EP1263676A1 - Method for reversibly storing hydrogen on the basis of alkali metals and aluminium - Google Patents
Method for reversibly storing hydrogen on the basis of alkali metals and aluminiumInfo
- Publication number
- EP1263676A1 EP1263676A1 EP01931491A EP01931491A EP1263676A1 EP 1263676 A1 EP1263676 A1 EP 1263676A1 EP 01931491 A EP01931491 A EP 01931491A EP 01931491 A EP01931491 A EP 01931491A EP 1263676 A1 EP1263676 A1 EP 1263676A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aluminum
- metals
- metal
- hydrides
- alkali
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 40
- 239000001257 hydrogen Substances 0.000 title claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 26
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 21
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 20
- 239000004411 aluminium Substances 0.000 title abstract 2
- 230000002441 reversible effect Effects 0.000 claims abstract description 14
- 239000011232 storage material Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims abstract description 9
- 150000008046 alkali metal hydrides Chemical class 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 26
- 238000003860 storage Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 7
- 150000004678 hydrides Chemical class 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 4
- -1 alcoholates Chemical class 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 150000002902 organometallic compounds Chemical class 0.000 claims description 3
- 150000003623 transition metal compounds Chemical class 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 229910000765 intermetallic Inorganic materials 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000011734 sodium Substances 0.000 description 17
- 229910000104 sodium hydride Inorganic materials 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 5
- 239000012312 sodium hydride Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 101100010166 Mus musculus Dok3 gene Proteins 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 240000007124 Brassica oleracea Species 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 208000001848 dysentery Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000002909 rare earth metal compounds Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000007704 transition Effects 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
-
- 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 method for the reversible storage of hydrogen, alkali metals or their hydrides and aluminum metal being doped with transition metal catalysts being used as hydrogen storage materials.
- the disadvantages of the previous method of the SGK are that the preparation and purification of the commercial sodium alanate, the production of Na 3 AIH 6 or Na 2 LiAIH 6 and the subsequent doping in organic solvents are preparative and relatively complex and in most cases easy to use volatile, highly flammable (ether, pentane) and prone to peroxide (ether, THF) solvent required.
- the starting materials for their production can be used in the form of alkali metal hydrides or alkali metals (in particular NaH or Na), Al powder and dopants.
- the alanates formed from these starting materials in a hydrogenation step are immediately functional as H 2 stores and have improved storage properties compared to PCT / WO 97/03919.
- Na and Li alanates can be prepared by mixing the corresponding alkali metal hydrides (or alkali metals) and aluminum in ethers, amines and aliphatic or aromatic hydrocarbons, if appropriate in the presence of catalytic amounts of organoaluminum Compounds reacted with hydrogen under pressure.
- 3,138,433 (1964) describes, inter alia, a method for the preparation of NaAIH 4 from NaH, Al and hydrogen under pressure in THF, using Ti, Zr, Hf and Th tetrahalides as catalysts; in the only patent example contained therein, however, a yield of NaAIH of max. 21.8% stated.
- a direct synthesis of Na 3 AIH 6 is possible in 98% yield according to Inorg. Chem. 5 (1966) 1615, by reacting Na and activated Al powder in diglyme in the presence of Et 3 Al with hydrogen under pressure (350 bar).
- a synthesis of NaAIH 4 from the elements Na, AI and H is also possible in the absence of organic solvents according to Dokl. Akad.
- the alkali metal alanates prepared by the processes mentioned were not taken into consideration for the purposes of hydrogen storage.
- the preparation of the storage material according to the present invention is very simple and completely dispenses with organic solvents.
- the aluminum powder used in the present process is cheaper and easier to handle than the sodium alanate previously used. It was particularly surprising that the hydrogenation of aluminum in the presence of alkali metals or metal hydrides at temperatures well below the melting points of the metal / metal hydride starting materials involved and the metal alianate products, ie in solid form, succeeds (in contrast to the direct synthesis cited above) according to Dymova et al., Dokl. Akad. Nauk SSSR 215 (1974) 1369, English 256 "Direct Synthesis of Alkali Metal Aluminum Hydrides in the Melt").
- aluminum powder is mixed with powdered sodium hydride and mixed with catalytic amounts of titanium tetrabutylate.
- the mass obtained in this way can be directly reversible Hydrogen storage can be used. If Al and NaH are used in a molar ratio of 1: 1, NaAIH 4 is obtained in the hydrogenation, while Na 3 AIH 6 is obtained in a molar ratio of 1: 3 after the hydrogenation.
- Another particular advantage of the present process for the reversible storage of hydrogen is that, by simplifying the previously known method according to PCT / WO 97/03919, the desorption and absorption kinetics could be significantly improved.
- FIG. 2 shows the course of hydrogenation of a hydrogenation cycle according to the previous method at 170 ° C. and according to the present method at 118 ° C. and illustrates the clearly gained activity.
- FIG. 3 shows 33 hydrogenation / dehydrogenation cycles of a material according to the present method and prove the reversibility of the new materials.
- a typical storage material preparation according to the present invention is that aluminum powder, untreated or after briefly heating in vacuo to about 200 ° C., is stirred vigorously with finely powdered sodium hydride under a protective gas (eg argon). Subsequently, with stirring (or possibly with grinding), catalytic amounts of titanium tetra-n-butoxide (0.1 to 10 mol% based on aluminum, preferably 1 to 5 mol%) are added dropwise. In this way, a gray, slightly sticky, but still pourable powder mixture is obtained, which is introduced into an autoclave.
- the first step is to hydrogenate under pressures between 5 and 150 bar and temperatures between 20 and 200 ° C. The mixture is then dehydrated against elevated pressure or normal pressure at temperatures between 50 and 250 ° C.
- the aluminum is preferably used in the form of a fine cut (see Examples 1 and 5: surface It. BET measurement 12.2 or 2.0 m 2 / g).
- the aluminum used can optionally be preactivated by grinding, exposure to ultrasound or chemical activation.
