CA1083979A - Storage of gas - Google Patents
Storage of gasInfo
- Publication number
- CA1083979A CA1083979A CA268,849A CA268849A CA1083979A CA 1083979 A CA1083979 A CA 1083979A CA 268849 A CA268849 A CA 268849A CA 1083979 A CA1083979 A CA 1083979A
- Authority
- CA
- Canada
- Prior art keywords
- hydrogen
- palladium
- gas
- storage
- compound
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
- 238000003860 storage Methods 0.000 title claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 42
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012528 membrane Substances 0.000 claims abstract description 28
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 17
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 9
- 239000007769 metal material Substances 0.000 claims abstract description 7
- 229910019758 Mg2Ni Inorganic materials 0.000 claims abstract description 6
- 229910010340 TiFe Inorganic materials 0.000 claims abstract description 5
- 229910002335 LaNi5 Inorganic materials 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910001252 Pd alloy Inorganic materials 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 description 14
- 238000009792 diffusion process Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000428533 Rhis Species 0.000 description 1
- 208000036366 Sensation of pressure Diseases 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- -1 hydrogén Chemical class 0.000 description 1
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
Classifications
-
- 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
- C01B3/001—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 characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
- C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
- C01B3/0063—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof only containing a rare earth metal and only one other metal
- C01B3/0068—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof only containing a rare earth metal and only one other metal the other metal being nickel
-
- 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
-
- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
- C01B3/505—Membranes containing palladium
-
- 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
Abstract
ABSTRACT OF DISCLOSURE
This invention relates to the storage of hydrogen, An apparatus for storing hydrogen according to the invention incorporates a membrane constructed from a metallic material containing a major proportion of palladium in gas-tight connection with a gas-tight heat-exchange chamber containing an intermetallic compound capable of reversibly absorbing hydrogen, The metallic material may be palladium or a 20 wt % silver palladium alloy, The intermetallic compound may be LaNi5, TiFe, TiFe alloys, or Mg2Ni, The invention also includes method of storing hydrogen using an apparatus as described above,
This invention relates to the storage of hydrogen, An apparatus for storing hydrogen according to the invention incorporates a membrane constructed from a metallic material containing a major proportion of palladium in gas-tight connection with a gas-tight heat-exchange chamber containing an intermetallic compound capable of reversibly absorbing hydrogen, The metallic material may be palladium or a 20 wt % silver palladium alloy, The intermetallic compound may be LaNi5, TiFe, TiFe alloys, or Mg2Ni, The invention also includes method of storing hydrogen using an apparatus as described above,
Description
~IL08~979 This inven-tion relates to the storage of hydro~en, In view o~ the increasing importance of hydrogen as a source o~ energy, i-t i~ now a ~requent requirement to store hydrogcn in an accessible form. The conventional method ~or the storage of hydrogen on a small scale involves the use of tilick-walled pressurlsed cylinders which are weighty and bulky, and in certain circumstances constitute an explosion hazard. On a larger scale it is more conven-ient to store hydrogen in the liquid state, but this may only be achieved by the use of cryogenic techniques involving expensive lique-faction equipment, It is known that some metals will absorb hydrogen to a lesser or greater e~tent, resulting in potentially very compact stores, but in most cases -the hydrides formed are too stable to be of application as hydrogen storage media, Certain intermetallic compounds, however, have pressure-composition-temperature relationships-which are suitable for the absorption and thus storage of hydrogen, , ~, ; A limitation in the use o~ such intermetallic compounds, however, arises ~rom the fac-t that in addition to the propensity for hydrogen absorption, the hydride ~orming metal component inevitably forms compounds o~ high ., ~ .1 .
thermodynamic stability wlth many other gaseous molecules 1 such as 2~ H20, N2, CO and CO2 etc. The formation of these `' high stability compounds is an irrevers~le effect in the .,'' ' ~ - 2 ., :: ~ .
