;
  • Each compression module may comprise one or more metal hydride compression elements equipped with pipelines for input and output of a heat transfer fluid and a hydrogen input - output pipeline.
  • the compression element may comprise at least one metal hydride container which may be made as a pressure container filled with a hydride-forming material and equipped with a heat exchanger comprising pipelines for input and output of a heat transfer fluid .
  • the container may also comprise a heat transfer matrix disposed within the metal hydride material to form a metal hydride bed .
  • the container may also comprise a hydrogen input - output pipeline allowing hydrogen gas to flow to / from the metal hydride bed inside the container, through a filter element.
  • the hydride-forming material disposed in the container may be an AB 5 -type hydrogen storage intermetallic alloy where A is Lanthanum which may or may not be partially substituted with Cerium, Mischmetal or Calcium, and B is Nickel which may or may not be partially substituted with at least one component or a plurality of components selected from the group consisting of Cobalt, Aluminium, Manganese, Tin and Copper.
  • the hydride-forming material may also be an AB-type hydrogen storage intermetallic alloy where A is Titanium, and B is Iron which may or may not be partially substituted with at least one component or a plurality of components selected from the group consisting of Titanium, Vanadium and Manganese; the alloy may or may not be additionally doped by Oxygen.
  • the hydride-forming material may be an AB 2 -type hydrogen storage intermetallic alloy where A is Titanium which may or may not be partially substituted with Zirconium, and B includes a plurality of components selected from the group consisting of Iron, Chromium, Manganese, Nickel, Vanadium and Copper.
  • the pressure container may be made as a cylinder with spherical end caps.
  • the pressure container according to the preferred embodiment of the invention may be made of stainless steel, aluminium, or a multilayer composite material.
  • the pressure container may have an internal volume ranging from 2 to 10 litres and length-to-diameter ratio from 5 to 10.
  • One of the end caps of the pressure container may comprise the hydrogen input - output pipeline, and another - the pipelines for input and output of a heat transfer fluid.
  • the heat exchanger may be located inside the container and may be connected to the pipelines for input and output of a heat transfer fluid.
  • the internal heat exchanger may be made as two coaxial pipes. One end of the internal pipe and the space between the pipes may be connected to the pipelines for input and output of a heat transfer fluid which may be located from one side of the coaxial pipe assembly.
  • the external pipe may be plugged from the other end, and the other end of the internal pipe may form a gap with the plugged end of the external pipe to allow the heat transfer fluid to pass from / to the internal pipe to / from the space between the pipes.
  • the heat transfer matrix may be formed by a plurality of heat conductive lamellar fins which may be in a firm thermal contact with outer surface of the external pipe.
  • the fins may be preferably installed in a transversal position and made of copper, aluminium or lamellar recompressed expanded graphite.
  • the fins may be perforated .
  • the pressure container according to the preferred embodiment of the invention may comprise one or more gas arteria which may be longitudinally disposed within the metal hydride bed .
  • the gas arteria may or may not be connected to the hydrogen input - output pipeline.
  • the gas arteria may be made as tubular filter elements.
  • the ends of the tubular filter elements may be plugged .
  • the filter elements may be made of a porous material .
  • the compression element may also comprise a plurality of the pressure containers whose hydrogen input - output pipelines may be connected to a common hydrogen input - output pipeline, and the pipelines for input and output of the heat transfer fluid may be connected to the common input and output pipelines of the heat transfer fluid.
  • All compression elements within one compression module may have common pipelines for input and output of the heat transfer fluid which may be formed by the connection of the corresponding heat transfer fluid pipelines of the compression elements to input and output heat transfer fluid manifolds.
  • the compression elements in the compression module may have separate hydrogen input - output pipelines.
  • the gas-distributing system of the compressor according to the invention may comprise low-pressure hydrogen input pipeline, low-pressure manifold, and gas manifolds of the compression elements.
  • the said members of the gas- distributing system may be connected via a system of pipelines and one-way (check) valves which may prevent backflow of hydrogen from the higher pressure to the lower pressure zones of the system .
  • the compressor may comprise two (first and second) compression modules each of which may comprise one compression element to form layout of a one-stage hydrogen compressor.