- sodium hydride or sodium other alkali metal hydrides or alkali metals (in particular Li and K) can be used individually or in combinations.
- the molar ratio between aluminum and alkali metal can vary between 1: 0.3 and 1: 5. If aluminum and Na or NaH are used in a molar ratio of - 1: 1 or - 1: 3, the hydrogenation gives NaAIH 4 or Na 3 AIH 6 .
- the alkali metals or their hydrides can optionally be pretreated before use by grinding or exposure to ultrasound.
- Transition metals or transition metal compounds or alloys of groups 3-11 of the PSE and rare earth metals are used individually or in combinations, which can be bound to elements of groups 14-17 or hydrogen, as catalysts.
- the transition metal or rare earth metal compounds are preferably used in the form of halides, hydrides, alcoholates, amides or organometallic compounds. Halides, alcoholates and organometallic compounds of titanium, zirconium and rare earth metals are particularly preferred.
- Example 1 Al and NaH powder mixture doped with titanium tetra-n-butoxide as a reversible hydrogen storage; 33-cycle test
- the aluminum used was an AI cut (Lunasol) from the Frankfurt bronze paint and sheet metal factory Julius Schopflocher AG with a surface area of 12.2m 2 / g (It. BET measurement).
- the NaH was finely pulverized in a glass ball mill.
- the aluminum powder was briefly heated to 200 ° C. at 0.1 mbar (aluminum content according to elementary analysis by H. Kolbe, Mülheim a.d.Ruhr: 91.7% by weight).
- Fig. 1 shows the course of dehydrogenation (8th cycle, 3.96% by weight H 2 ) compared to the prior art.
- Fig. 3 shows the dependence of the hydrogen storage capacity (measured using the amount of H 2 released during dehydrogenation) on the number of cycles.
- the storage material was removed from the autoclave in hydrogenated form and examined by infrared spectroscopy.
- the IR spectrum shows AIH 4 and AIH 6 bands, in addition to weak CH and CO bands (alcoholate groups).
- Example 2 Al and NaH powder mixture doped with titanium tetra-n-butylate as a reversible hydrogen storage using untreated aluminum cut
- the storage material preparation was carried out analogously to Example 1, but the untreated commercial product was used here instead of the aluminum heated in a vacuum.
- the material was examined in 7 cycles and reached a storage capacity of 3.7% by weight H 2 in the 3rd hydrogenation process and 3.6% by weight H 2 in the 7th hydrogenation step.
- Example 3 Al and NaH powder mixture doped with ⁇ -TiCI 3 as a reversible hydrogen storage agent
- the storage material preparation was carried out analogously to Example 1, but the aluminum grinding was not baked in a vacuum, but rather before it was used Mechanically grind in a glass ball mill. Instead of Ti (OBu) 4 were
- the material was cyclized and reached a capacity of 2.5% by weight H 2 in the 1st hydrogenation and 2.9% by weight in the 5th hydrogenation step (at 135 ° C / ⁇ 140bar)
- the storage material preparation was carried out analogously to Example 1, but the aluminum grinding was not baked in a vacuum, but was mechanically ground in a glass ball mill before being used.
- the molar ratio between aluminum and sodium hydride was 1: 2.9.
- the material reached a capacity of 2.2 wt .-% H 2 and 5.
- hydrogenation step (at 117 ° C / 35 bar) 1, 5 wt .-% H 2 in the 1st hydrogenation.
- Example 5 Al and NaH powder mixture doped with titanium tetra-n-butylate as reversible hydrogen storage using spherical Al powder ⁇ 20 ⁇
- the storage material preparation was carried out analogously to Example 2, with a spherical Al powder ( ⁇ 20 ⁇ ) from Aldrich (surface according to BET measurement: 2.0 m 2 / g) being used in the untreated form instead of the Al grinding.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to a method for reversibly storing hydrogen. The inventive method is characterised in that reversible hydrogen storage materials are used. Said materials contain mixtures of an aluminium metal comprising alkali metals and/or alkali metal hydrides and transition metal and/or rare-earth element metal catalysts.
Description
Verfahren zur reversiblen Speicherung von Wasserstoff auf der Basis von Process for the reversible storage of hydrogen on the basis of
Alkalimetallen und AluminiumAlkali metals and aluminum
Die vorliegende Erfindung betrifft ein Verfahren zur reversiblen Speicherung von Wasserstoff, wobei Alkalimetalle oder ihre Hydride und Aluminiummetall unter Dotierung mit Übergangsmetall-Katalysatoren als Wasserstoffspeicher-Materialien verwendet werden.The present invention relates to a method for the reversible storage of hydrogen, alkali metals or their hydrides and aluminum metal being doped with transition metal catalysts being used as hydrogen storage materials.
Nach der Patentanmeldung der Studiengesellschaft Kohle mbH (SGK) PCT/WO 97/03919 ist ein Verfahren zur reversiblen Speicherung von Wasserstoff bekannt, das als Speichermaterialien die Alkalimetallalanate der allgemeinen Formel M1p(i-x)M2 pxAIH3+p (1) M1 = Na, K; M2 = Li, K; 0<x<~0.8; 1 <p<3 verwendet. Zur Verbesserung der Hydrier-/Dehydrierkinetik werden die Alkalimetallalanate mit Übergangsmetallverbindungen in katalytischen Mengen dotiert. Besondere Verwendung finden die Alanate NaAIH , Na3AIH6 und Na2LiAIH6.According to the patent application of the Studiengesellschaft kohl mbH (SGK) PCT / WO 97/03919, a process for the reversible storage of hydrogen is known which uses the alkali metal alanates of the general formula M 1 p (i- x ) M 2 px AIH 3+ p ( 1) M 1 = Na, K; M 2 = Li, K; 0 <x <~ 0.8; 1 <p <3 used. To improve the hydrogenation / dehydrogenation kinetics, the alkali metal alanates are doped with transition metal compounds in catalytic amounts. The alanates NaAIH, Na 3 AIH 6 and Na 2 LiAIH 6 find particular use.
