Hydrogen storage by reversible hydrogenation of pi-conjugated substrates
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C01B-003/00
F17C-011/00
출원번호
US-0833484
(2004-04-27)
등록번호
US-7429372
(2008-09-30)
발명자
/ 주소
Pez,Guido Peter
Scott,Aaron Raymond
Cooper,Alan Charles
Cheng,Hansong
출원인 / 주소
Air Products and Chemicals, Inc.
대리인 / 주소
Boyer,Michael K.
인용정보
피인용 횟수 :
14인용 특허 :
7
초록▼
Processes are provided for the storage and release of hydrogen by means of a substantially reversible catalytic hydrogenation of extended pi-conjugated substrates which include large polycyclic aromatic hydrocarbons, polycyclic aromatic hydrocarbons with nitrogen heteroatoms, polycyclic aromatic hyd
Processes are provided for the storage and release of hydrogen by means of a substantially reversible catalytic hydrogenation of extended pi-conjugated substrates which include large polycyclic aromatic hydrocarbons, polycyclic aromatic hydrocarbons with nitrogen heteroatoms, polycyclic aromatic hydrocarbons with oxygen heteroatoms, polycyclic aromatic hydrocarbons with alkyl, alkoxy, nitrile, ketone, ether or polyether substituents, pi-conjugated molecules comprising 5 membered rings, pi-conjugated molecules comprising six and five membered rings with nitrogen or oxygen hetero atoms, and extended pi-conjugated organic polymers. The hydrogen, contained in the at least partially hydrogenated form of the extended pi-conjugated system, can be facilely released for use by a catalytic dehydrogenation of the latter in the presence of a dehydrogenation catalyst which can be effected by lowering the hydrogen gas pressure, generally to pressures greater than 0.1 bar or raising the temperature to less than 250�� C. or less, or by a combination of these two process parameters.
대표청구항▼
What is claimed is: 1. A process for the storage and subsequent release of hydrogen comprising: a) contacting hydrogen, in the presence of a hydrogenation catalyst under hydrogenation conditions, with an extended pi-conjugated substrate to effect storage of hydrogen by forming an at least partially
What is claimed is: 1. A process for the storage and subsequent release of hydrogen comprising: a) contacting hydrogen, in the presence of a hydrogenation catalyst under hydrogenation conditions, with an extended pi-conjugated substrate to effect storage of hydrogen by forming an at least partially hydrogenated extended pi-conjugated substrate; wherein the extended pi-conjugated substrate in step a) comprises at least one member selected from the group consisting of, extended pi-conjugated substrates with nitrogen heteroatoms, extended pi-conjugated substrates with heteroatoms other than nitrogen, pi-conjugated monocyclic substrates with multiple nitrogen heteroatoms, pi-conjugated substrates with at least one triple bonded group, a pitch, extended pi-conjugated substrates with greater than three rings, extended pi-conjugated substrates with at least two rings wherein one ring is a five membered ring, and any combination of two or more of the foregoing and b) contacting the at least partially hydrogenated extended pi-conjugated substrate under dehydrogenation conditions in the presence of an effective amount of a dehydrogenation catalyst to release hydrogen from the at least partially hydrogenated extended pi-conjugted substrate. 2. The process of claim 1, wherein the extended pi-conjugated substrate comprises at least one member selected from the group consisting of pyrene, perylene, coronene, ovalene, picene, rubicene, fluorene, indene, acenanaphthylene, pyranthrone; and any combination of two or more of the foregoing. 3. The process of claim 2 wherein the substrate comprises a fluorene. 4. The process of claim 1, wherein the extended pi-conjugated substrate comprises at least one extended pi-conjugated substrate with nitrogen heteroatoms selected from the group consisting of phenanthroline, quinoline, N-methylindole, 1,2-dimethylindole, 1-ethyl-2-methylindole, carbazole, N-methylcarbazole, N-ethylcarbazole, N-n-propylcarbazole, N-iso-propylcarbazole, acridine, indolo[2,3-b]carbazole, indolo[3,2-a]carbazole 1,4,5,8,9,12-hexaazatriphenylene, pyrazine[2,3-b]pyrazine, N,N",N'-trimethyl-6,11-dihydro-5H-diindolo[2,3-a:2',3'-c]carbazole, 1,7-dihydrobenzo[1,2-b:5,4-b']dipyrrole, 4H-benzo[def]carbazole; and any combination of two or more of the foregoing. 5. The process of claim 1, wherein the extended pi-conjugated substrate comprises at least one extended pi-conjugated substrate with heteroatoms other than nitrogen selected from the group consisting of dibenzofuran, dibenzothiaphene, phosphindole, P-methoxyphosphindole, P-methylphosphindole, dimethylsilaindene, boraindole, borafluorene, methylboraindole; and any combination of two or more of the foregoing. 