  • each of two compression modules may comprise two (first and second) compression elements, to form layout of two-stage hydrogen compressor.
  • the first compression element may comprise one hydride-forming material which may provide hydrogen compression from low to medium pressure; and the second compression element may comprise another hydride-forming material which may provide hydrogen compression from medium to high pressure.
  • the hydride-forming material of the first compression element may be characterised by equilibrium hydrogen pressure below the low pressure of hydrogen supplied to the compressor at the temperature close to the temperature of the cold heat transfer fluid, and by the equilibrium hydrogen pressure above the medium pressure of hydrogen discharged to the associated second compression element at the temperature close to the temperature of the hot heat transfer fluid .
  • the hydride-forming material of the second compression element may be characterised by equilibrium hydrogen pressure below the medium pressure of hydrogen discharged from the associated first compression element, at the temperature close to the temperature of the cold heat transfer fluid, and by the equilibrium hydrogen pressure above the high pressure of hydrogen discharged from the compressor, at the temperature close to the temperature of the hot heat transfer fluid.
  • the heat transfer fluid distributing system may comprise at least four flow switches each of them may have one common port which can be alternatively connected to one of three ports, a, b and c.
  • the hot fluid system may comprise pipelines for inlet and outlet of a hot fluid which may be connected to hot fluid manifolds.
  • the hot fluid manifold connected to the inlet pipeline may be connected to the ports a and c of the first and second flow switches.
  • the hot fluid manifold connected to the outlet pipeline may be connected to the ports a and c of the third and fourth flow switches.
  • the cold fluid system may comprise pipelines for inlet and outlet of a cold fluid which may be connected to cold fluid manifolds.
  • the cold fluid manifold connected to the inlet pipeline may be connected to the ports c and a of the first and second flow switches.
  • the cold fluid manifold connected to the outlet pipeline may be connected to the ports c and a of the third and fourth flow switches.
  • the heating / cooling conduit may comprise pipelines which may connect the common port of the first flow switch to the pipeline for input of the heat transfer fluid to the first compression module, the pipeline for output of the heat transfer fluid from the first compression module to the common port of the third flow switch, the common port of the second flow switch to the pipeline for input of the heat transfer fluid to the second compression module, the pipeline for output of the heat transfer fluid from the second compression module to the common port of the fourth flow switch.
  • the heating / cooling conduit may also comprise pipelines which may connect the ports b of any pair of flow switches which are connected to sources and sinks of the hot and cold fluid. These connections may additionally comprise a circulation pump and a buffer tank which may be connected in series with each other and the connecting pipelines.
  • the input pipeline of the circulation pump is connected to the buffer tank.
  • the compressor may also comprise a control system which may provide switching of the flow switches and powering the circulation pump.
  • the control system may comprise a switching means and a timing means.
  • a method of operating a compressor includes a cyclic sequence of the following steps: of generating of higher pressure hydrogen in the first compression module with the simultaneous suction of lower pressure hydrogen in the second compression module; of temperature equilibration of the first and second compression modules; of generating of higher pressure hydrogen in the second compression module, with the simultaneous suction of lower pressure hydrogen in the first compression module; and of temperature equilibration of the first and second compression modules.
  • Step (a) may be realised by heating the compression elements belonging to the first compression module to a higher temperature, and simultaneous cooling the compression elements which belong to the second compression module to a lower temperature.
  • Step (c) may be realised by heating the compression elements belonging to the second compression module to a higher temperature, and simultaneous cooling the compression elements which belong to the first compression module to a lower temperature.
  • the heating may be provided by the hot heat transfer fluid.
  • the cooling may be provided by the cold heat transfer fluid.
  • Step (b) may provide first module to be cooled down and the second module to be heated up to an intermediate temperature.
  • Step (d) may provide first module to be heated up and the second module to be cooled down to an intermediate temperature.
  • Steps (b) and (d) may be realised by a circulation of the heat transfer fluid in between the first and second compression modules.
  • Steps (a) to (d) may be realised by switching the flow switches to the positions a, b and c and switching the circulation pump on and off by means of the control block in the following cyclic sequence stages:
  • step (a) and step (c) may be equal to a first time set-point of the timing means of the control block.
  • the durations of step (b) and step (d) may be equal to a second time set-point of the timing means of the control block.