'............. ., . ,...... , :. , ~ . ' ~ 33~75~
hydrogen storage material and in practice results in progressiVe de-terioration or "poisoning" of the store. The source of these poison~
ing elements is normally from impurities in the hydrogen bein~ stored and these impurities are, from a practical point of view, almost un-avoidable in hydrogen obtained from commercial sources. It is, there-fore, one object of the present invention to provide an apparatus and method for the storage o hydrogen which may contain i-mpurities.
According to one aspect of the present invention appara-tus for the storage of hydrogen comprises a membrane constructed from a metallic material containing a major proportion of palladium in gas-tight connection with a gas-tight heat-exchange chamber containing an intermetallic compound capable of reversibly absorbing hydrogen.
According to a second aspect of the present invention a method for storing hydrogen comprises:
(a) causing hydrogen to diffuse into a gas-tight chamber through a membrane constructed from a metallic material containing a major proportion of palladium, and (b) contacting the so-diffused gas with a compound -'~ 20 within said chamber capable of reversibly ab-sorbing hydrogen.
Preferably, the palladium containing membrane is constructed ;, from pure palladium, 20% by weight silver-palladium or another alloy containing a major proportion .:
:.
- . " ,, - ,: - - " ,.
~0~3~9 by weight of palladi. um .
The chamber containing the intermetallic compound is capable of acting as a heat~exchanger by the provision internally or externally surrounding the chamber, of a heating elemen-t or heat-exchange tubes for the passage of a heat~exchange fluid.
Examples of intermetallic compounds which are .
suitable ~or use in the present invention are LaNi5 which may be used at 1-3 atmospheres pressure and near ambient temperature and TiFe alloys. Another suitable inter- .
metallic compound is Mg2Ni operating at 250C.
The invention will now be described by way of example ~ith reference to the iaccompanyinj~ drawings, in which:-Figure 1 shows in diagrammati.c form, a diffusion and storage apparatus according to the present invention; "
Figures 2 and 5 show two different types of , .
dif~usion membrane assemblies having a plurality of :
rectilinear membranes;
Figure 4 is a sec-tion throllgh an apparatlls aocording to .
the present invention utilising tubular membranes; and, ~.,, Figure 5 shows an alternative embodiment of the present invention In Figure 1 a diffusion membrane 2 made ~rom a palladiw~
;~, alloy is i.n planar form and is mounted in a vessel V.
Impure hydrogen is -fed via an lnlet pipe 1 to the upstream side of the membrane 2 and waste products are removed via a li bleed 3. A storage compound 5 is located in the vessel j .
., .
. ~i . . . . ~ 4 ~
., ... i , .. , . .. " , , . . . :, : , ., . : ,., . . :: -, "" ` ~01~3~79 adjacent to the membrane 2 and a valved outlet 6 is provided for controlling exit o-f the s.tored gas.. Palladium alloy membranes in such applications will only opera-te efficiently at elevated temperatures oE 150 - 400C, and it is, therefore, essential to use a storage compound which is compatible with these operating conditions. The titanium-iron materials already mentioned are, consequently, appropriate as also is the compound Mg2Ni, but the method can equally be applied to any storage substance having the required pressure - composition - relationships with respect to hydrogen.
A heater 4 which may either be external to or housed within the system serves to.maintain the diffusion membrane and compound at the operating tempera-ture.
~i .~ In the diffusion membrane assemblies o-E Figures 2 and 3, ~.
¦ hydrogen from any convenient source is passed under pressure ~ to inlet 1 oE a diffusion unit employing a plurality of ,3 rectilinear membranes 2 made from palladium, palladium-/~ silver or another alloy of palladium The ingoing hydrogen-containing gas may be of comparatively low purity and ;l normally completely unacceptable as a hydrogen storage ource, :Eor example directly Erom the ca-talyt:Lc re:Eorming oE
~, a hydrocarbon fuel. The hydrogen is separated from this ingoing gas by di:Efusion through the palladium alloy :;
~,~i membranes and issues from the membranes with a very low .' impurity content, usually a smali fraction o-f one par-t per :'I
million by volume The impurities or waste products are i removed from a "bleed" orifice 3 of the diffusion unit.