6. The process of claim 1, wherein the extended pi-conjugated substrate comprises at least one member selected from the group consisting of polypyrrole, polyindole, poly(methylcarbazole), polyaniline, poly(9-vinylcarbazole); and any combination of two or more of the foregoing. 7. The process of claim 1, wherein the extended pi-conjugated substrate comprises at least one member selected from the group consisting of N-lithiocarbazole, N-lithioindole, N-lithiodiphenylamine, N-sodiumcarbazole, N-potassiumcarbazole, the tetramethylammonium salt of carbazole; and any combination of two or more of the foregoing. 8. The process of claim 1, wherein the extended pi-conjugated substrate comprises at least one pi-conjugated monocyclic substrate with multiple nitrogen heteroatoms selected from the group consisting of pyrazine, N-methylimidazole; and any combination thereof. 9. The process of claim 1, wherein the extended pi-conjugated substrate comprises at least one pi-conjugated substrate with at least one triple bonded group selected from the group consisting of terephthalonitrile (1,4-dinitrilobenzene), benzonitrile, 1,3,5-trinitrilobenzene; and any combination of two or more of the foregoing. 10. The process of claim 1, wherein the extended pi-conjugated substrate comprises at least one pitch or pitch fraction selected from the group consisting of natural pitch, synthetic pitch, synthetic pitch containing molecules with nitrogen heteroatoms, and combinations thereof. 11. The process of claim 1, wherein step a) and step b) are conducted within a single vessel. 12. The process of claim 1 wherein the hydrogenation catalyst also functions as the dehydrogenation catalyst. 13. The process of claim 12, wherein the extended pi-conjugated substrate in step a) resides in the liquid state and step a) is conducted in a first vessel; and the at least partially hydrogenated extended pi-conjugated substrate of step b) has a melting point of below about minus 10�� C. and step b) is conducted in a second vessel. 14. The process of claim 1, wherein the extended pi-conjugated substrate in step a) resides in the liquid state and step a) is conducted in a first vessel; and the at least partially hydrogenated extended pi-conjugated substrate in step b) resides in the liquid state and step b) is conducted in a second vessel. 15. The process of claim 1, wherein the at least partially hydrogenated extended pi-conjugated substrate of step b) has a melting point below about 100�� C. 16. The process of claim 1, wherein the hydrogen released in step b) is at least 1% by weight of the weight of the at least partially hydrogenated extended pi-conjugated substrate. 17. The process of claim 1, wherein the hydrogen released in step b) is at least 5% by weight of the weight of the at least partially hydrogenated extended pi-conjugated substrate. 18. The process of claim 1, wherein the hydrogen released in step b) is at least 7% by weight of the weight of the at least partially hydrogenated extended pi-conjugated substrate. 19. The process of claim 1 further comprising c) removing the hydrogenation catalyst from the at least partially hydrogenated extended pi-conjugated substrate obtained from step a) prior to conducting step b). 20. The process of claim 1 wherein step b) is conducted at a temperature below about 300�� C. and at a hydrogen partial pressure greater than approximately 0.1 bar. 21. The process of claim 1 wherein step b) is conducted at a temperature below about 250�� C. and at a hydrogen partial pressure greater than approximately 0.1 bar. 22. The process of claim 1 wherein step b) is conducted at a temperature below about 200�� C. and at a hydrogen partial pressure greater than approximately 0.1 bar. 23. The process of claim 1 wherein step b) is conducted at a temperature below about 150�� C. and at a hydrogen partial pressure greater than approximately 0.1 bar. 24. The process of claim 1 wherein step b) is conducted at a temperature below about 250�� C. and at a hydrogen partial pressure greater than approximately 1 bar. 25. The process of claim 1, wherein the modulus of the standard enthalpy change of hydrogenation of the extended pi-conjugated substrate in step a) is less than about 15.0 kcal/mol H2. 26. The process of claim 25, wherein the modulus of the standard enthalpy change of hydrogenation is determined experimentally. 27. The process of claim 25, wherein the modulus of the standard enthalpy change of hydrogenation is calculated by the ab initio density functional theory method. 