Die Nachteile des bisherigen Verfahrens der SGK bestehen darin, daß die Darstellung und Reinigung des kommerziellen Natriumalanats, die Herstellung von Na3AIH6 oder Na2LiAIH6 und die anschließende Dotierung in organischen Lösemitteln präparativ relativ aufwendig sind und in den meisten Fällen den Einsatz leicht flüchtiger, hochentzündlicher (Ether, Pentan) und zur Peroxidbildung neigender (Ether, THF) Lösemittel erfordert.The disadvantages of the previous method of the SGK are that the preparation and purification of the commercial sodium alanate, the production of Na 3 AIH 6 or Na 2 LiAIH 6 and the subsequent doping in organic solvents are preparative and relatively complex and in most cases easy to use volatile, highly flammable (ether, pentane) and prone to peroxide (ether, THF) solvent required.
Es wurde nun überraschenderweise gefunden, daß an Stelle der übergangsmetalldotierten Alkalimetallalanate als Wasserstoffspeicher die Ausgangsmaterialien zu deren Herstellung in Form von Alkalimetallhydriden oder Alkalimetallen (insbesondere NaH bzw. Na), AI-Pulver und Dotierungsmitteln eingesetzt werden können. Die aus diesen Ausgangsmaterialien in einem Hydrierschritt entstehenden Alanate sind unmittelbar als H2-Speicher funktionsfähig und verfügen über im Vergleich zu PCT/WO 97/03919 verbesserte Speichereigenschaften.It has now surprisingly been found that, instead of the transition metal-doped alkali metal alanates as hydrogen stores, the starting materials for their production can be used in the form of alkali metal hydrides or alkali metals (in particular NaH or Na), Al powder and dopants. The alanates formed from these starting materials in a hydrogenation step are immediately functional as H 2 stores and have improved storage properties compared to PCT / WO 97/03919.
Verfahren zur Herstellung von Alkalimetall-Alanaten aus Alkalimetallhydriden (oder Alkalimetallen), Aluminium und Wasserstoff sind bekannt. Eine Übersicht der Methoden zur Darstellung von NaAIH4, Na3AIH6 und Na2LiAIH6 ist in J. Alloys
& Compounds, ... 2000 ..., gegeben. So lassen sich nach der deutschen Patentschrift 1 136 987 (1962) Na- und Li-Alanate herstellen, indem man die entsprechenden Alkalimetallhydride (oder Alkalimetalle) und Aluminium in Ethern, Aminen und aliphatischen oder aromatischen Kohlenwasserstoffen, ggf. in Gegenwart katalytischer Mengen von Organoaluminium-Verbindungen, mit Wasserstoff unter Druck umsetzt. Die US-Patentschrift 3,138,433 (1964) beschreibt u.a. eine Methode zur Darstellung von NaAIH4 aus NaH, AI und Wasserstoff unter Druck in THF, wobei Ti-, Zr-, Hf und Th-Tetrahalogenide als Katalysatoren verwendet werden; in dem einzigen darin vorhandenen Patentbeispiel wird allerdings eine Ausbeute an NaAIH von max. 21.8 % angegeben. Eine Direktsynthese von Na3AIH6 gelingt in 98 %-iger Ausbeute nach Inorg. Chem. 5 (1966) 1615, indem man Na und aktiviertes AI-Pulver in Diglyme in Gegenwart von Et3AI mit Wasserstoff unter Druck (350 bar) umsetzt. Eine Synthese von NaAIH4 aus den Elementen Na, AI und H ist auch in Abwesenheit von organischen Lösemitteln nach Dokl. Akad. Nauk SSSR 215 (1974) 1369, engt. 256 dadurch möglich, daß man den Prozeß in der Schmelze (>175 bar, <280°C) durchführt. Die nach den genannten Verfahren dargestellten Alkalimetall-Alanate wurden für die Zwecke der Wasserstoffspeicherung nicht in Betracht gezogen.Processes for the production of alkali metal alanates from alkali metal hydrides (or alkali metals), aluminum and hydrogen are known. An overview of the methods for the preparation of NaAIH 4 , Na 3 AIH 6 and Na 2 LiAIH 6 is in J. Alloys & Compounds, ... 2000 ..., given. Thus, according to German Patent 1 136 987 (1962), Na and Li alanates can be prepared by mixing the corresponding alkali metal hydrides (or alkali metals) and aluminum in ethers, amines and aliphatic or aromatic hydrocarbons, if appropriate in the presence of catalytic amounts of organoaluminum Compounds reacted with hydrogen under pressure. US Pat. No. 3,138,433 (1964) describes, inter alia, a method for the preparation of NaAIH 4 from NaH, Al and hydrogen under pressure in THF, using Ti, Zr, Hf and Th tetrahalides as catalysts; in the only patent example contained therein, however, a yield of NaAIH of max. 21.8% stated. A direct synthesis of Na 3 AIH 6 is possible in 98% yield according to Inorg. Chem. 5 (1966) 1615, by reacting Na and activated Al powder in diglyme in the presence of Et 3 Al with hydrogen under pressure (350 bar). A synthesis of NaAIH 4 from the elements Na, AI and H is also possible in the absence of organic solvents according to Dokl. Akad. Nauk SSSR 215 (1974) 1369, narrow. 256 possible by carrying out the process in the melt (> 175 bar, <280 ° C). The alkali metal alanates prepared by the processes mentioned were not taken into consideration for the purposes of hydrogen storage.