.
. i - , . . . .
~83979 The high purity hydrogen issues f'rom the di~fusion membranes a-t a pressure less than the partial pressure of' hydrogen in -the input gas, Preferably the heater (4 in Figure 1) is in the form of` a heat exchange chamber containi.ng intermetallic compQund surrounding the di~fusion membranes so that the diff'used gas lS then in contact with the inter-metallic compound 5. The chamber will have previously been exposed to high pressure hydrogen or some other activating proce~ure during its manufacture to ensure that i' the compound is converted into the activated condition necessary f'or rapid hydrogen ad~forption and desorption.
Hydrogen will be absorbed by the compound resulting in the well-known exothermic reaction and the heat liberated is removed by the heat-exchanger part of' the chamber, In the di~-fusion UIlit of' Figure 4 the diffusion membranes 3 of palladium alloy are o~ tubular ~orm, Impure hydrogen is ~ed to an inlet 1 f'itted with a valve iA on the upstream side o~ the membranes and waste products are removed via "b].eed" orifice 3 as in the case o~ the apparatus ~hown in Figures 2 and 3. The intermetallic storage ¢ompound 5 is located in a heat-e~changer chamber adjacent to the tubular membranes 2. A valved outlet 6 for the stored gas is provided as indica-ted. Palladi.wm alloy i:
membranes in such applications will only operate ef'f'iciently at elevated temperatures o~, say, 150-500QC, and it is, theref'ore, essential to use a storage compound ' which is compatible with these operating conditions.
,:
, :: . ,. ,: ,, . , . , .. - .. , ~ .. .. .. .
39~9 The titanilml-ir~on materia:Ls alrea~y mentionecl previous].y are consequently appropriate, as.also is the compound Mg2Ni, but the method herein described can equally be ~ applied to any storage substance having the required : press-ure-composition-relationships.with respect to hydrogén.
Some form of heater 4/4A which may either be'éxternal to or contained in the system is included to maintain the diffusion membrane and compound at the operating temperature.
When the store is fully charged, the inlet valve ~; lA is closed and the store is ready fo~ use. 1~l0n hydrogen is required, the outlet valve 6 is opened. Dehydrogenation of the intermetallic compound is an endothermic process and heat will be supplied as required vi.a the heat-exchange element 4 or tubes 4A, 'rhis heat requirement may be employed as a controllable factor in removing hydrogen from the store, only the quantity of.heat (conveniently as electrical power) necessary to "boil o-ff" the requisite quantity of ' hydrogen from the intermetallic compound being supplied at any one time ' When the store is depleted of hydrogen, va].ved outlet 6 is closed and the cycle repeated Due to the extremely ' high purity of the hydrogen stored in'the combined diffusion cell storage vessel system, poison.Lng effects . will be negligible over many cycles and a long operating '~ life for the store will result.
.1 An alternative embodiiuent of the present invention is illustrated in ~igure 5. The storage intermetallic ~
is contained in a.multiplicity of thin-walled palladium alloy , . .. .
._ 7 . .
. . .. : . . ~ ,~ ,.,., " ,, . ." . . .. -.. ' '.1 .. .. ... . . ..
~L0~3979 "
containers 2~. These may be formed f`rom palladium - 23/~
silver foil ~.002 in. thick, folded and welded on three sides to ~orm-small "ravioli-like" units or envelopes shown encircled in Figure 5. Alternative units may equally well be forme~ by other means such as packing the compound into thin-walled tubes, or vapour depositing or plating the palladium base envelope onto the storage ~edium, provided the compound is physically separated by the hydrogen permeable membrane from the impure gas. In operation of -the apparatus, the hydrogen from a source is supplied to the vessel V via inlet 1 and was~ products removed via a valved "bleed" 3.