28. The process of claim 1 wherein the at least partially hydrogenated extended pi-conjugted substrate in step a) comprises a mixture of at least two different at least partially hydrogenated extended pi-conjugted substrates. 29. The process of claim 28, wherein the mixture of at least two different at least partially hydrogenated extended pi-conjugted substrates is a eutectic mixture. 30. The process of claim 29, wherein the eutectic mixture comprises 1-ethyl-2-methylindole and 1,2-dimethylindole. 31. The process of claim 1 wherein the extended pi-conjugated substrate in step a) has a normal freezing point above about 200�� C. and is subjected to step a) while present in a mixture of at least two different extended pi-conjugated substrates with a freezing point of less than about 200�� C. 32. The process of claim 31, wherein the eutectic mixture comprises a mixture of an extended pi-conjugated substrate with nitrogen heteroatoms, an extended pi-conjugated substrate with heteroatoms other than nitrogen, and any combination of thereof. 33. The process of claim 32, wherein the eutectic mixture comprises N-methylcarbazole, N-ethylcarbazole, N-propylcarbazole, N-isopropylcarbazole or any combination of two or more of the foregoing. 34. The process of claim 31, wherein the eutectic mixture is a liquid at-10�� C. 35. The process of claim 1 wherein the at least partially hydrogenated extended pi-conjugated substrate from step a) has a freezing point of less than about 200�� C. 36. The process of claim 1 wherein the at least partially hydrogenated extended pi-conjugated substrate from step a) has a freezing point of less than about 100�� C. 37. The process of claim 1 wherein the at least partially hydrogenated extended pi-conjugated substrate from step a) has a freezing point of less than about-10�� C. 38. The process of claim 1 wherein the extended pi-contugated substrate additionally comprises a ring substituent selected from the group consisting of an alkyl group, an alkoxy group, an ether group, and a polyether group. 39. The process of claim 1 wherein the extended pi-conjugated substrate in step a) is contained within a natural pitch. 40. The process of claim 1 wherein the hydrogenation catalyst in step a) comprises a metal selected from groups 4, 5, 6 and 8, 9, 10 of the Periodic Table according to the International Union of Pure and Applied Chemistry. 41. The process of claim 1 wherein the hydrogenation catalyst in step a) comprises a metal selected from the group consisting of titanium, zirconium, cobalt, niobium, tantalum, iron, molybdenum, tungsten, ruthenium, rhodium, iridium, nickel, palladium, and platinum. 42. The process of claim 1 wherein the dehydrogenation catalyst in step b) comprises a metal selected from groups 4, 5, 6 and 8, 9, 10 of the Periodic Table according to the International Union of Pure and Applied Chemistry. 43. The process of claim 1 wherein the dehydrogenation catalyst in step b) comprises a metal selected from the group consisting of titanium, zirconium, cobalt, niobium, tantalum, iron, molybdenum, tungsten, ruthenium, rhodium, iridium, nickel, palladium, and platinum. 44. The process of claim 1 wherein the dehydrogenation catalyst in step b) comprises an acidic support selected from the group consisting of silica-alumina, gamma-alumina, zeolites in the proton-exchanged form, sulfonated zirconia, solid perfluorinated polymeric sulfonic acids, aluminum trifluoride, aluminum chlorofluorides, zinc chloride, aluminum chloride, tin chloride, copper trifluoromethane sulfonate, scandium trichloride, hexafluoroacetylacetonate of complexes of the members of the Lanthanide series of elements according to the Periodic Table according to the International Union of Pure and Applied Chemistry. 45. The process of claim 1 wherein the extended pi-conjugated substrate in step a) comprises coronene and wherein step b) is conducted at a temperature of below about 250�� C. and at a hydrogen partial pressure above about 0.1 bar. 46. The process of claim 1 wherein the extended pi-conjugated substrate in step a) comprises pyrene and wherein step b) is conducted at a temperature of below about 200�� C. and at a hydrogen partial pressure above about 0.1 bar. 47. The process of claim 1 wherein the extended pi-conjugated substrate in step a) comprises carbazole and wherein step b) is conducted at a temperature of below about 250�� C. and at a hydrogen partial pressure above about 0.1 bar. 48. The process of claim 1, wherein the at least partially hydrogenated extended pi-conjugated substrate comprises a mixture of conformers of the at least partially hydrogenated substrate. 