  • the cold heat transfer fluid may be water at the temperature 10 to 30°C.
  • the hot heat transfer fluid may be water at the temperature 60 to 100°C.
  • the hot heat transfer fluid may be steam at the temperature 100 to 200°C and the pressure up to 16 bar.
  • the hot heat transfer fluid may be a superheated water at the temperature 100 to 200°C and the pressure up to 16 bar.
  • Figure 1 Piping diagram of a one-stage thermally driven metal hydride hydrogen compressor
  • the one-stage thermally driven metal hydride hydrogen compressor representing one embodiment of the invention includes the following components, as indicated by the corresponding reference numerals shown in Figure 1 :
  • the two-stage thermally driven metal hydride hydrogen compressor representing another embodiment of the invention includes the following components, as indicated by the corresponding reference numerals shown in Figure 2 :
  • the key component of any embodiment of this invention is the compression element (11-14) comprising one or more metal hydride containers.
  • the hydride container includes the following components, as indicated by the corresponding reference numerals shown in Figure 3 :
  • a compressor comprises at least two compression modules (10) schematically shown in Figures 1 and 2.
  • the compression module comprises one ( Figure 1 : 11 and 12), two ( Figure 2 : 11 and 13, 12 and 14) or more compression elements each of them is connected to the gas-distributing system of the compressor by means of hydrogen input / output pipeline (20) and to the heating / cooling conduit of the compressor by means of the input (60) and output (61) pipelines for the heat transfer fluid.
  • the compression module comprises more than one compression elements (see Figure 2 as an example)
  • their input pipelines (60) are connected to the input manifold of the heat transfer fluid (64) and the output ones (61) - to the output manifold of the heat transfer fluid (65).
  • Hydrogen input / output pipelines (20) of the associated compression elements (11-14) are connected to the associated gas manifolds (24).
  • the gas-distributing system of the compressor comprises low-pressure hydrogen input port (21) connected through low-pressure manifold (22) and one-way (check) valves (23) to gas manifolds (24) of the compression elements (11, 12) forming the first stage of the compressor.
  • the gas manifolds (24) of the compression elements (11, 12) are also connected, through one-way (check) valves (23) to the high-pressure manifold (25) connected to the high-pressure hydrogen output port (26).
  • the gas manifolds (24) of the first stage compression elements (11, 12) are connected, through one-way (check) valves (23), to the gas manifolds (24) of the second stage compression elements (14, 13) located in the opposite compression module (10). Further, the gas manifolds (24) of the second stage compression elements (13, 14) are connected, through one-way (check) valves (23), to the high-pressure manifold (25) connected to the high-pressure hydrogen output port (26).
  • a similar arrangement when the gas manifold of a compression element of n th stage of the compressor is connected through one-way valve to the gas manifold of a compression element of (n + l) th stage belonging to the opposite compression module can be realised in other embodiments of the invention realising a multi-stage compression layout.
  • the gas systems of the first and last stages are arranged in a similar manner as it is shown in Figure 2, i.e. the low-pressure manifold of the compressor is connected, through one-way valves (23), to gas manifolds (24) of the compression elements of the first stage, and gas manifolds (24) of the compression elements of the last stage are connected, through one-way valves (23), to the high-pressure manifold (25) of the compressor.
  • the pipelines for input and output of the heat transfer fluid belonging to the associated compression modules can be alternatively connected to the hot and cold fluid systems through the heat transfer fluid distribution system comprising four flow switches (31-34).
  • the flow switches can also provide the connection of the pipelines for input and output of the heat transfer fluid of both compression modules to the auxiliary part of the heating / cooling conduit by connecting the ports (b) of the flow switches (31 and 32) and (33 and 34).
  • the said connections should also accommodate in series circulation pump (62) and buffer tank (63).
  • the circulation pump (62) and buffer tank (63) are shown to be connected in between ports (b) of the flow switches (31 and 32), but alternative connection in between ports (b) of the flow switches (33 and 34) is also possible within invention.