Im Gegensatz dazu ist die Präparation des Speichermaterials nach der vorliegenden Erfindung sehr einfach und verzichtet vollständig auf organische Lösemittel. Das nach dem vorliegenden Verfahren verwendete Aluminium-Pulver ist billiger und einfacher in der Handhabung als das bisher verwendete Natriumalanat. Besonders überraschend war es, daß die Hydrierung von Aluminium in Gegenwart von Alkalimetallen oder -metallhydriden bei Temperaturen deutlich unterhalb der Schmelzpunkte der beteiligten Metall- /Metallhydrid-Edukte und der Metallaianat-Produkte, also in fester Form, gelingt (im Gegensatz zur oben zitierten Direktsynthese nach Dymova et al., Dokl. Akad. Nauk SSSR 215 (1974) 1369, engl. 256 „ Direct Synthesis of Alkali Metal Aluminium Hydrides in the Melt").In contrast, the preparation of the storage material according to the present invention is very simple and completely dispenses with organic solvents. The aluminum powder used in the present process is cheaper and easier to handle than the sodium alanate previously used. It was particularly surprising that the hydrogenation of aluminum in the presence of alkali metals or metal hydrides at temperatures well below the melting points of the metal / metal hydride starting materials involved and the metal alianate products, ie in solid form, succeeds (in contrast to the direct synthesis cited above) according to Dymova et al., Dokl. Akad. Nauk SSSR 215 (1974) 1369, English 256 "Direct Synthesis of Alkali Metal Aluminum Hydrides in the Melt").
Nach der vorliegenden Erfindung wird beispielsweise Aluminium-Pulver mit pulverförmigem Natriumhydrid gemischt und mit katalytischen Mengen Titantetrabutylat vermengt. Die so erhaltene Masse kann direkt als reversibler
Wasserstoffspeicher verwendet werden. Setzt man AI und NaH im Molverhältnis 1 : 1 ein, so erhält man bei der Hydrierung NaAIH4, während man bei einem Molverhältnis von 1 : 3 nach der Hydrierung Na3AIH6 erhält.According to the present invention, for example aluminum powder is mixed with powdered sodium hydride and mixed with catalytic amounts of titanium tetrabutylate. The mass obtained in this way can be directly reversible Hydrogen storage can be used. If Al and NaH are used in a molar ratio of 1: 1, NaAIH 4 is obtained in the hydrogenation, while Na 3 AIH 6 is obtained in a molar ratio of 1: 3 after the hydrogenation.
Ein weiterer besonderer Vorteil des vorliegenden Verfahrens zur reversiblen Speicherung von Wasserstoff ist, daß unter Vereinfachung der bisher bekannten Methode nach PCT/WO 97/03919, die Desorptions- und Absorptionskinetik deutlich verbessert werden konnte.Another particular advantage of the present process for the reversible storage of hydrogen is that, by simplifying the previously known method according to PCT / WO 97/03919, the desorption and absorption kinetics could be significantly improved.
In Figur 1 ist die Wasserstoffdesorption bei 160°C unter Normaldruck nach der vorliegenden Erfindung gegenüber dem bisher bekannten Verfahren der Studiengesellschaft Kohle dargestellt. Zur vollständigen Speicherentladung werden nach dem bisherigen Verfahren - 10 h benötigt, während die Desorption nach der vorliegenden Erfindung nur ~1 h dauert.In Figure 1, the hydrogen desorption at 160 ° C under normal pressure according to the present invention compared to the previously known method of the study company coal. According to the previous method, - 10 h is required for complete storage discharge, while the desorption according to the present invention only takes ~ 1 h.
Figur 2 stellt den Hydrierverlauf eines Hydrierzyklusses nach dem bisherigen Verfahren bei 170°C und nach dem vorliegenden Verfahren bei 118°C dar und veranschaulicht die deutlich hinzugewonnene Aktivität.FIG. 2 shows the course of hydrogenation of a hydrogenation cycle according to the previous method at 170 ° C. and according to the present method at 118 ° C. and illustrates the clearly gained activity.
In Figur 3 sind 33 Hydrier-/Dehydrierzyklen eines Materials nach dem vorliegenden Verfahren aufgezeichnet und belegen die Reversibilität der neuen Materialien.FIG. 3 shows 33 hydrogenation / dehydrogenation cycles of a material according to the present method and prove the reversibility of the new materials.
Eine typische Speichermaterial-Vorbereitung nach der vorliegenden Erfindung besteht darin, daß Aluminium-Pulver, unbehandelt oder nach kurzzeitigem Erhitzen im Vakuum auf ca. 200°C, mit feinpulvrigem Natriumhydrid unter Schutzgas (z.B. Argon) intensiv verrührt wird. Anschließend werden unter Rührung (oder evt. unter Vermahlung) katalytische Mengen Titantetra-n-butylat (0,1 bis 10 mol-% bezogen auf Aluminium, vorzugsweise 1 bis 5 mol-%) zugetropft. Auf diese Weise erhält man ein graues, leicht klebriges, jedoch noch schüttfähiges Pulvergemisch, das in einen Autoklaven eingebracht wird. Zunächst wird unter Drücken zwischen 5 und 150 bar und Temperaturen zwischen 20 und 200°C hydriert. Anschließend wird gegen erhöhten Druck oder Normaldruck bei Temperaturen zwischen 50 und 250°C dehydriert und auf diese Weise periodisch in einer geeigneten Druckanlage zyklisiert (Beispiel 1 ).
Um eine möglichst gute Hydrierkinetik und hohe Speicherkapazitäten zu erzielen, wird das Aluminium vorzugsweise in Form eines feinen Schliffs eingesetzt (s. Beispiele 1 und 5: Oberflächen It. BET-Messung 12,2 bzw. 2,0 m2/g).A typical storage material preparation according to the present invention is that aluminum powder, untreated or after briefly heating in vacuo to about 200 ° C., is stirred vigorously with finely powdered sodium hydride under a protective gas (eg argon). Subsequently, with stirring (or possibly with grinding), catalytic amounts of titanium tetra-n-butoxide (0.1 to 10 mol% based on aluminum, preferably 1 to 5 mol%) are added dropwise. In this way, a gray, slightly sticky, but still pourable powder mixture is obtained, which is introduced into an autoclave. The first step is to hydrogenate under pressures between 5 and 150 bar and temperatures between 20 and 200 ° C. The mixture is then dehydrated against elevated pressure or normal pressure at temperatures between 50 and 250 ° C. and cycled in this way periodically in a suitable pressure system (example 1). In order to achieve the best possible hydrogenation kinetics and high storage capacities, the aluminum is preferably used in the form of a fine cut (see Examples 1 and 5: surface It. BET measurement 12.2 or 2.0 m 2 / g).
