# US 8,784,771 B2 · Process for preparing Ti-doped hydrides > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,784,771 B2 - Document ID: US8784771B2 - Status: Granted - Kind: B2 - Application number: 12/599,940 - Filed: 2008-05-14 - Published: 2010-09-16 - Granted: 2014-07-22 - Earliest claimed: 2007-05-15 - Assignees: Shell Oil Company - Applicants: Jacobus Johannes Cornelis Geerlings; Peter Marie Paulus; Hans Arie Stil - Inventors: Jacobus Johannes Cornelis Geerlings; Peter Marie Paulus; Hans Arie Stil - Web page: https://patentgrep.com/patent/US8784771B2 ## CPC - C01B 3/0031: Intermetallic compounds; Metal alloys - C01B 6/24: Hydrides containing at least two metals; Addition complexes thereof (C01B6/13 - C01B6/23 take precedence) - Y02E 60/32: Hydrogen storage - Y02E 60/36: Hydrogen production from non-carbon containing sources, e.g. by water electrolysis - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION ## Abstract The present invention provides a process for the preparation of Ti-doped alkali metal and/or alkaline-earth metal aluminum hydride, comprising intimately mixing: an alkali metal and/or alkaline-earth metal aluminum hydride, or at least one alkali metal hydride and/or alkaline-earth metal hydride, metallic aluminum and H2, with in the range of from 0.5 to 20 mol % of Ti(OCH3)4, based on the moles of Al in the prepared Ti-doped alkali metal and/or alkaline-earth metal aluminum hydride. The invention further relates to a Ti-doped alkali metal and/or alkaline-earth metal aluminum hydride, obtainable by a process according to the invention, a hydrogen storage material comprising a Ti-doped alkali metal and/or alkaline-earth metal aluminum hydride according the invention, a process for reversibly desorbing and/or absorbing hydrogen, the use of a Ti-doped alkali metal and/or alkaline-earth metal aluminum hydride according to invention to store hydrogen and the use of Ti(OCH3)4 as Ti-dopant for an alkali metal and/or alkaline-earth metal aluminum hydride. ## Claims ### Claim 1 A Ti(OCH3)4-doped alkali metal and/or alkaline-earth metal aluminium hydride, obtained by a process, comprising intimately mixing: an alkali metal and/or alkaline-earth metal aluminium hydride, or at least one alkali metal hydride and/or alkaline-earth metal hydride, metallic aluminium and H2, with from 0.5 to 20 mol % of Ti(OCH3)4, based on the moles of Al in the prepared Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride. ### Claim 2 (depends on 1) A Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride according to claim 1, wherein the Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride is Ti-doped NaAlH4, LiMg (AlH4)3 or Na2LiAlH6. ### Claim 3 (depends on 1) A Ti(OCH3)4-doped alkali metal and/or alkaline-earth metal aluminium hydride according to claim 1, obtained by a process wherein an alkali metal and/or alkaline-earth metal aluminium hydride is mixed with Ti(OCH3)4 and the alkali metal and/or alkaline-earth metal aluminium hydride is an aluminium hydride of the general formula: A p ⁡ ( 1 - x ) m n + ⁢ B px n m + ⁢ AlH 3 + p with A, B=an alkali or alkaline-earth metal, n,m=metal ion valence, i.e. 1, 2 or 3, 0≦x≦1, and 1≦p≦3. ### Claim 4 (depends on 1) A Ti(OCH3)4-doped alkali metal and/or alkaline-earth metal aluminium hydride according to claim 1, obtained by a process wherein at least one alkali and/or alkaline-earth metal hydride, metallic aluminium and H2 are mixed with Ti(OCH3)4 and the alkali and/or alkaline-earth metal is selected from the group consisting of Na, Ca, Li and Mg. ### Claim 5 (depends on 4) A Ti(OCH3)4-doped alkali metal and/or alkaline-earth metal aluminium hydride according to claim 4, obtained by a process wherein: a) 3 parts NaH, 4.5 parts H2 and at least 3 parts Al, or b) 2 parts LiH, 2 parts MgH2, 9 parts H2 and at least 6 parts Al, or c) 4 parts NaH, 2 parts LiH, 3 parts H2 and at least 2 parts Al are mixed with Ti(OCH3)4. ### Claim 6 (depends on 1) A Ti(OCH3)4-doped alkali metal and/or alkaline-earth metal aluminium hydride according to claim 1, obtained by a process wherein Ti(OCH3)4 is mixed in an amount in the range of from 1 to 10 mol %, based on the moles of Al in the prepared Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride. ### Claim 7 (depends on 6) A Ti(OCH3)4-doped alkali metal and/or alkaline-earth metal aluminium hydride according to claim 6, obtained by a process wherein Ti(OCH3)4 is mixed in an amount in the range of from 2 to 5 mol %, based on the moles of Al in the prepared Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride. ### Claim 8 (depends on 1, 2) A process for reversibly desorbing and/or absorbing hydrogen using a Ti-doped alkali metal and/or alkaline earth metal aluminum hydride prepared by intimately mixing an alkali metal and/or an alkaline-earth metal aluminum hydride; or at least one alkali metal hydride and/or alkaline earth metal hydride, metallic aluminum and H2 with from 0.5 to 20 mol % of Ti(OCH3)4, based on the moles of Al in the prepared Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride comprising: dehydrogenating the at least partially hydrogenated Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride by subjecting the Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride to a temperature of in the range of from 20 to 140° C. and removing a hydrogen-comprising gas to obtain a hydrogen-comprising gas and an at least partially dehydrogenated Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride; and/or hydrogenating the at least partially dehydrogenated Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride according to claim 1 or 2 by contacting the at least partially dehydrogenated Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride with a hydrogen-comprising gas at a temperature in the range of from 115 to 180° C. and a hydrogen partial pressure above the equilibrium hydrogen pressure of the at least partially dehydrogenated Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride to reversibly store hydrogen. ### Claim 9 (depends on 8) A process according to claim 8, wherein during hydrogenating the at least partially dehydrogenated Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride is contacted with the hydrogen-comprising gas at a temperature of in the range of from 120 to 160° C. ### Claim 10 (depends on 8) A process according to claim 8, wherein during hydrogenation the at least partially dehydrogenated Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride is contacted with an hydrogen-comprising gas at a pressure in the range of from 1 to 700 bar. ### Claim 11 (depends on 8) A process according to claim 8, wherein during hydrogenation the at least partially dehydrogenated Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride is contacted with an hydrogen-comprising gas at a pressure in the range of from 10 to 150 bar. ### Claim 12 (depends on 8) A process according to claim 8, wherein during hydrogenation the at least partially dehydrogenated Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride is contacted with an hydrogen-comprising gas at a pressure in the range of from 50 to 100 bar. ### Claim 13 A hydrogen storage material comprising a Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride obtained by a process comprising intimately mixing: an alkali metal and/or alkaline-earth metal aluminium hydride, or at least one alkali metal hydride and/or alkaline-earth metal hydride, metallic aluminium and H2, with from 0.5 to 20 mol % of Ti(OCH3)4, based on the moles of Al in the prepared Ti-doped alkali metal and/or alkaline-earth metal aluminium hydride.