  • the flow switches (31-34) can be made by different ways, in particular, as manifolds of three shut-off valves having common port on one side and separate ports on the other side, as 4-way switching valves, or specially designed gas distribution devices having a common port(s) which can be alternatively connected to one of three associated ports. Independently of the particular realisation, each flow switch (31-34) should be able to provide alternative connections of its common port to one of three associated ports, a, b and c.
  • the flow switches (31-34) have to be remotely actuated using solenoids, electric motors, or pneumatic / electro-pneumatic actuators.
  • the compressor also comprises hot fluid system formed by the hot fluid input pipeline (41), hot fluid manifolds (43) and hot fluid output pipeline (42).
  • the distribution of the hot fluid to the compression modules (10) is provided by the heat transfer fluid distribution system, through flow switches (31-34), where the hot fluid manifold (43) connected to the input pipeline (41) is connected to the ports a and c of the first (31) and the second (32) flow switches, respectively.
  • the hot fluid manifold (43) connected to the output pipeline (42) is connected to the ports a and c of the third (33) and the fourth (34) flow switches, respectively.
  • the cold fluid system of the compressor comprises the cold fluid input (51) and output (52) pipelines each connected to its own cold fluid manifold (53).
  • the manifold (53) connected to the input pipeline (51) is connected to the ports c and a of the first (31) and the second (32) flow switches, respectively.
  • the cold fluid manifold (53) connected to the output pipeline (52) is connected to the ports c and a of the third (33) and the fourth (34) flow switches, respectively.
  • Hydrogen compression is provided by the periodic heating and cooling of the metal hydride material(s) disposed in metal hydride containers.
  • All compression elements within one compression module have common pipelines for input (60) and output (61) of the heat transfer fluid formed by the connection of the corresponding heat transfer fluid pipelines of the compression elements to input (64) and output (65) heat transfer fluid manifolds.
  • the compression elements in the compression module have separate hydrogen input - output pipelines (20) connected to the associated gas manifolds (24).
  • the metal hydride containers may have any layout comprising the necessary components, viz. gas-proof pressure container (shell), hydride- forming material, heat exchanger, pipelines for input and output of heat transfer fluid, heat transfer matrix, and hydrogen input - output pipeline with filter element.
  • gas-proof pressure container shell
  • hydride- forming material e.g., hydride-forming material
  • heat exchanger e.g., heat exchanger
  • pipelines for input and output of heat transfer fluid e.g., heat transfer matrix
  • hydrogen input - output pipeline with filter element e.g., hydrogen input - output pipeline with filter element.
  • An optimal (for large-scale industrial hydrogen compressor applications) layout of a metal hydride container ( Figure 3) is suggested as a preferred embodiment of the present invention.
  • the metal hydride container comprises a pressure cylinder with spherical end caps (11) preferably made of stainless steel, but aluminium or multilayer composite material (if fit into specified pressure / temperature ratings) can be used as well.
  • the container can have internal volume from 2 to 10 litres, and length-to-diameter aspect ratio from 5 to 10.
  • the specified upper limit of the internal volume and lower limit of the aspect ratio are determined by the fact that the overrunning these limits will result in too long characteristic heat transfer distances in the metal hydride bed and, correspondingly, too slow hydrogen absorption / desorption processes.
  • the containers with lower internal volume and higher aspect ratio can be made in a more efficient layout providing shorter cycle time, but their application generates a number of problems discussed above.
  • the cylinder (11) is filled with a hydride-forming material (15) in the form of powder, granules or composite structures.
  • a hydride-forming material in the form of powder, granules or composite structures.
  • the usage of powder is preferable since it facilitates the procedure of filling the metal hydride container having a complicated internal geometry with the material (15) and, from the other hand, increases the hydrogen storage capacity of the container due to absence of inert binder necessary for making the granules or composite structures.
  • the kind and specific composition of the hydride-forming material depends on a number of factors, including hydrogen pressure / temperature operating conditions, purity of feeding hydrogen, required productivity, and compressor layout (one- or multi-stage). In the latter case the proper selection of the material is the most important factor, since thermodynamic and other performances of two materials applied in a previous and a next stage should be carefully aligned to each other.