In Abwandlung zu der beschriebenen Speichermaterial-Vorbereitung kann das eingesetzte Aluminium gegebenfalls durch Vermahlung, Einwirkung von Ultraschall oder chemische Aktivierung voraktiviert werden. Anstelle von Natriumhydrid oder Natrium können auch andere Alkalimetallhydride oder Alkalimetalle (insbesondere Li und K) einzeln oder in Kombinationen eingesetzt werden. Das Molverhältnis zwischen Aluminium und Alkalimetall kann zwischen 1 : 0,3 und 1 : 5 variieren. Setzt man Aluminium und Na oder NaH im Molverhältnis - 1 : 1 bzw. - 1 : 3 ein, so erhält man bei der Hydrierung NaAIH4 bzw. Na3AIH6. Die Alkalimetalle oder deren Hydride können ggf. vor ihrer Verwendung durch Vermählen oder Einwirkung von Ultraschall vorbehandelt werden. Als Katalysatoren werden Übergangsmetalle oder Übergangsmetall-Verbindungen bzw. -Legierungen der Gruppen 3 - 11 des PSE und der Seltenerdmetalle einzeln oder in Kombinationen verwendet, die an Elemente der Gruppen 14-17 oder Wasserstoff gebunden sein können. Die Übergangsmetall- bzw. Seltenerdmetallverbindungen werden vorzugsweise in Form von Halogeniden, Hydriden, Alkoholaten, Amiden oder metallorganischen Verbindungen eingesetzt. Besonders bevorzugt sind Halogenide, Alkoholate und metallorganische Verbindungen des Titans, Zirkons und der Seltenerdmetalle.In a modification of the storage material preparation described, the aluminum used can optionally be preactivated by grinding, exposure to ultrasound or chemical activation. Instead of sodium hydride or sodium, other alkali metal hydrides or alkali metals (in particular Li and K) can be used individually or in combinations. The molar ratio between aluminum and alkali metal can vary between 1: 0.3 and 1: 5. If aluminum and Na or NaH are used in a molar ratio of - 1: 1 or - 1: 3, the hydrogenation gives NaAIH 4 or Na 3 AIH 6 . The alkali metals or their hydrides can optionally be pretreated before use by grinding or exposure to ultrasound. Transition metals or transition metal compounds or alloys of groups 3-11 of the PSE and rare earth metals are used individually or in combinations, which can be bound to elements of groups 14-17 or hydrogen, as catalysts. The transition metal or rare earth metal compounds are preferably used in the form of halides, hydrides, alcoholates, amides or organometallic compounds. Halides, alcoholates and organometallic compounds of titanium, zirconium and rare earth metals are particularly preferred.
Die Fortschritte des vorliegenden Verfahrens gegenüber dem bisherigen Verfahren der SGK (PCT /VO 97/03919) ergeben sich aus folgenden Verbesserungen:The progress of the present procedure compared to the previous procedure of the SGK (PCT / VO 97/03919) results from the following improvements:
■ Edukte sind kommerziell leicht zugänglich ■ Educts are easily accessible commercially
■ geringere Verfahrenskosten■ lower procedural costs
■ erheblich vereinfachte Speichermaterial-Präparation ■ considerably simplified storage material preparation
■ keine Verwendung von organischen Lösemitteln ■ no use of organic solvents
■ deutlich verbesserte Hydrier- und Dehydrierkinetik
Die Erfindung wird durch die nachfolgenden Beispiele näher erläutert, ohne jedoch auf sie beschränkt zu sein. Sämtliche Versuche wurden in einer Schutzatmosphäre, z.B. Argon, durchgeführt. ■ significantly improved hydrogenation and dehydrogenation kinetics The invention is explained in more detail by the following examples, but without being limited to them. All experiments were carried out in a protective atmosphere, such as argon.
Beispiel 1 (mit Titantetra-n-butylat dotiertes AI- und NaH-Pulvergemisch als reversibler Wasserstoffspeicher; 33-Zyklentest)Example 1 (Al and NaH powder mixture doped with titanium tetra-n-butoxide as a reversible hydrogen storage; 33-cycle test)
Das eingesetzte Aluminium war ein AI-Schliff (Lunasol) der Frankfurter Bronzefarben- und Blattmetallfabrik Julius Schopflocher AG mit einer Oberfläche von 12,2m2/g (It. BET-Messung).The aluminum used was an AI cut (Lunasol) from the Frankfurt bronze paint and sheet metal factory Julius Schopflocher AG with a surface area of 12.2m 2 / g (It. BET measurement).
Das NaH wurde in einer Glaskugelmühle fein pulverisiert. Das Aluminium-Pulver wurde bei 0,1 mbar kurzzeitig auf 200°C erhitzt (Aluminium-Gehalt It. Elementaranalyse der Fa. H. Kolbe, Mülheim a.d. Ruhr : 91 ,7 Gew.-%).The NaH was finely pulverized in a glass ball mill. The aluminum powder was briefly heated to 200 ° C. at 0.1 mbar (aluminum content according to elementary analysis by H. Kolbe, Mülheim a.d.Ruhr: 91.7% by weight).