For discharging -the store the source should be disconnected9 and the hydrogen passed via valved outlet valve 6 -to a user.
In this embodiment, during the discharge cycle it is necessary for the hydrogen to be desorbed by the inter~
metallic compound and subsequently, permeate in a reverse direction through the thin palladium alloy walls or membranes before being available at the outlet 6. Heating is provided as previously described at 1~. It is ~urther desirable that the upstream volume or volume not fi].led ~ith encapsula-ted .compound be l~ept to a minimum in the unit sho~n in F:L~ure 5 to ensure that any impur:Lty oarryover in the issuing gas is also kept to a minimum. Alternatively, this free volume may be purged ~ith pure hydrogen before attempting -to dis-charge the store.
~ - 8 -~, . ' ' ' , .
., . ; . . . .
' . . ' : , ,: : ' ' : ' . ' ':: ', . . '~'' ' ' ' ' : : ': . ' ' .
thermodynamic stability wlth many other gaseous molecules 1 such as 2~ H20, N2, CO and CO2 etc. The formation of these `' high stability compounds is an irrevers~le effect in the .,'' ' ~ - 2 ., :: ~ .
'............. ., . ,...... , :. , ~ . ' ~ 33~75~
hydrogen storage material and in practice results in progressiVe de-terioration or "poisoning" of the store. The source of these poison~
ing elements is normally from impurities in the hydrogen bein~ stored and these impurities are, from a practical point of view, almost un-avoidable in hydrogen obtained from commercial sources. It is, there-fore, one object of the present invention to provide an apparatus and method for the storage o hydrogen which may contain i-mpurities.
According to one aspect of the present invention appara-tus for the storage of hydrogen comprises a membrane constructed from a metallic material containing a major proportion of palladium in gas-tight connection with a gas-tight heat-exchange chamber containing an intermetallic compound capable of reversibly absorbing hydrogen.
According to a second aspect of the present invention a method for storing hydrogen comprises:
(a) causing hydrogen to diffuse into a gas-tight chamber through a membrane constructed from a metallic material containing a major proportion of palladium, and (b) contacting the so-diffused gas with a compound -'~ 20 within said chamber capable of reversibly ab-sorbing hydrogen.
Preferably, the palladium containing membrane is constructed ;, from pure palladium, 20% by weight silver-palladium or another alloy containing a major proportion .:
:.
- . " ,, - ,: - - " ,.
~0~3~9 by weight of palladi. um .
The chamber containing the intermetallic compound is capable of acting as a heat~exchanger by the provision internally or externally surrounding the chamber, of a heating elemen-t or heat-exchange tubes for the passage of a heat~exchange fluid.
Examples of intermetallic compounds which are .
suitable ~or use in the present invention are LaNi5 which may be used at 1-3 atmospheres pressure and near ambient temperature and TiFe alloys. Another suitable inter- .
metallic compound is Mg2Ni operating at 250C.
The invention will now be described by way of example ~ith reference to the iaccompanyinj~ drawings, in which:-Figure 1 shows in diagrammati.c form, a diffusion and storage apparatus according to the present invention; "
Figures 2 and 5 show two different types of , .
dif~usion membrane assemblies having a plurality of :
rectilinear membranes;
Figure 4 is a sec-tion throllgh an apparatlls aocording to .
the present invention utilising tubular membranes; and, ~.,, Figure 5 shows an alternative embodiment of the present invention In Figure 1 a diffusion membrane 2 made ~rom a palladiw~
;~, alloy is i.n planar form and is mounted in a vessel V.
Impure hydrogen is -fed via an lnlet pipe 1 to the upstream side of the membrane 2 and waste products are removed via a li bleed 3. A storage compound 5 is located in the vessel j .
., .