  • the following kinds of the hydride- forming material can be applied taking into account the possibility of variation of their performances by the variation in the component composition :
  • AB 5 -type hydrogen storage intermetallic alloys where A is Lanthanum which can be partially substituted with Cerium, Mischmetal or Calcium (to decrease thermal stability of the hydride), and B is Nickel which can be partially substituted with at least one component or a plurality of components selected from the group consisting of Cobalt, Aluminium, Manganese, Tin and Copper (to increase thermal stability of the hydride and, in some cases, to add poisoning tolerance and to prolong operating cycle life of the material).
  • the AB 5 -type materials are the most flexible in possibility of variation of their thermodynamic characteristics by the component substitution, easy activated and relatively tolerant to the poisoning with impurities, so it is preferable to use them for the first stage of hydrogen compression.
  • AB-type hydrogen storage intermetallic alloys where A is Titanium, and B is Iron which can be partially substituted with at least one component or a plurality of components selected from the group consisting of Titanium, Vanadium and Manganese.
  • This kind of materials is less expensive and is characterised by higher hydrogen capacity than AB 5 -type alloys, but it is less flexible as to variation of its thermodynamic performances by the component substitution, has unfavourable thermodynamic features (two plateaux or significant plateau slope of pressure-composition isotherms) and is extremely sensitive to poisoning with gas impurities (the poisoning tolerance, however, can be increased in some extent by additional doping of the AB-type material by Oxygen).
  • the best use of this kind of materials is one for the second stage of hydrogen compressor in multi-stage layout.
  • AB 2 -type hydrogen storage intermetallic alloy where A is Titanium which may or may not be partially substituted with Zirconium, and B includes a plurality of components selected from the group consisting of Iron, Chromium, Manganese, Nickel, Vanadium and Copper. These alloys are characterised by higher hydrogen absorption capacity, flexibility in adjusting their thermodynamic properties by variation in component composition, possibility to achieve high equilibrium hydrogen pressures at moderate heating temperatures. They are, however, more expensive than AB 5 and AB and are easy deactivated by impurities (though in a lesser extent than AB). Their best use is in the second (and further, if necessary) stages of hydrogen compressor in multi-stage layout.
  • the cylinder (11) also comprises an internal heat exchanger made as two pipes (66, 67) of different diameter placed coaxially to each other and to the axis of the cylinder (11).
  • the internal (66) and external (67) pipes of the heat exchanger are coming through one of the end caps of the container through a tee-union assembly one end of which is leak-proof-connected to the cap, and the others (60, 61) form the input and output pipelines for the heat transfer fluid .
  • the input pipeline communicates with the internal pipe of the heat exchanger, and the output one with the space between the internal and external pipes. According to the embodiment under consideration, this feature is insignificant, and the opposite connection of the input and output pipes of the heat transfer fluid can also be applied.
  • the opposite sides of the pipes (66, 67) are ended close to the opposite end cap.
  • the external pipe (67) is plugged at the end, and the corresponding end of the internal pipe (66) ends at the shorter distance to form a gap with the plugged end .
  • the heat transfer fluid is allowed to pass from / to the internal pipe (66) to / from the space between the pipes forming a core tube of the heat exchanger where heat transfer fluid flows from / to the pipeline (60) to / from pipeline (61).
  • the heat exchanger is hold only from the side of the corresponding end cap of the container where pipelines (60, 61) are located .
  • the other end of the heat exchanger (corresponding to the plugged end of the pipe 67) is not fastened .
  • the outer pipe (67) of the heat exchanger is equipped by a plurality of heat conductive lamellar fins (68) which are in a firm thermal contact with outer surface of the pipe (67).
  • the fins (68) are preferably installed in a transversal position and made of heat- conductive material, such as copper, aluminium or lamellar recompressed expanded graphite.
  • the fins are also perforated to allow the hydride-forming material (15) to be easy loaded into the container and to be uniformly distributed in its inner space.
  • Gas fittings connecting the internal space of the container comprising the metal hydride bed (hydride forming material 15 and heat transfer matrix formed by fins 68) and hydrogen input / output pipeline (20) are installed in the end cap opposite to one carrying the pipelines (60, 61) for input and output of heat transfer fluid.
  • the fittings can include gas-proof connection equipped with in-line filter (16) and shut-off valve (18).
  • one or more gas arteria are introduced in the container.
  • the arteria are located longitudinally passing through the metal hydride bed.