753mg (31 ,4mmol) des pulverisierten Natriumhydrids wurden mit 980mg (33,3mmol) des im Vakuum erhitzten Aluminium-Schliffs durch Rühren mit einem Magnetrührkern unter Argon intensiv vermengt. Dann wurde das gerührte Pulver langsam aus einer feinen Tropfspitze mit 0,21 ml (0,62mmol = 1 ,9mol-% bezogen auf AI) Titantetra-n-butylat versetzt und noch kurzzeitig weiter gerührt. 1850mg des erhaltenen grauen, leicht klebrigen, jedoch schüttfähigen Materials wurden in einen Autoklav (-40 ml Volumen) mit Glaseinsatz gegeben. Der Autoklav war mit einer Innentemperaturfühlung, einer elektrischen Heizung mit Rampenfunktion, einem elektrischen Druckumformer und einem Mehrkanalschreiber ausgestattet. Um die Eignung des Materials als reversibler Wasserstoffspeicher zu testen, wurde es einer Serie von 33 Hydrier-/Rehydrierzyklen (Zyklentest) unterworfen (siehe Tabelle 1 ). Der Zyklentest wurde in einem sog. offenen System durchgeführt, d.h., daß bei jeder Hydrierung frischer Wasserstoff (99,9%) einem Wasserstoffdruckbehälter entnommen wurde und bei jeder Dehydrierung Wasserstoff gegen Normaldruck desorbiert wurde.
Tabelle 1753 mg (31.4 mmol) of the powdered sodium hydride were mixed intensively with 980 mg (33.3 mmol) of the aluminum section, which was heated in a vacuum, by stirring with a magnetic stirrer core under argon. Then the stirred powder was slowly mixed with 0.21 ml (0.62mmol = 1.9mol% based on Al) of titanium tetra-n-butoxide from a fine dropping tip and briefly stirred further. 1850 mg of the gray, slightly sticky, but pourable material obtained was placed in an autoclave (-40 ml volume) with a glass insert. The autoclave was equipped with an internal temperature sensor, an electric heater with ramp function, an electric pressure transducer and a multi-channel recorder. In order to test the suitability of the material as a reversible hydrogen storage, it was subjected to a series of 33 hydrogenation / rehydration cycles (cycle test) (see Table 1). The cycle test was carried out in a so-called open system, ie fresh hydrogen (99.9%) was taken from a hydrogen pressure vessel with each hydrogenation and hydrogen was desorbed against normal pressure with each dehydrogenation. Table 1
Zyklentest (Beispiel 1)Cycle test (example 1)
ZyklenTemp. End- Zeit Gew.- Zyklen- Temp. End- Zeit Gew.- zahl [°C] druck3' [h] % H2 zahl [°C] drucka) [h] % H2 ZyklenTemp. End time Wt. Cycle temp. End time Wt. Number [° C] pressure 3 '[h]% H 2 number [° C] pressure a) [h]% H 2
[bar] [bar][bar] [bar]
a) Zur Ermittlung des Anfangsdrucks müssen zum Enddruck pro Gew.-% H2 -4 bar addiert werden. b) siehe Abb. 2 c) siehe Abb. 1
Hydrierung: Die Hydrierungen wurden bei Temperaturen zwischen 103 und 165°C, in der Mehrzahl bei ~120°C, bei abnehmendem Wasserstoffdruck im Autoklaven durchgeführt (siehe Abb. 2; 7. Zyklus).a) To determine the initial pressure, add 2-4 bar per wt.% H 2 to the final pressure. b) see Fig. 2 c) see Fig. 1 Hydrogenation: The hydrogenations were carried out at temperatures between 103 and 165 ° C, the majority at ~ 120 ° C, with decreasing hydrogen pressure in the autoclave (see Fig. 2; 7th cycle).
Dehydrierung: Die Probe wurde schnell von Raumtemperatur auf 160°C erhitzt und bei dieser Temperatur bis zum Ende der Wasserstoffentwicklung konstant gehalten. Der zeitliche Verlauf der Wasserstoffentwicklung wurde mit Hilfe einer automatischen Gasbürette (Chem. Ing. Tech., 55 (1983) S.156) zusammen mit der Innentemperatur der Probe aufgezeichnet. Abb. 1 stellt den Dehydrierverlauf (8. Zyklus, 3,96 Gew.-% H2) im Vergleich zum bisherigen Stand der Technik dar.Dehydration: The sample was quickly heated from room temperature to 160 ° C and kept constant at this temperature until the end of the evolution of hydrogen. The evolution of hydrogen over time was recorded with the aid of an automatic gas burette (Chem. Ing. Tech., 55 (1983) p.156) together with the internal temperature of the sample. Fig. 1 shows the course of dehydrogenation (8th cycle, 3.96% by weight H 2 ) compared to the prior art.
Die Abhängigkeit der Wasserstoffspeicherkapazität (gemessen anhand der bei der Dehydrierung abgegeben H2-Menge) von der Zyklenzahl zeigt die Abb. 3.Fig. 3 shows the dependence of the hydrogen storage capacity (measured using the amount of H 2 released during dehydrogenation) on the number of cycles.
Nach insgesamt 34 Hydriervorgängen wurde das Speichermaterial in hydrierter Form aus dem Autoklaven entnommen und infrarotspektroskopisch untersucht. Das IR-Spektrum zeigt AIH4- und AIH6-Banden, neben schwachen CH- und C-O- Banden (Alkoholat-Gruppen).After a total of 34 hydrogenation processes, the storage material was removed from the autoclave in hydrogenated form and examined by infrared spectroscopy. The IR spectrum shows AIH 4 and AIH 6 bands, in addition to weak CH and CO bands (alcoholate groups).
Beispiel 2 (mit Titantetra-n-butylat dotiertes AI- und NaH-Pulvergemisch als reversibler Wasserstoffspeicher unter Verwendung von unbehandeltem Aluminium-Schliff)Example 2 (Al and NaH powder mixture doped with titanium tetra-n-butylate as a reversible hydrogen storage using untreated aluminum cut)
Die Speichermaterial-Präparation erfolgte analog Beispiel 1 , jedoch wurde anstelle des im Vakuum ausgeheizten Aluminiums hier das unbehandelte kommerzielle Produkt eingesetzt. Das Material wurde in 7 Zyklen untersucht und erreichte im 3. Hydriervorgang eine Speicherkapazität von 3,7 Gew.-% H2 und im 7. Hydrierschritt 3,6 Gew.-% H2.The storage material preparation was carried out analogously to Example 1, but the untreated commercial product was used here instead of the aluminum heated in a vacuum. The material was examined in 7 cycles and reached a storage capacity of 3.7% by weight H 2 in the 3rd hydrogenation process and 3.6% by weight H 2 in the 7th hydrogenation step.