. ~i . . . . ~ 4 ~
., ... i , .. , . .. " , , . . . :, : , ., . : ,., . . :: -, "" ` ~01~3~79 adjacent to the membrane 2 and a valved outlet 6 is provided for controlling exit o-f the s.tored gas.. Palladium alloy membranes in such applications will only opera-te efficiently at elevated temperatures oE 150 - 400C, and it is, therefore, essential to use a storage compound which is compatible with these operating conditions. The titanium-iron materials already mentioned are, consequently, appropriate as also is the compound Mg2Ni, but the method can equally be applied to any storage substance having the required pressure - composition - relationships with respect to hydrogen.
A heater 4 which may either be external to or housed within the system serves to.maintain the diffusion membrane and compound at the operating tempera-ture.
~i .~ In the diffusion membrane assemblies o-E Figures 2 and 3, ~.
¦ hydrogen from any convenient source is passed under pressure ~ to inlet 1 oE a diffusion unit employing a plurality of ,3 rectilinear membranes 2 made from palladium, palladium-/~ silver or another alloy of palladium The ingoing hydrogen-containing gas may be of comparatively low purity and ;l normally completely unacceptable as a hydrogen storage ource, :Eor example directly Erom the ca-talyt:Lc re:Eorming oE
~, a hydrocarbon fuel. The hydrogen is separated from this ingoing gas by di:Efusion through the palladium alloy :;
~,~i membranes and issues from the membranes with a very low .' impurity content, usually a smali fraction o-f one par-t per :'I
million by volume The impurities or waste products are i removed from a "bleed" orifice 3 of the diffusion unit.
.
. i - , . . . .
~83979 The high purity hydrogen issues f'rom the di~fusion membranes a-t a pressure less than the partial pressure of' hydrogen in -the input gas, Preferably the heater (4 in Figure 1) is in the form of` a heat exchange chamber containi.ng intermetallic compQund surrounding the di~fusion membranes so that the diff'used gas lS then in contact with the inter-metallic compound 5. The chamber will have previously been exposed to high pressure hydrogen or some other activating proce~ure during its manufacture to ensure that i' the compound is converted into the activated condition necessary f'or rapid hydrogen ad~forption and desorption.
Hydrogen will be absorbed by the compound resulting in the well-known exothermic reaction and the heat liberated is removed by the heat-exchanger part of' the chamber, In the di~-fusion UIlit of' Figure 4 the diffusion membranes 3 of palladium alloy are o~ tubular ~orm, Impure hydrogen is ~ed to an inlet 1 f'itted with a valve iA on the upstream side o~ the membranes and waste products are removed via "b].eed" orifice 3 as in the case o~ the apparatus ~hown in Figures 2 and 3. The intermetallic storage ¢ompound 5 is located in a heat-e~changer chamber adjacent to the tubular membranes 2. A valved outlet 6 for the stored gas is provided as indica-ted. Palladi.wm alloy i:
membranes in such applications will only operate ef'f'iciently at elevated temperatures o~, say, 150-500QC, and it is, theref'ore, essential to use a storage compound ' which is compatible with these operating conditions.
,:
, :: . ,. ,: ,, . , . , .. - .. , ~ .. .. .. .
39~9 The titanilml-ir~on materia:Ls alrea~y mentionecl previous].y are consequently appropriate, as.also is the compound Mg2Ni, but the method herein described can equally be ~ applied to any storage substance having the required : press-ure-composition-relationships.with respect to hydrogén.
Some form of heater 4/4A which may either be'éxternal to or contained in the system is included to maintain the diffusion membrane and compound at the operating temperature.
When the store is fully charged, the inlet valve ~; lA is closed and the store is ready fo~ use. 1~l0n hydrogen is required, the outlet valve 6 is opened. Dehydrogenation of the intermetallic compound is an endothermic process and heat will be supplied as required vi.a the heat-exchange element 4 or tubes 4A, 'rhis heat requirement may be employed as a controllable factor in removing hydrogen from the store, only the quantity of.heat (conveniently as electrical power) necessary to "boil o-ff" the requisite quantity of ' hydrogen from the intermetallic compound being supplied at any one time ' When the store is depleted of hydrogen, va].ved outlet 6 is closed and the cycle repeated Due to the extremely ' high purity of the hydrogen stored in'the combined diffusion cell storage vessel system, poison.Lng effects . will be negligible over many cycles and a long operating '~ life for the store will result.