  • at least one gas arterium can be connected to the inner side of gas fitting penetrating through the corresponding end cap of the container, it is not compulsory, and the gas arteria (plugged from both ends) can be just placed within the container in the proper position (as shown in Figure 3 for one arterium 17).
  • the contamination of gas flow by a fine hydride powder is prevented by the in-line filter (16).
  • Typical example of realisation of the described layout is a stainless steel container having internal volume of about 4 litres and length-to-diameter aspect ratio about 7.
  • Hydrogen storage capacity of the metal hydride container was found to be about 2 m 3 H 2 STP. 90% charge / discharge time of the container mainly depends on pressure / temperature conditions and flow rate of the heat transfer fluid, and was estimated to be approximately 1 to 2 hours.
  • metal hydride container of this type is incorporated in a compression element of the metal hydride compressor according to the present invention
  • productivity from 0.9 to 1.8 m 3 /h will be achieved using a single container in the compression element (in total 2 containers for one-stage and 4 for two-stage layout).
  • compression elements comprising ten containers in total 20 for one-stage and 40 for two-stage layout
  • productivity 9 to 18 m 3 /h will result in the productivity 9 to 18 m 3 /h.
  • step (d) is followed by step (a).
  • Steps (a) to (d) are realised by switching the flow switches (31) to the positions a, b and c and switching the circulation pump on and off by means of the control system (70) in the following cyclic sequence :
  • step (a) the hot fluid, from the input pipeline (41), manifold (43) and port a of first flow switch (31) flows through the first compression module (10), via corresponding input (60) and output (61) pipelines.
  • the metal hydride containers in the compression elements (11, 13) associated with this module are heated up, and the hot fluid is removed through port a of the third flow switch (33), manifold (43) and output pipeline (42).
  • the cold fluid, from the input pipeline (51), manifold (53) and port c of second flow switch (32) flows through the second compression module.
  • the metal hydride containers in the compression elements (12, 14) associated with this module are cooled down, and the cold fluid is removed through port a of the fourth flow switch (34), manifold (53) and output pipeline (52).
  • the step (a) continues for the specified period of time (approximately 0.5 to 3 hours, depending of size of the metal hydride containers and their geometric features, pressure / temperature conditions and flow rates of both cold and hot fluids) necessary for the desorption of high-pressure hydrogen from compression elements (11) of the first compression module and low-pressure hydrogen absorption in compression elements (12) of the second compression module.
  • the last also concerns the compression modules of the second stage, viz., (13, hydrogen desorption) and (14, hydrogen absorption).
  • the compressor would use hot and cold fluids available in the consumer's technological infrastructure.
  • the duration of the step (a), to be equal to the duration of the step (c) is predetermined by a first time set-point to be set by timing means of the control system (70).
  • the compression elements (11, 13) in the first compression module are heated to a higher temperature, T h that can be above the boiling point of water, if steam or superheated water is used as a hot fluid .
  • the control system (70) switches flow switches (31-34) into position b and the circulation pump (62) on.
  • the heat transfer fluid (preferably water) to be in the buffer tank at a medium temperature (7 " m ⁇ 50- 70°C) begins to circulate along the heating / cooling conduit, now connecting the buffer (63), pump (62), and heat exchangers in the metal hydride containers of the hot (11, 13) and cold ( 12, 14) compression modules.
  • the hot containers are cooled down and cold ones heated up to the temperature approaching T m from above and below, respectively.
  • the heat accumulated in the hot containers is used to pre-heat the cold containers, and partial heat recovery takes place. Since Ti ⁇ T m ⁇ T h , the temperature stresses in the cooled and heated containers are lower than in the case if the cold and hot fluids would directly used for temperature equilibration by an immediate switching from step (a) to step (c).
  • the duration of the step (b), to be equal to the duration of the step (d) is pre-determined by a second time set- point to be set by timing means of the control system (70).
  • Step (c) is similar to the step (a), providing cooling down the metal hydride containers (11, 13) of the first module resulting in lower-pressure hydrogen absorption therein, and heating up the metal hydride containers ( 12, 14) of the second module providing higher-pressure hydrogen desorption there-from .