Beispiel 3 (mit ß-TiCI3 dotiertes AI- und NaH-Pulvergemisch als reversibler W asse rstof f sp e i ch e r)Example 3 (Al and NaH powder mixture doped with β-TiCI 3 as a reversible hydrogen storage agent)
Die Speichermaterial-Präparation erfolgte analog Beispiel 1 , jedoch wurde der Aluminium-Schliff nicht im Vakuum ausgeheizt, sondern vor seiner Verwendung
in einer Glaskugelmühle mechanisch vermählen. Anstelle Ti(OBu)4 wurdenThe storage material preparation was carried out analogously to Example 1, but the aluminum grinding was not baked in a vacuum, but rather before it was used Mechanically grind in a glass ball mill. Instead of Ti (OBu) 4 were
2 mol-% ß-TiCI3 zur Dotierung eingesetzt.2 mol% ß-TiCI 3 used for doping.
Das Material wurde zyklisiert und erreichte bei der 1. Hydrierung eine Kapazität von 2,5 Gew.-% H2 und im 5. Hydrierschritt (bei 135°C / ~140bar) 2,9 Gew.-%The material was cyclized and reached a capacity of 2.5% by weight H 2 in the 1st hydrogenation and 2.9% by weight in the 5th hydrogenation step (at 135 ° C / ~ 140bar)
H2.H 2 .
Beispiel 4 (mit Titantetra-n-butylat dotiertes AI- und NaH-Pulvergemisch [Molverh. = 1 2,9] zur Herstellung von NasAIHε als reversiblerExample 4 (Al and NaH powder mixture doped with titanium tetra-n-butylate [mol ratio = 1 2.9]) for the preparation of NasAIHε as reversible
Wasserstoffspeicher)Hydrogen storage)
Die Speichermaterial-Präparation erfolgte analog Beispiel 1 , jedoch wurde der Aluminium-Schliff nicht im Vakuum ausgeheizt, sondern vor seiner Verwendung in einer Glaskugelmühle mechanisch vermählen. Das Molverhältnis zwischen Aluminium und Natriumhydrid betrug 1 : 2,9. Das Material erreichte bei der 1. Hydrierung eine Kapazität von 2,2 Gew.-% H2 und im 5. Hydrierschritt (bei 117°C/35bar) 1 ,5 Gew.-% H2.The storage material preparation was carried out analogously to Example 1, but the aluminum grinding was not baked in a vacuum, but was mechanically ground in a glass ball mill before being used. The molar ratio between aluminum and sodium hydride was 1: 2.9. The material reached a capacity of 2.2 wt .-% H 2 and 5. hydrogenation step (at 117 ° C / 35 bar) 1, 5 wt .-% H 2 in the 1st hydrogenation.
Beispiel 5 (mit Titantetra-n-butylat dotiertes AI- und NaH-Pulvergemisch als reversibler Wasserstoff -Speicher unter Verwendung von kugelförmigem AI-Pulver ~20μ)Example 5 (Al and NaH powder mixture doped with titanium tetra-n-butylate as reversible hydrogen storage using spherical Al powder ~ 20μ)
Die Speichermaterial-Präparation erfolgte analog Beispiel 2, wobei anstelle des AI-Schliffs ein kugelförmiges AI-Pulver (~20μ) der Fa. Aldrich (Oberfläche It. BET- Messung: 2.0m2/g) in unbehandelter Form eingesetzt wurde. Das Material erreichte bei der 1. Hydrierung (165°C/150bar) eine Kapazität von 0,9 Gew.-% H2 und im 2. Hydrierschritt (165 bis 182°C/150bar) 1 ,5 Gew.-% H2.
The storage material preparation was carried out analogously to Example 2, with a spherical Al powder (~ 20μ) from Aldrich (surface according to BET measurement: 2.0 m 2 / g) being used in the untreated form instead of the Al grinding. The material reached in the first hydrogenation (165 ° C / 150bar) a capacity of 0.9 wt .-% H 2 and in the second hydrogenation step (165-182 ° C / 150 bar) 1, 5 wt .-% H 2 ,
Claims
1 . Verfahren zur reversiblen Speicherung von Wasserstoff, dadurch gekennzeichnet, daß reversible Wasserstoffspeicher-Materialien verwendet werden, die Gemische von Aluminiummetall mit Alkalimetallen und/oder Alkalimetallhydriden und Übergangsmetall- und/oder Seltenerdmetallkatalysatoren enthalten.1 . Process for the reversible storage of hydrogen, characterized in that reversible hydrogen storage materials are used which contain mixtures of aluminum metal with alkali metals and / or alkali metal hydrides and transition metal and / or rare earth metal catalysts.
2. Verfahren nach Anspruch 1 , wobei als Alkalimetalle Li-, Na- und/oder K- Metall verwendet werden.2. The method according to claim 1, wherein Li, Na and / or K metal are used as alkali metals.
3. Verfahren nach den Ansprüchen 1 und 2, wobei als Alkalimetallhydride LiH, NaH und/oder KH eingesetzt werden.3. Process according to claims 1 and 2, wherein LiH, NaH and / or KH are used as alkali metal hydrides.
4. Verfahren nach Anspruch 3, wobei als Alkalimetallhydrid NaH eingesetzt wird.4. The method according to claim 3, wherein NaH is used as the alkali metal hydride.
5. Verfahren nach den Ansprüchen 1 bis 4, wobei das Molverhältnis zwischen Aluminium und Alkalimetall von 1 : 0,3 bis 1 : 5 beträgt.5. The method according to claims 1 to 4, wherein the molar ratio between aluminum and alkali metal is from 1: 0.3 to 1: 5.
6. Verfahren nach Anspruch 5, wobei zur Bildung von MAIH4 Aluminium und M oder MH bevorzugt im Molverhältnis - 1 : 1 eingesetzt werden (M = Li, Na und/oder K).6. The method according to claim 5, wherein for the formation of MAIH 4 aluminum and M or MH are preferably used in a molar ratio - 1: 1 (M = Li, Na and / or K).
7. Verfahren nach Anspruch 5, wobei zur Bildung von M3AIH6 Aluminium und M oder MH bevorzugt im Molverhältnis - 1 : 3 eingesetzt werden (M = Li, Na und/oder K).7. The method according to claim 5, wherein to form M 3 AlH 6 aluminum and M or MH are preferably used in a molar ratio - 1: 3 (M = Li, Na and / or K).
8. Verfahren nach den Ansprüchen 1 bis 7, wobei die Alkali- und Erdalkalimetalle oder deren Hydride als feinteilige Pulver eingesetzt werden.8. The method according to claims 1 to 7, wherein the alkali and alkaline earth metals or their hydrides are used as finely divided powders.
9. Verfahren nach Anspruch 8, wobei die Alkalimetalle oder deren Hydride vor ihrer Verwendung durch Vermählen oder Einwirkung von Ultraschall vorbehandelt werden. 9. The method according to claim 8, wherein the alkali metals or their hydrides are pretreated before use by grinding or exposure to ultrasound.
10. Verfahren nach Anspruch 1 , wobei Aluminium als feinteiliges Pulver, vorzugsweise als feiner Aluminium-Schliff, eingesetzt wird.10. The method according to claim 1, wherein aluminum is used as a finely divided powder, preferably as a fine aluminum cut.
11. Verfahren nach Anspruch 10, wobei das Aluminium vor seiner Verwendung durch Erhitzen im Vakuum, Anwendung von Ultraschall, Vermahlung oder chemische Aktivierung gegebenfalls vorbehandelt wird.11. The method according to claim 10, wherein the aluminum is optionally pretreated before use by heating in a vacuum, application of ultrasound, grinding or chemical activation.
12. Verfahren nach den Ansprüchen 1 bis 11 , wobei als Katalysatoren Übergangsmetalle und/oder Übergangsmetall-Verbindungen oder - Legierungen der Gruppen 3 bis 11 des PSE und der Seltenerdmetalle zugesetzt werden.12. The method according to claims 1 to 11, wherein as catalysts transition metals and / or transition metal compounds or - alloys of groups 3 to 11 of the PSE and the rare earth metals are added.
13. Verfahren nach Anspruch 12, wobei die Metalle der Übergangsmetalloder Seltenerdmetall-Katalysatoren an Elemente der Gruppen 14 -17 des PSE oder Wasserstoff gebunden sind.13. The method of claim 12, wherein the metals of the transition metal or rare earth catalysts are bound to elements of groups 14 -17 of PSE or hydrogen.
14. Verfahren nach Anspruch 13, wobei die Übergangsmetall- oder Seltenerdmetall-Katalysatoren in Form von Halogeniden, Hydriden, Alkoholaten, Amiden, metallorganischen Verbindungen und/oder intermetallischen Verbindungen oder deren Hydriden eingesetzt werden.14. The method according to claim 13, wherein the transition metal or rare earth catalysts in the form of halides, hydrides, alcoholates, amides, organometallic compounds and / or intermetallic compounds or their hydrides are used.
15. Verfahren nach Anspruch 14, wobei Titan und Zirkon als Übergangsmetalle eingesetzt werden.15. The method according to claim 14, wherein titanium and zirconium are used as transition metals.
16. Verfahren nach den Ansprüchen 12 bis 15, wobei die Übergangsmetalle oder deren Verbindungen in Mengen von 0,1 bis 10 mol-% bezogen auf Aluminium, bevorzugt in Mengen von 1 bis 5 mol-%, eingesetzt werden.16. The method according to claims 12 to 15, wherein the transition metals or their compounds in amounts of 0.1 to 10 mol% based on aluminum, preferably in amounts of 1 to 5 mol%, are used.
17. Verfahren nach den Ansprüchen 1 bis 16, dadurch gekennzeichnet, daß alle Komponenten des Gemisches vor der ersten Hydrierung mechanisch vermengt, verrührt oder vermählen werden. 17. The method according to claims 1 to 16, characterized in that all components of the mixture are mechanically mixed, stirred or ground before the first hydrogenation.
18. Verfahren nach Anspruch 1 , wobei die Hydrierungen bei Drücken zwischen 5 und 150 bar und Temperaturen zwischen 20 und 200°C erfolgen.18. The method according to claim 1, wherein the hydrogenations are carried out at pressures between 5 and 150 bar and temperatures between 20 and 200 ° C.
19. Verfahren nach Anspruch 1 , wobei die Dehydrierungen bei Temperaturen zwischen 50 und 250°C erfolgen. 19. The method according to claim 1, wherein the dehydrogenations take place at temperatures between 50 and 250 ° C.
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US7384574B2 (en) * | 2003-07-17 | 2008-06-10 | Westinghouse Savannah River Co. | Hydrogen storage material and process using graphite additive with metal-doped complex hydrides |
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2001
- 2001-03-02 WO PCT/EP2001/002363 patent/WO2001068515A1/en active Application Filing
- 2001-03-02 CA CA002403403A patent/CA2403403A1/en not_active Abandoned
- 2001-03-02 EP EP01931491A patent/EP1263676A1/en not_active Withdrawn
- 2001-03-02 JP JP2001567622A patent/JP2003527280A/en active Pending
- 2001-03-02 US US10/221,466 patent/US6814782B2/en not_active Expired - Fee Related
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US6814782B2 (en) | 2004-11-09 |
JP2003527280A (en) | 2003-09-16 |
WO2001068515A1 (en) | 2001-09-20 |
DE10012794A1 (en) | 2001-09-20 |
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