.1 An alternative embodiiuent of the present invention is illustrated in ~igure 5. The storage intermetallic ~
is contained in a.multiplicity of thin-walled palladium alloy , . .. .
._ 7 . .
. . .. : . . ~ ,~ ,.,., " ,, . ." . . .. -.. ' '.1 .. .. ... . . ..
~L0~3979 "
containers 2~. These may be formed f`rom palladium - 23/~
silver foil ~.002 in. thick, folded and welded on three sides to ~orm-small "ravioli-like" units or envelopes shown encircled in Figure 5. Alternative units may equally well be forme~ by other means such as packing the compound into thin-walled tubes, or vapour depositing or plating the palladium base envelope onto the storage ~edium, provided the compound is physically separated by the hydrogen permeable membrane from the impure gas. In operation of -the apparatus, the hydrogen from a source is supplied to the vessel V via inlet 1 and was~ products removed via a valved "bleed" 3.
For discharging -the store the source should be disconnected9 and the hydrogen passed via valved outlet valve 6 -to a user.
In this embodiment, during the discharge cycle it is necessary for the hydrogen to be desorbed by the inter~
metallic compound and subsequently, permeate in a reverse direction through the thin palladium alloy walls or membranes before being available at the outlet 6. Heating is provided as previously described at 1~. It is ~urther desirable that the upstream volume or volume not fi].led ~ith encapsula-ted .compound be l~ept to a minimum in the unit sho~n in F:L~ure 5 to ensure that any impur:Lty oarryover in the issuing gas is also kept to a minimum. Alternatively, this free volume may be purged ~ith pure hydrogen before attempting -to dis-charge the store.
~ - 8 -~, . ' ' ' , .
., . ; . . . .
' . . ' : , ,: : ' ' : ' . ' ':: ', . . '~'' ' ' ' ' : : ': . ' ' .
Claims (8)
CLAIMED ARE DEFINED AS FOLLOWS:
1. Apparatus for the storage of hydrogen comprising a membrane constructed from a metallic material containing a major proportion of palladium in gas-tight connection with a gas-tight heat-exchange chamber containing an intermetallic compound capable of reversibly absorbing hydrogen.
2. Apparatus according to Claim 1 wherein the metallic material is palladium or an alloy consisting essentially of 20 wt % silver and balance palladium.
3. Apparatus according to Claim 1 wherein the intermetallic compound is LaNi5, TiFe or alloys thereof, or Mg2Ni.
4. Apparatus as defined in claim 1 wherein the metallic material is palladium or an alloy consisting essentially of 20% silver and balance palladium, and wherein the inter-metallic compound is LaNi5, TiFe or alloys thereof, or Mg2Ni.
5. Apparatus as defined in Claim 1, 2 or 3 wherein the heat exchange chamber includes heating means for applying heat to the intermetallic compound.
6. Apparatus as defined in Claim 1, 2 or 3 wherein the heat exchange chamber includes heating means for applying heat to the inter-metallic compound and is located internally or externally relative to the chamber.