49. The process of claim 1, wherein the extended pi-conjugated substrate is a liquid at the dehydrogenation conditions of step b). 50. The process of claim 1, wherein the at least partially hydrogenated extended pi-conjugated substrate is a liquid at the dehydrogenation conditions of step b). 51. The process of claim 1, wherein the extended pi-conjugated substrate and the at least partially hydrogenated extended pi-conjugated substrate are liquids at the dehydrogenation conditions of step b). 52. The process of claim 1, wherein the extended pi-conjugated substrate is a solid at the dehydrogenation conditions of step b). 53. The process of claim 1, wherein the at least partially hydrogenated extended pi-conjugated substrate is a solid at the dehydrogenation conditions of step b). 54. The process of claim 1, wherein substantially none of the extended pi-conjugated substrate sublimes during the dehydrogenation of step b). 55. The process of claim 1, wherein the modulus of the standard enthalpy change of hydrogenation is determined experimentally. 56. The process of claim 1, wherein the modulus of the standard enthalpy change of hydrogenation is calculated by the ab initio density functional theory method. 57. A process for the storage of hydrogen comprising contacting hydrogen with an extended pi-conjugated substrate in the presence of an effective amount of a hydrogenation catalyst under hydrogenation conditions to at least partially hydrogenate the extended pi-conjugated substrate wherein the substrate comprises at least one member selected from the group consisting of extended pi-conjugated substrates with at least one heteroatom, extended pi-coniugated substrates with greater than three rings and extended pi-coniugated substrates with at least two rings wherein one ring is a five membered ring. 58. A process for the storage of hydrogen comprising contacting hydrogen gas at a hydrogen partial pressure greater than about 6.7 bar and at a temperature of between about 50�� C. and about 300�� C. with a solid extended pi-conjugated substrate in the presence of an effective amount of a hydrogenation catalyst to at least partially hydrogenate the extended pi-conjugated substrate wherein the substrate comprises at least one member selected from the group consisting of extended pi-coniugated substrates with at least one heteroatom, extended pi-coniugated substrates with greater than three rings and extended pi-conjugated substrates with at least two rings wherein one ring is a five membered ring. 59. A process for the storage and subsequent release of hydrogen comprising: a) contacting hydrogen, in the presence of a hydrogenation catalyst under hydrogenation conditions, with an extended pi-conjugated substrate to effect storage of hydrogen by forming an at least partially hydrogenated extended pi-conjugated substrate wherein the substrate comprises at least one member selected from the group consisting of extended pi-conjugated substrates with at least one heteroatom, extended pi-conjugated substrates with greater than three rings, and extended pi-coniugated substrates with at least two rings wherein one ring is a five membered ring; and thereafter b) contacting the at least partially hydrogenated extended pi-conjugated substrate under dehydrogenation conditions in the presence of an effective amount of a dehydrogenation catalyst to release hydrogen from the at least partially hydrogenated extended pi-conjugted substrate; wherein the extended pi-conjugated substrate and the at least partially hydrogenated extended pi-conjugated substrate are liquids at the dehydrogenation conditions of step b). 60. A process for releasing hydrogen comprising: providing a substrate comprising at least one at least partially hydrogenated member selected from the group consisting of heteroatoms, extended pi-conjugated substrates with heteroatoms other than nitrogen, pi-conjugated monocyclic substrates with multiple nitrogen heteroatoms, pi-conjugated substrates with at least one triple bonded group, a pitch, extended pi-conjugated substrates with greater than three rings, extended pi-conjugated substrates with at least two rings wherein one ring is a five membered ring, and any combination of two or more of the foregoing; contacting the substrate with an effective amount of at least one catalyst under conditions sufficient to remove hydrogen from the substrate. 61. The process of claim 60 wherein the substrate comprises at least one member selected from the group consisting of N-ethylcarbazole, 1-Ethyl-2-methylindole and 1,2-Dimethylindole. 62. The process of claim 60 wherein the substrate comprises a fluorene.
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