  • the present invention allows to build reasonably efficient industrial-scale metal hydride hydrogen compressors driven by waste industrial heat which are simpler, less costly and labour-consuming, and more safe and reliable in the operation than the known prototypes. Due to high selectivity of the processes of reversible hydrogen absorption / desorption in metal hydrides, the operation of the compressor will result in a useful side effect of additional hydrogen purification during its compression . As a result, the output high pressure hydrogen will be delivered at high purity (better than 99.999%) and, therefore, will have a high commercial value.
  • the invention can be used in power engineering (for example, to provide cooling of turbo-generators at thermal or nuclear power plants), integrated hydrogen energy-technological systems for industrial and domestic applications, as well chemical engineering, gas service, etc., for filling gas cylinders with hie pressure high-purity hydrogen gas.

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  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

L'invention se rapporte à un compresseur d'hydrogène à hydrure métallique, qui est entraîné thermiquement et qui comprend, en liaison fonctionnelle appropriée : au moins deux modules de compression ; un système de distribution de gaz ; un système de distribution de fluide à transfert de chaleur comprenant au moins quatre commutateurs d'écoulement, chacun d'eux possédant un orifice commun qui peut être, en variante, relié à l'un des trois orifices, a, b et c ; un système à fluide chaud ; un système à fluide froid ; un conduit de chauffage/refroidissement ; et un système de commande. L'invention s'étend également à un procédé de fonctionnement d'un compresseur.
PCT/IB2012/050686 2011-02-21 2012-02-15 Compresseur d'hydrogène à hydrure métallique WO2012114229A1 (fr)

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Cited By (12)

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WO2014121251A2 (fr) * 2013-02-04 2014-08-07 Parker-Hannifin Corporation Compresseur de gaz
WO2014126455A1 (fr) * 2013-02-14 2014-08-21 Universiti Malaya Compresseur hybride métallique et son procédé de fonctionnement
WO2015031822A3 (fr) * 2013-08-30 2015-06-11 Heliix, Inc. Compresseur thermique
WO2016147134A1 (fr) * 2015-03-18 2016-09-22 University Of The Western Cape Compresseur d'hydrogène à hydrure métallique à plusieurs étages
US9816497B2 (en) 2013-02-03 2017-11-14 Go Natural Cng, Llc Compressors for natural gas and related devices, systems, and methods
FR3056263A1 (fr) * 2016-09-21 2018-03-23 Commissariat A L'energie Atomique Et Aux Energies Alternatives Compresseur d'hydrogene a hydrure metallique
WO2019120800A1 (fr) 2017-12-22 2019-06-27 Ecole Polytechnique Federale De Lausanne (Epfl) Procédé et dispositif de commande de compresseur hybride métallique
JP2019171328A (ja) * 2018-03-29 2019-10-10 住友精化株式会社 ガス昇圧方法およびガス昇圧装置
EP3722653A1 (fr) 2019-04-08 2020-10-14 Ecole Polytechnique Federale De Lausanne (EPFL) EPFL-TTO Système combiné de stockage-compression d'hydrogène pour le remplissage de réservoirs d'hydrogène haute pression
US11002255B2 (en) 2019-08-20 2021-05-11 Lowry Inheritors Trust Carbon negative clean fuel production system
US11428476B2 (en) * 2020-09-04 2022-08-30 Photon Vault, Llc Thermal energy storage and retrieval system
US11519655B2 (en) 2020-07-31 2022-12-06 Photon Vault, Llc Thermal energy storage and retrieval systems and methods

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US4085590A (en) * 1976-01-05 1978-04-25 The United States Of America As Represented By The United States Department Of Energy Hydride compressor
US4402187A (en) * 1982-05-12 1983-09-06 Mpd Technology Corporation Hydrogen compressor
US20040042957A1 (en) * 2000-03-17 2004-03-04 David Martin Method and apparatus for providing pressurized hydrogen gas
WO2010087723A1 (fr) * 2009-01-30 2010-08-05 Institutt For Energiteknikk Compresseur d'hydrogène à hydrure métallique à fonctionnement continu, et son procédé d'exploitation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10359032B2 (en) 2013-02-03 2019-07-23 Go Natural Cng, Llc Compressors for natural gas and related devices, systems, and methods
US9816497B2 (en) 2013-02-03 2017-11-14 Go Natural Cng, Llc Compressors for natural gas and related devices, systems, and methods
US10731636B2 (en) 2013-02-03 2020-08-04 Go Natural Cng, Llc Compressors for natural gas and related devices, systems, and methods
WO2014121251A3 (fr) * 2013-02-04 2014-10-02 Parker-Hannifin Corporation Compresseur de gaz
WO2014121251A2 (fr) * 2013-02-04 2014-08-07 Parker-Hannifin Corporation Compresseur de gaz
WO2014126455A1 (fr) * 2013-02-14 2014-08-21 Universiti Malaya Compresseur hybride métallique et son procédé de fonctionnement
WO2015031822A3 (fr) * 2013-08-30 2015-06-11 Heliix, Inc. Compresseur thermique
WO2016147134A1 (fr) * 2015-03-18 2016-09-22 University Of The Western Cape Compresseur d'hydrogène à hydrure métallique à plusieurs étages
RU2672202C1 (ru) * 2015-03-18 2018-11-12 Юниверсити Оф Дзе Вестерн Кэйп Многоступенчатый металлогидридный водородный компрессор
JP2019536946A (ja) * 2016-09-21 2019-12-19 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ 金属水素化物による水素コンプレッサ
US11204021B2 (en) 2016-09-21 2021-12-21 Commissariat A L'energie Atomique Et Aux Energies Alternatives Hydrogen compressor with metal hydride
JP7129972B2 (ja) 2016-09-21 2022-09-02 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ 金属水素化物による水素コンプレッサ
WO2018055277A1 (fr) 2016-09-21 2018-03-29 Commissariat A L'energie Atomique Et Aux Energies Alternatives Compresseur d'hydrogene a hydrure metallique
FR3056263A1 (fr) * 2016-09-21 2018-03-23 Commissariat A L'energie Atomique Et Aux Energies Alternatives Compresseur d'hydrogene a hydrure metallique
KR20200099189A (ko) * 2017-12-22 2020-08-21 에꼴 뽈리떼끄닉 뻬데랄 드 로잔느 (으뻬에프엘) 금속 수소화물 압축기 제어 장치 및 방법
WO2019120800A1 (fr) 2017-12-22 2019-06-27 Ecole Polytechnique Federale De Lausanne (Epfl) Procédé et dispositif de commande de compresseur hybride métallique
US11440796B2 (en) 2017-12-22 2022-09-13 Ecole Polytechnique Federale De Lausanne (Epfl) Metal hydride compressor control device and method
AU2018386368B2 (en) * 2017-12-22 2024-01-25 Ecole Polytechnique Federale De Lausanne (Epfl) Metal hydride compressor control device and method
KR102654175B1 (ko) * 2017-12-22 2024-04-04 에꼴 뽈리떼끄닉 뻬데랄 드 로잔느 (으뻬에프엘) 금속 수소화물 압축기 제어 장치 및 방법
JP2019171328A (ja) * 2018-03-29 2019-10-10 住友精化株式会社 ガス昇圧方法およびガス昇圧装置
EP3722653A1 (fr) 2019-04-08 2020-10-14 Ecole Polytechnique Federale De Lausanne (EPFL) EPFL-TTO Système combiné de stockage-compression d'hydrogène pour le remplissage de réservoirs d'hydrogène haute pression
WO2020207790A1 (fr) 2019-04-08 2020-10-15 Ecole Polytechnique Federale De Lausanne (Epfl) Système combiné de stockage-compression d'hydrogène pour le remplissage de réservoirs d'hydrogène haute pression
US12104751B2 (en) 2019-04-08 2024-10-01 Ecole Polytechnique Federale De Lausanne (Epfl) Combined hydrogen storage - compression system for the filling of high pressure hydrogen tanks
US11002255B2 (en) 2019-08-20 2021-05-11 Lowry Inheritors Trust Carbon negative clean fuel production system
US11519655B2 (en) 2020-07-31 2022-12-06 Photon Vault, Llc Thermal energy storage and retrieval systems and methods
US11428476B2 (en) * 2020-09-04 2022-08-30 Photon Vault, Llc Thermal energy storage and retrieval system

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