7. Apparatus according to Claim 1, 2 or 3 wherein the membrane is formed into a rectilinear envelope.
8. Apparatus according to Claim 1, 2 or 3 wherein the membrane is formed into a tube.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB53375/75 | 1975-12-31 | ||
| GB53375/75A GB1572796A (en) | 1975-12-31 | 1975-12-31 | Storage of hydrogen gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1083979A true CA1083979A (en) | 1980-08-19 |
Family
ID=10467582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA268,849A Expired CA1083979A (en) | 1975-12-31 | 1976-12-29 | Storage of gas |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS52107295A (en) |
| CA (1) | CA1083979A (en) |
| DE (1) | DE2658648A1 (en) |
| FR (1) | FR2337303A1 (en) |
| GB (1) | GB1572796A (en) |
| NL (1) | NL7614565A (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4216198A (en) * | 1977-12-19 | 1980-08-05 | Billings Energy Corporation | Self-regenerating method and system of removing oxygen and water impurities from hydrogen gas |
| DE2906642A1 (en) * | 1978-02-24 | 1979-08-30 | Mpd Technology | COMPRESSED GAS TANK |
| CA1136417A (en) * | 1978-07-17 | 1982-11-30 | Rodney L. Leroy | Hydrogen injection into gas pipelines and other pressurized gas containers |
| DE3175832D1 (en) * | 1980-11-13 | 1987-02-19 | Seikisui Chemical Co Ltd | Heat pump device |
| JPS57156301A (en) * | 1981-03-23 | 1982-09-27 | Sekisui Chem Co Ltd | Apparatus for containing metallic hydride |
| JP2640518B2 (en) * | 1987-11-04 | 1997-08-13 | サエス・ゲッテルス・ソシエタ・ペル・アチオニ | Method and apparatus for purifying hydrogen gas |
| WO1997035805A1 (en) * | 1996-03-28 | 1997-10-02 | Saes Pure Gas, Inc. | Method and apparatus for purifying hydrogen gas |
| DE19849216A1 (en) * | 1998-10-26 | 2000-04-27 | Andreas Noack | Separator for e.g. regeneration of activated carbon packing comprises two separate regions, with diffusion of preferentially-adsorbed component of gas or vapor mixture against temperature generation |
| JP2000351607A (en) * | 1999-06-09 | 2000-12-19 | Mitsubishi Heavy Ind Ltd | Hydrogen-producing apparatus |
| JP2001015142A (en) * | 1999-06-30 | 2001-01-19 | Mitsubishi Heavy Ind Ltd | Running method of fuel-cell vehicle and fuel-cell vehicle |
| FR2803045B1 (en) * | 1999-12-22 | 2002-10-11 | Cit Alcatel | OPTICAL FIBER AND FIBER OPTIC CABLE COMPRISING AT LEAST ONE HYDROGEN-ABSORBING INTERMETALLIC ELEMENT |
| DE102009053593B4 (en) * | 2009-11-17 | 2013-07-04 | Walter Graf | Process and apparatus for hydrogen transfer in methane fermenters |
| CN111892014B (en) * | 2020-07-30 | 2023-10-31 | 钢铁研究总院 | Air suction film and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL291485A (en) * | 1962-04-17 | |||
| US3376107A (en) * | 1963-10-10 | 1968-04-02 | Oka Akira | Stoichiometric transition metal hydrides |
| NL6906305A (en) * | 1969-01-24 | 1970-10-27 | ||
| US3516263A (en) * | 1969-03-25 | 1970-06-23 | Atomic Energy Commission | Method of storing hydrogen |
| JPS5531387B2 (en) * | 1974-12-02 | 1980-08-18 |
-
1975
- 1975-12-31 GB GB53375/75A patent/GB1572796A/en not_active Expired
-
1976
- 1976-12-23 DE DE19762658648 patent/DE2658648A1/en not_active Withdrawn
- 1976-12-28 JP JP15764576A patent/JPS52107295A/en active Pending
- 1976-12-29 CA CA268,849A patent/CA1083979A/en not_active Expired
- 1976-12-30 NL NL7614565A patent/NL7614565A/en not_active Application Discontinuation
- 1976-12-31 FR FR7639726A patent/FR2337303A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| NL7614565A (en) | 1977-07-04 |
| JPS52107295A (en) | 1977-09-08 |
| FR2337303A1 (en) | 1977-07-29 |
| FR2337303B1 (en) | 1981-12-24 |
| GB1572796A (en) | 1980-08-06 |
| DE2658648A1 (en) | 1977-07-14 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |