WO2007001164A1 - Metal oxide catalyst for hydrogen generation and method of producing the same - Google Patents
Metal oxide catalyst for hydrogen generation and method of producing the same Download PDFInfo
- Publication number
- WO2007001164A1 WO2007001164A1 PCT/KR2006/002532 KR2006002532W WO2007001164A1 WO 2007001164 A1 WO2007001164 A1 WO 2007001164A1 KR 2006002532 W KR2006002532 W KR 2006002532W WO 2007001164 A1 WO2007001164 A1 WO 2007001164A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- hydrogen generation
- catalyst
- metal oxide
- borohydride
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000001257 hydrogen Substances 0.000 title claims abstract description 90
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 90
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 75
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims description 47
- 229910052751 metal Inorganic materials 0.000 claims description 74
- 239000002184 metal Substances 0.000 claims description 70
- 230000003647 oxidation Effects 0.000 claims description 33
- 238000007254 oxidation reaction Methods 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 11
- XPFAJCSMHOQBQB-UHFFFAOYSA-N 2-aminoacetic acid;nitric acid Chemical compound O[N+]([O-])=O.NCC(O)=O XPFAJCSMHOQBQB-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002736 metal compounds Chemical class 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 229910020598 Co Fe Inorganic materials 0.000 claims description 5
- 229910002519 Co-Fe Inorganic materials 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- -1 wovens Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005485 electric heating Methods 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000003456 ion exchange resin Substances 0.000 claims description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910001509 metal bromide Inorganic materials 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 229910001511 metal iodide Inorganic materials 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- FZHLWVUAICIIPW-UHFFFAOYSA-M sodium gallate Chemical compound [Na+].OC1=CC(C([O-])=O)=CC(O)=C1O FZHLWVUAICIIPW-UHFFFAOYSA-M 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- HVTHJRMZXBWFNE-UHFFFAOYSA-J sodium zincate Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Zn+2] HVTHJRMZXBWFNE-UHFFFAOYSA-J 0.000 claims description 2
- 239000008247 solid mixture Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052713 technetium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000012448 Lithium borohydride Substances 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- FLLNLJJKHKZKMB-UHFFFAOYSA-N boron;tetramethylazanium Chemical compound [B].C[N+](C)(C)C FLLNLJJKHKZKMB-UHFFFAOYSA-N 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 238000000197 pyrolysis Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 16
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000001994 activation Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000004471 Glycine Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QRXDDLFGCDQOTA-UHFFFAOYSA-N cobalt(2+) iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Co+2].[O-2] QRXDDLFGCDQOTA-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000009474 immediate action Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- PCIREHBGYFWXKH-UHFFFAOYSA-N iron oxocobalt Chemical compound [Fe].[Co]=O PCIREHBGYFWXKH-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
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- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/68—Vanadium, niobium, tantalum or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
- C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
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- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates to a metal oxide or mixed-metal oxide catalyst for hydrogen generation from metal borohydride.
- the invention also relates to a method of making, sintering, activating a metal oxide catalyst, regenerating a deactivated metal oxide catalyst, and the use of the catalyst for oxidative reaction on various chemical systems.
- Transition metal oxides have been employed as a catalyst in a variety of chemical processes, such as oxidation (U.S. Pat. No. 6,124,499), NOx treatment (U.S. Pat. No. 6,916,945), oxidation and ammoxidation of an alkane (U.S. Pat. No. 6,777,571 ), transesterification (U.S. Pat. No. 5,350,879) and oxidative coupling of methane (U.S. Pat. No 4,826,796). Nonetheless, metal oxides or mixed-metal oxides have not been investigated or used for the application of hydrogen generation from metal borohydride solution in our best knowledge.
- the catalytic activity of the metal oxides is closely associated with preparation conditions, electronic structures, degree of crystallization, oxidation states, surface area, and so on. Furthermore, the careful control of surface structures, compositions, phase or particle sizes of the metal oxides may play a critical role for diverse chemical catalyses.
- Hydrogen is one of fundamental gases, which is largely necessitated in synthetic chemical companies. In aspect of clean energy, hydrogen has been gained much attention for the applications of fuel cells, hydrogen combustion engines, turbines etc. Due to recent increasing demands of hydrogen gas, several different methods of hydrogen storage systems have been developed, which include compressed or liquefied hydrogen, H 2 adsorption on carbon nano-tube, activated carbon, or metals or mixed metal alloys. Compressed or liquefied H 2 is relatively easy to control the H 2 flow rate and pressure, but involves potential safety issues. The adsorption methods for H 2 storage also have many problems including low hydrogen density per unit volume, deterioration of the materials, and slow response time for H 2 generation, etc. Recently, hydrogen generation from aqueous borohydride solution using a catalyst has stirred many interests in scientific communities since it is not only stable in normal operation condition, but also releases hydrogen gas in safe and controllable way.
- the present invention provides a catalyst for hydrogen generation having high hydrogen generation efficiency and low manufacturing cost.
- the present invention also provides a method of manufacturing a catalyst for hydrogen generation having high hydrogen generation efficiency and low manufacturing cost.
- the present invention also provides another method of manufacturing a catalyst for hydrogen generation having high hydrogen generation efficiency and low manufacturing cost.
- the present invention also provides a method of regenerating a deactivated catalyst for hydrogen generation.
- a hydrogen generation catalyst comprising one or more metal oxides.
- a method of making the hydrogen generation catalyst from a metal source comprising oxidations of the metal in a temperature of about 200 to about 1200 degrees centigrade in the air or ozone.
- a method of making the metal oxide catalyst from a metal compound comprising decomposing the metal compound by heating.
- a method of regenerating deactivated metal oxide catalyst for hydrogen generation comprising: (a) sonicating the catalyst in solvent;
- FIG. 1 shows an X-ray diffraction pattern of an iron oxide catalyst according to an embodiment of the present invention.
- FIG. 2 shows a graph of hydrogen flow rate versus time for a Co 3 Fe 2 -oxide catalyst prepared from a glycine-nitrate process.
- FIG. 3 shows a graph of hydrogen flow rate versus time for a CoFe 4 -mixed oxide catalyst prepared from thermal oxidation in a microwave oven.
- FIG. 4 shows a graph of hydrogen flow rate versus time for a partially sintered Fe- oxide catalyst prepared from thermal oxidation in a microwave oven.
- FIG. 5 shows a graph of hydrogen flow rate versus time for a sintered Fe-oxide catalyst prepared from thermal oxidation in a microwave oven, and sintered at 1150 degree C.
- FIG. 6 shows a plot of maximum hydrogen flow rates versus a Co/Fe molar ratio for Co-Fe oxide catalysts prepared from a glycine-nitrate process.
- the present invention is directed to provide a cost-effective metal oxide catalyst for hydrogen generation having a high performance catalytic activity.
- the present invention also provides a method of making a supported and an unsupported catalyst based on metal oxides and a process of hydrogen generation.
- the present invention provides catalysts for hydrogen generation including one or more metal oxides.
- the metal oxide may include one or more transition metal oxides.
- the metal oxide catalyst for hydrogen generation comprises one or more transition metal oxide comprising oxides of metal elements selected from a group of Sc, T, V, Cr, Mn 1 Fe, Ni, Cu 1 Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and mixtures thereof, wherein transition metal oxide has mono, multiple oxidation states, or mixtures thereof.
- the transition metal oxides herein comprising oxides of metal elements selected from a group of Fe, Co, Ni, Cu, Ru, Rh, and mixtures thereof).
- the metal oxide catalyst comprises one or more transition metal oxides coupled with one or more non-transition metal oxides, wherein non-transition metal comprises Li, Na, Sr, K, Rb Cs, Fr, Mg, Ca, Sr, Ba, Ra, Al, Si, Fe, Ga, In, Sn, Pb or mixtures thereof.
- Some mixed-metal oxides show an inhibiting effect on hydrogen generation. Oxides of metal elements selected from Mo, Zn, V, W, and so on possessing an agtanotic effect on hydrogen generation are also useful for controlling hydrogen flow rates.
- the hydrogen generation catalyst herein refers to, but not particularly limited to, mixed-metal oxides comprising oxides of metal elements selected from Fe, Co, Cu, Ni, Ru, Rh, and a combination thereof.
- the oxidation states of those metals may be mono, multiple, or mixtures thereof.
- the ratio of Co to Fe may range from 0.001 to 1000. If the ratio of Co to Fe is less than 0.001 , hydrogen is hardly generated. If the ratio of Co to Fe is greater than 1000, the generation rate of hydrogen does not increase any more and since Co is expensive, it is not economical.
- mixed-metal oxide catalysts show not only higher catalytic activity due to a synergistic effect, but also much shorter activation time compared to single metal oxide catalysts.
- the metal or mixed-metal oxide may be coupled with ferromagnetic materials.
- the metal oxide catalyst can have a form of powder, chip, disk, rod, wire, mesh, bead, monolith with/without porosity, strip with/without porosity, or metal oxide particles supported on a substrate comprising metals, ceramics, polymers, glass, fibers, fabrics, textiles, wovens, nonwovens, alloys, zeolites, molecular sieves, ion exchange resins, graphite, metal oxide, metal carbide, metal boride, metal nitride, and mixtures thereof.
- the metal oxide may be supported by a carrier, or may be in the form of unsupported catalyst.
- the surface area of the metal oxide catalyst may range from 1 m 2 /g to 500 m 2 /g.
- the preparation of metal oxide may be carried out using a method of thermal or hydrothermal oxidation of metal or a decomposition process of a variety of metal compounds.
- An unsupported metal oxide catalyst is prepared by thermal oxidation of metal in an oxidative environment such as air or ozone.
- the temperature of thermal oxidation typically may be in the range of 200 ⁇ 1200 degree C, preferably 400 ⁇ 800 degree C. If the temperature of thermal oxidation is less than 200 degree C, oxidation does not occur sufficiently, thereby the metal oxide is not obtained sufficiently. If the temperature of thermal oxidation is greater than 1200 degree C, the catalyst becomes denser by melting and the activity of the catalyst is reduced.
- the color of oxidized metal may be an indication of degree of its surface oxidation.
- metal oxide The simplest way to make metal oxide is a microwave assisted thermal oxidation process in the air.
- the microwave heating process not only oxidizes metal powder, but also sinters the metal oxide particles within 0.5 - 20 minutes depending on the power (preferably 500 - 950 W) of the microwave.
- metals may be oxidized and sintered by open frame or electric discharge heating in the air or ozone. Structure analysis of those metal oxide samples are carried out by using a method of X-ray diffraction (XRD).
- FIG 1 shows an XRD pattern indicating the complete conversion of iron metal to iron oxide.
- the heating may be performed using, for example, a microwave oven, an electric high temperature furnace, an electric heating oven, a heat gun, a hot plate or combinations thereof, but is not limited thereto.
- the metal may be oxidized and sintered at the same time.
- metal oxide is to oxidize metal in an electric furnace at a temperature of 200 ⁇ 1200 degree C (preferably 400 ⁇ 800 degree C) in the air or ozone for 10 minutes to 12 hours (preferably 1 to 2 hours).
- Metal oxide also can be prepared by hydrothermal oxidation or steam oxidation. These processes may take more time to complete compared with the microwave heating process, and often require additional thermal treatments for the use of a catalyst for hydrogen generation.
- Another embodiment of the invention is to make metal oxide catalyst by thermal decomposition of metal compounds.
- Precursors of metal oxide catalysts may be, without limitation, metal fluoride, metal chloride, metal bromide, metal iodide, metal nitrate, metal carbonate, metal hydroxide, metal borate, metal acetate, metal oxalate, or an organometallic compound.
- a glycine-nitrate method may be employed for the preparation of metal oxide or mixed-metal oxide powder with high surface area. The size and porosity of the metal oxide particles can be controlled by adjusting the amount of glycine. Details of the glycine-nitrate method may be found in http://picturethis.pnl.gov/PictureT.nsf/AII/ 3QWS7T7opendocument.
- a supported metal oxide catalyst is prepared through a decomposition process of a metal compound that is bound to, entrapped within, and coated on a substrate comprising metals, ceramics, polymers, glass, fibers, fabrics, textiles, wovens, nonwovens, fibers, alloys, zeolites, molecular sieves, ion exchange resins, graphite, metal oxide, metal carbide, metal boride, metal nitride, and mixtures thereof.
- Another preparation method of a supported catalyst is the oxidation of coated metal on a substrate by heating in the air or ozone. Coating of metal film on a substrate can be achieved by an electroplating or electrodeless plating process, but is not limited to these processes.
- a process of hydrogen generation according to the present invention is initiated by contacting a metal oxide catalyst with a solution comprising metal borohydride, a base, and proton donor solvent.
- a base used herein plays a role to stabilize metal borohydride in a solution.
- a common base used in a metal borohydride solution may be lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium sulfide, sodium zincate, sodium gallate, sodium silicate, and mixtures thereof but is not limited thereto.
- Hydrogen generation from a metal borohydride solution results from solvorolysis of metal borohydride by proton donor solvent.
- any proton donor solvents can be used for the solvolysis of metal borohydride.
- the preferred solvent is water and any alcohol comprising without limitation, ethylene glycol, glycerol, methanol, ethanol, isopropanol, isobutanol, propanol, propanediol, butanol, and mixtures thereof.
- Another process of hydrogen generation starts by mixing a proton donor solvent with a solid system comprising a metal oxide catalyst and solid metal borohydride. Hydrogen generation of this process may be controlled by the amount of the added solvent to a solid mixture of the metal oxide catalyst and metal borohydride.
- the catalyst is activated, an instant increase of the amount of hydrogen gas is observed.
- heating is desirable.
- the preferred heating temperature is in the range of about 30 ⁇ 100 degree C (preferably 40 ⁇ 80 degree C).
- the activation process is not necessary unless the process of hydrogen generation needs immediate action.
- activation of metal oxide catalysts may be related with the amount of the catalysts, concentrations of metal borohydride and stabilizer, and particle sizes of the catalysts. Mixed-metal oxide catalysts often showed shorter activation time for hydrogen generation.
- the deactivated metal oxide catalyst can be re-activated through the following process: (1 ) sonicating the catalyst in solvent; (2) rinsing the catalysts with solvent several times; and (3) heating the catalyst at 200 ⁇ 1200 degree C (preferably 400 ⁇ 800 degree C).
- the solvent may be Dl water, but is not limited thereto.
- the heating may be performed using a high temperature furnace, electric heating oven, heat gun, hot plate, a microwave oven, an electric furnace or a combination thereof.
- the heating temperature is less than 200 degree C, the deactivated metal oxide is not properly regenerated. If the heating temperature is greater than 1200 degree C, the catalyst becomes denser by melting and the activity of the catalyst is reduced.
- Example 1 Preparation of a shaped CoFe 4 -oxide catalyst using a microwave assisted thermal oxidation process.
- Co-4Fe metal 1.7678 g of Co metal powder and 4.468 g g of Fe metal powder were mixed with a mechanical agitator for 10 minutes.
- Paste of Co-4Fe metal was prepared by mixing the Co-4Fe metal powder with deionized (Dl) water. The paste was spread out flat (approximately 2-3 mm thick) on a ceramic plate and chopped into 2 - 3 mm pieces. The shaped paste was dried and heated in a microwave oven with a power of 950 W for 10 minutes.
- Example 2 Preparation of an unsupported iron oxide catalyst using a microwave assisted thermal oxidation process.
- An iron oxide catalyst was prepared by thermal oxidation of 20 g of iron metal powder in a microwave oven for 10 minutes. The power of the microwave was set to
- Example 3 Preparation of mixed-metal oxide catalysts using a microwave assisted thermal oxidation process.
- mixed-metal oxide catalysts were prepared by thermal oxidation of mixed- metal powder in a microwave oven for 10 minutes.
- the other preparation conditions were the same as example 1.
- two kinds of metal powder mixture with a molar ratio of 50:50 were mixed by using a mechanical agitator before heating.
- TABLE 2 summaries a combination of coupled metal oxides with a molar ratio of 50:50.
- Example 4 Preparation of a shaped iron oxide catalyst using a microwave assisted thermal oxidation process. 30 g of iron metal powder was spread out flat on a ceramic plate and packed with a flat plastic plate. The packed flat iron metal powder was chopped into 2 - 3 mm pieces, and heated in a microwave oven with a power of 950 W for 10 minutes. The further sintering of the iron oxide catalyst was carried out by heating at 1150 degree C in an electric furnace for 2 hours. The sintered sample was crushed and grounded for the X- ray diffraction (XRD) analysis. FIG. 1 shows a XRD pattern of synthesized iron oxide sample in a microwave oven. The XRD phase shows no sign of the Fe metal phase implying complete oxidation.
- XRD X- ray diffraction
- Example 5 Preparation of an unsupported iron oxide catalyst in a high temperature furnace.
- Iron metal powder contained in an alumina crucible was placed in a high temperature furnace and heated at 800 degree C for 2 hours in air. The resulting sample was oxidized and sintered simultaneously.
- Cobalt-iron oxide catalysts with various molar ratios of cobalt and iron were synthesized using a glycine-nitrate process.
- an aqueous solution containing glycine and mixture of either cobalt nitrate/iron chloride or cobalt chloride/iron nitrate was prepared and heated until excess water had boiled away. Continuous heating of the remaining material resulted in self-ignition, which generated fine black powder.
- the molar ratios of glycine and metal salts in this invention were 1 : 1.
- Fig 6 shows a plot of maximum hydrogen flow rates of Co-Fe oxide catalysts having a molar ratio of Co: Fe from 0.25 to 9.
- Example 7 Preparation of a supported iron-cobalt oxide catalyst 2 M solution of cobalt and iron nitrates was prepared by dissolving equal molar cobalt and iron nitrates in de-ionized water. 2 ml of the resulting solution was introduced into a 100 ml beaker containing 3 g of molecular sieves (Yakuri Pure Chemicals Co. LTD, Osaka, Japan). The cobalt and iron ions impregnated molecular sieves were dried in an oven at 100 degree C for 1 hour, and consecutively heated on a hot plate with a maximum temperature setting for 1 hour.
- Hydrogen generation experiments were carried out to measure a flow rate of hydrogen.
- Several metal oxide and mixed-metal oxide samples were employed. The experiment was carried out by adding 20 ml of a sodium borohydride solution containing 16 wt. % NaBH 4 , 3.5 wt. % NaOH, and 80.5 wt. % of Dl water to a reaction vessel containing a certain amount (0.01 -0.3 g) of metal or mixed-metal oxide powder samples.
- FIGS. 2-6 shows a graph of the hydrogen flow rates of the various metal oxide catalysts.
- FIG.S 2-5 The plots of hydrogen flow rate vs. time of various metal oxide catalysts are shown in FIG.S 2-5.
- the hydrogen flow rate hit a peak of -50000 ml/min-g without temperature control (see FIG. 2).
- the CoFe 4 -oxide produced from a microwave assisted thermal oxidation process revealed the maximum hydrogen flow rate of 3065 ml/min-g (see FIG. 3), but its activation commenced immediately.
- the maximum hydrogen flow rates of Fe-oxide samples are 2193 and 2473 ml/min-g for partially sintered Fe-Oxide (microwave heating) and sintered Fe-Oxide (microwave heating + additional heating at 1150 degree C), respectively (see FIGS 4-5). Although it seemed that additional thermal treatments did not make big differences on the hydrogen flow rates, sintered catalysts are more favorable in terms of convenience of use and mechanical strength. In the system of the Co-Fe oxides prepared from a glycine-nitrate process, decreasing the amount of Fe contents elevated the maximum hydrogen flow rates, but it remained constant after the molar ratio of Co/Fe of 1.5 (see FIG. 6).
- the hydrogen flow rate may depend on concentration of sodium borohydride, the particle size and amount of the catalysts, compositions of hetero metals and so on. Maximum hydrogen flow rates of various mixed metal oxides are summarized in Table 1. Unlike a Co-Fe oxide system, Fe- or Co-oxide coupled with zinc oxide had no catalytic activity on hydrogen generation. Other metal oxides coupled with Co-oxides are relatively weak catalytic activities on hydrogen generation.
- Hydrogen can be manufactured efficiently and economically by using the metal oxide catalyst for hydrogen generation of the present invention.
Abstract
The present invention provides metal oxide catalysts and preparation method thereof. More particularly, provided are metal oxide catalysts for hydrogen generation including one or more metal oxide and preparation method thereof. Hydrogen can be manufactured efficiently and economically by using the metal oxide catalyst for hydrogen generation of the present invention.
Description
METAL OXIDE CATALYST FOR HYDROGEN GENERATION AND METHOD OF
PRODUCING THE SAME
TECHNICAL FIELD The present invention relates to a metal oxide or mixed-metal oxide catalyst for hydrogen generation from metal borohydride. The invention also relates to a method of making, sintering, activating a metal oxide catalyst, regenerating a deactivated metal oxide catalyst, and the use of the catalyst for oxidative reaction on various chemical systems.
BACKGROUND ART
Transition metal oxides have been employed as a catalyst in a variety of chemical processes, such as oxidation (U.S. Pat. No. 6,124,499), NOx treatment (U.S. Pat. No. 6,916,945), oxidation and ammoxidation of an alkane (U.S. Pat. No. 6,777,571 ), transesterification (U.S. Pat. No. 5,350,879) and oxidative coupling of methane (U.S. Pat. No 4,826,796). Nonetheless, metal oxides or mixed-metal oxides have not been investigated or used for the application of hydrogen generation from metal borohydride solution in our best knowledge. On the whole, the catalytic activity of the metal oxides is closely associated with preparation conditions, electronic structures, degree of crystallization, oxidation states, surface area, and so on. Furthermore, the careful control of surface structures, compositions, phase or particle sizes of the metal oxides may play a critical role for diverse chemical catalyses.
Hydrogen is one of fundamental gases, which is largely necessitated in synthetic chemical companies. In aspect of clean energy, hydrogen has been gained much attention for the applications of fuel cells, hydrogen combustion engines, turbines etc. Due to recent increasing demands of hydrogen gas, several different methods of hydrogen storage systems have been developed, which include compressed or liquefied hydrogen, H2 adsorption on carbon nano-tube, activated carbon, or metals or mixed metal alloys. Compressed or liquefied H2 is relatively easy to control the H2 flow rate and pressure, but involves potential safety issues. The adsorption methods for H2 storage also have many problems including low hydrogen density per unit volume, deterioration of the materials, and slow response time for H2 generation, etc. Recently, hydrogen generation from aqueous borohydride solution using a catalyst has stirred many interests in scientific communities since it is not only stable in normal operation
condition, but also releases hydrogen gas in safe and controllable way.
It has been widely known that hydrogen gas is generated by hydrolysis of sodium borohydride in the aid of acid, transition metals, or their salts (Kaufam, C. M. and Sen, B., J. Chem. Soc. Dalton Trans. 1985, 307-313). U.S. Pat. No. 6,534,033 disclosed that a transition metal catalyst was employed to generate hydrogen gas from a stabilized metal borohydride solution. Those metal catalysts, such as ruthenium, rhodium, or cobalt metal supported on various substrates exhibited high activity for hydrogen generation. Other metal catalysts, including silver, iron, nickel, copper, and so on are often inactive or less active for hydrogen generation at room temperature based on unpublished tests. Some metal catalysts such as copper and nickel, showed improved activity after they were heated in nitrogen at 600 - 800 degree C. Usage of high performance metal catalyst, such as ruthenium, rhodium or platinum, is cost prohibitive for one-time use in various applications.
According to a recent publication (Kojima, Y. et al., Int. J. Hydrogen Energy, 2002, 27, 1029-1034), Toyota Central R&D Laboratories, Inc. reported that a catalyst containing platinum and UCOO2 has a high catalytic activity for hydrogen generation due to the synergistic effects of finely divided platinum metal on the metal oxide framework. However, this system still uses a precious metal like platinum, which is not attractive for practical application due to high production cost. From a practical point of view, a high performance catalyst for hydrogen generation having low production cost is highly advantageous.
DISCLOSURE TECHNICAL PROBLEM The present invention provides a catalyst for hydrogen generation having high hydrogen generation efficiency and low manufacturing cost.
The present invention also provides a method of manufacturing a catalyst for hydrogen generation having high hydrogen generation efficiency and low manufacturing cost. The present invention also provides another method of manufacturing a catalyst for hydrogen generation having high hydrogen generation efficiency and low manufacturing cost.
The present invention also provides a method of regenerating a deactivated
catalyst for hydrogen generation.
TECHNICAL SOLUTION
According to an aspect of the present invention, there is provided a hydrogen generation catalyst comprising one or more metal oxides.
According to another aspect of the present invention, there is provided a method of making the hydrogen generation catalyst from a metal source comprising oxidations of the metal in a temperature of about 200 to about 1200 degrees centigrade in the air or ozone. According to another aspect of the present invention, there is provided a method of making the metal oxide catalyst from a metal compound comprising decomposing the metal compound by heating.
According to another aspect of the present invention, there is provided a method of regenerating deactivated metal oxide catalyst for hydrogen generation comprising: (a) sonicating the catalyst in solvent;
(b) washing the catalyst with solvent; and
(c) heating the catalyst at about 200 - 1200 degree C.
DESCRIPTION OF DRAWINGS FIG. 1 shows an X-ray diffraction pattern of an iron oxide catalyst according to an embodiment of the present invention.
FIG. 2 shows a graph of hydrogen flow rate versus time for a Co3Fe2-oxide catalyst prepared from a glycine-nitrate process.
FIG. 3 shows a graph of hydrogen flow rate versus time for a CoFe4-mixed oxide catalyst prepared from thermal oxidation in a microwave oven.
FIG. 4 shows a graph of hydrogen flow rate versus time for a partially sintered Fe- oxide catalyst prepared from thermal oxidation in a microwave oven.
FIG. 5 shows a graph of hydrogen flow rate versus time for a sintered Fe-oxide catalyst prepared from thermal oxidation in a microwave oven, and sintered at 1150 degree C.
FIG. 6 shows a plot of maximum hydrogen flow rates versus a Co/Fe molar ratio
for Co-Fe oxide catalysts prepared from a glycine-nitrate process.
BEST MODE
The present invention is directed to provide a cost-effective metal oxide catalyst for hydrogen generation having a high performance catalytic activity. The present invention also provides a method of making a supported and an unsupported catalyst based on metal oxides and a process of hydrogen generation.
The present invention will now be described more fully hereinafter with reference to the accompanying figures, in which preferred embodiments of the invention are shown. This invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein.
The present invention provides catalysts for hydrogen generation including one or more metal oxides. The metal oxide may include one or more transition metal oxides.
The metal oxide catalyst for hydrogen generation comprises one or more transition metal oxide comprising oxides of metal elements selected from a group of Sc, T, V, Cr, Mn1 Fe, Ni, Cu1 Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and mixtures thereof, wherein transition metal oxide has mono, multiple oxidation states, or mixtures thereof. More preferably, the transition metal oxides herein comprising oxides of metal elements selected from a group of Fe, Co, Ni, Cu, Ru, Rh, and mixtures thereof). In another embodiment, the metal oxide catalyst comprises one or more transition metal oxides coupled with one or more non-transition metal oxides, wherein non-transition metal comprises Li, Na, Sr, K, Rb Cs, Fr, Mg, Ca, Sr, Ba, Ra, Al, Si, Fe, Ga, In, Sn, Pb or mixtures thereof. Some mixed-metal oxides show an inhibiting effect on hydrogen generation. Oxides of metal elements selected from Mo, Zn, V, W, and so on possessing an agtanotic effect on hydrogen generation are also useful for controlling hydrogen flow rates. By coupling with these metal elements with active metal oxides containing elements of Fe, Co, Cu, Ni, Ru, Rh and mixtures thereof, desirable hydrogen flow rate and controlled activation time can be achieved for specific applications. For high performance catalytic activity and cost-effectiveness, the present invention provides that the hydrogen generation catalyst herein refers to, but not particularly limited to, mixed-metal oxides comprising oxides of metal elements selected from Fe, Co, Cu, Ni, Ru, Rh, and a combination thereof. The oxidation states of those metals may be mono, multiple, or mixtures thereof. In this case, the ratio of Co to Fe
may range from 0.001 to 1000. If the ratio of Co to Fe is less than 0.001 , hydrogen is hardly generated. If the ratio of Co to Fe is greater than 1000, the generation rate of hydrogen does not increase any more and since Co is expensive, it is not economical.
These mixed-metal oxide catalysts show not only higher catalytic activity due to a synergistic effect, but also much shorter activation time compared to single metal oxide catalysts. In case of the convenient isolation of used catalysts, the metal or mixed-metal oxide may be coupled with ferromagnetic materials.
The metal oxide catalyst can have a form of powder, chip, disk, rod, wire, mesh, bead, monolith with/without porosity, strip with/without porosity, or metal oxide particles supported on a substrate comprising metals, ceramics, polymers, glass, fibers, fabrics, textiles, wovens, nonwovens, alloys, zeolites, molecular sieves, ion exchange resins, graphite, metal oxide, metal carbide, metal boride, metal nitride, and mixtures thereof.
That is, the metal oxide may be supported by a carrier, or may be in the form of unsupported catalyst. The surface area of the metal oxide catalyst may range from 1 m2/g to 500 m2/g.
The preparation of metal oxide may be carried out using a method of thermal or hydrothermal oxidation of metal or a decomposition process of a variety of metal compounds. An unsupported metal oxide catalyst is prepared by thermal oxidation of metal in an oxidative environment such as air or ozone. The temperature of thermal oxidation typically may be in the range of 200 ~ 1200 degree C, preferably 400 ~ 800 degree C. If the temperature of thermal oxidation is less than 200 degree C, oxidation does not occur sufficiently, thereby the metal oxide is not obtained sufficiently. If the temperature of thermal oxidation is greater than 1200 degree C, the catalyst becomes denser by melting and the activity of the catalyst is reduced. The color of oxidized metal may be an indication of degree of its surface oxidation.
The simplest way to make metal oxide is a microwave assisted thermal oxidation process in the air. The microwave heating process not only oxidizes metal powder, but also sinters the metal oxide particles within 0.5 - 20 minutes depending on the power (preferably 500 - 950 W) of the microwave. Alternatively, metals may be oxidized and sintered by open frame or electric discharge heating in the air or ozone. Structure analysis of those metal oxide samples are carried out by using a method of X-ray diffraction (XRD). FIG 1 shows an XRD pattern indicating the complete conversion of iron metal to iron oxide.
The heating may be performed using, for example, a microwave oven, an electric
high temperature furnace, an electric heating oven, a heat gun, a hot plate or combinations thereof, but is not limited thereto. In this case, the metal may be oxidized and sintered at the same time.
Alternative way of making metal oxide is to oxidize metal in an electric furnace at a temperature of 200 ~ 1200 degree C (preferably 400 ~ 800 degree C) in the air or ozone for 10 minutes to 12 hours (preferably 1 to 2 hours). Metal oxide also can be prepared by hydrothermal oxidation or steam oxidation. These processes may take more time to complete compared with the microwave heating process, and often require additional thermal treatments for the use of a catalyst for hydrogen generation. Another embodiment of the invention is to make metal oxide catalyst by thermal decomposition of metal compounds. Precursors of metal oxide catalysts may be, without limitation, metal fluoride, metal chloride, metal bromide, metal iodide, metal nitrate, metal carbonate, metal hydroxide, metal borate, metal acetate, metal oxalate, or an organometallic compound. For the preparation of metal oxide or mixed-metal oxide powder with high surface area, a glycine-nitrate method may be employed. The size and porosity of the metal oxide particles can be controlled by adjusting the amount of glycine. Details of the glycine-nitrate method may be found in http://picturethis.pnl.gov/PictureT.nsf/AII/ 3QWS7T7opendocument.
A supported metal oxide catalyst is prepared through a decomposition process of a metal compound that is bound to, entrapped within, and coated on a substrate comprising metals, ceramics, polymers, glass, fibers, fabrics, textiles, wovens, nonwovens, fibers, alloys, zeolites, molecular sieves, ion exchange resins, graphite, metal oxide, metal carbide, metal boride, metal nitride, and mixtures thereof. Another preparation method of a supported catalyst is the oxidation of coated metal on a substrate by heating in the air or ozone. Coating of metal film on a substrate can be achieved by an electroplating or electrodeless plating process, but is not limited to these processes.
A process of hydrogen generation according to the present invention is initiated by contacting a metal oxide catalyst with a solution comprising metal borohydride, a base, and proton donor solvent. A base used herein plays a role to stabilize metal borohydride in a solution. A common base used in a metal borohydride solution may be lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium sulfide, sodium zincate, sodium gallate, sodium silicate, and mixtures thereof but is not limited thereto. Hydrogen generation from a metal borohydride solution results from solvorolysis
of metal borohydride by proton donor solvent. Thus, any proton donor solvents can be used for the solvolysis of metal borohydride. The preferred solvent is water and any alcohol comprising without limitation, ethylene glycol, glycerol, methanol, ethanol, isopropanol, isobutanol, propanol, propanediol, butanol, and mixtures thereof. Another process of hydrogen generation starts by mixing a proton donor solvent with a solid system comprising a metal oxide catalyst and solid metal borohydride. Hydrogen generation of this process may be controlled by the amount of the added solvent to a solid mixture of the metal oxide catalyst and metal borohydride.
It often takes a few minutes to generate a hydrogen gas from a metal borohydride solution when a freshly made metal oxide catalyst is employed. The surface activation is engaged by immersion of the catalyst in a metal borohydride solution for 1 - 30 minutes.
Once the catalyst is activated, an instant increase of the amount of hydrogen gas is observed. To accelerate the surface activation of the freshly made metal oxide catalyst, heating is desirable. The preferred heating temperature is in the range of about 30 ~ 100 degree C (preferably 40 ~ 80 degree C). However, the activation process is not necessary unless the process of hydrogen generation needs immediate action. In general, activation of metal oxide catalysts may be related with the amount of the catalysts, concentrations of metal borohydride and stabilizer, and particle sizes of the catalysts. Mixed-metal oxide catalysts often showed shorter activation time for hydrogen generation.
After several uses of the metal oxide or mixed-metal catalyst, its catalytic activity may decline due to surface contamination and/or partial reduction. The deactivated metal oxide catalyst can be re-activated through the following process: (1 ) sonicating the catalyst in solvent; (2) rinsing the catalysts with solvent several times; and (3) heating the catalyst at 200 ~ 1200 degree C (preferably 400 ~ 800 degree C). The solvent may be Dl water, but is not limited thereto. The heating may be performed using a high temperature furnace, electric heating oven, heat gun, hot plate, a microwave oven, an electric furnace or a combination thereof.
If the heating temperature is less than 200 degree C, the deactivated metal oxide is not properly regenerated. If the heating temperature is greater than 1200 degree C, the catalyst becomes denser by melting and the activity of the catalyst is reduced.
MODE FOR INVENTION
This invention is more specifically illustrated by following Examples, which are not meant to limit the invention.
Example 1. Preparation of a shaped CoFe4-oxide catalyst using a microwave assisted thermal oxidation process.
1.7678 g of Co metal powder and 4.468 g g of Fe metal powder were mixed with a mechanical agitator for 10 minutes. Paste of Co-4Fe metal was prepared by mixing the Co-4Fe metal powder with deionized (Dl) water. The paste was spread out flat (approximately 2-3 mm thick) on a ceramic plate and chopped into 2 - 3 mm pieces. The shaped paste was dried and heated in a microwave oven with a power of 950 W for 10 minutes.
Example 2. Preparation of an unsupported iron oxide catalyst using a microwave assisted thermal oxidation process.
An iron oxide catalyst was prepared by thermal oxidation of 20 g of iron metal powder in a microwave oven for 10 minutes. The power of the microwave was set to
950 W. Upon generating the microwave, the iron metal powder started glowing red-hot within a minute. The microwave heating of the sample continued for 10 minutes. After completion of the heating, the resulting sample showing black was partially consolidated.
Example 3. Preparation of mixed-metal oxide catalysts using a microwave assisted thermal oxidation process.
Various mixed-metal oxide catalysts were prepared by thermal oxidation of mixed- metal powder in a microwave oven for 10 minutes. The other preparation conditions were the same as example 1. For the preparation of mixed-metal oxide catalysts, two kinds of metal powder mixture with a molar ratio of 50:50 were mixed by using a mechanical agitator before heating. TABLE 2 summaries a combination of coupled metal oxides with a molar ratio of 50:50.
TABLE 2. Summary of coupled metal oxides with a molar ratio of 50:50
Example 4. Preparation of a shaped iron oxide catalyst using a microwave assisted thermal oxidation process.
30 g of iron metal powder was spread out flat on a ceramic plate and packed with a flat plastic plate. The packed flat iron metal powder was chopped into 2 - 3 mm pieces, and heated in a microwave oven with a power of 950 W for 10 minutes. The further sintering of the iron oxide catalyst was carried out by heating at 1150 degree C in an electric furnace for 2 hours. The sintered sample was crushed and grounded for the X- ray diffraction (XRD) analysis. FIG. 1 shows a XRD pattern of synthesized iron oxide sample in a microwave oven. The XRD phase shows no sign of the Fe metal phase implying complete oxidation.
Example 5. Preparation of an unsupported iron oxide catalyst in a high temperature furnace.
Iron metal powder contained in an alumina crucible was placed in a high temperature furnace and heated at 800 degree C for 2 hours in air. The resulting sample was oxidized and sintered simultaneously.
Example 6. Preparation of an unsupported cobalt-iron oxide catalyst using a glycine-nitrate combustion process
Cobalt-iron oxide catalysts with various molar ratios of cobalt and iron were synthesized using a glycine-nitrate process. In this process, an aqueous solution containing glycine and mixture of either cobalt nitrate/iron chloride or cobalt chloride/iron nitrate was prepared and heated until excess water had boiled away. Continuous heating of the remaining material resulted in self-ignition, which generated fine black powder. The molar ratios of glycine and metal salts in this invention were 1 : 1. Fig 6 shows a plot of maximum hydrogen flow rates of Co-Fe oxide catalysts having a molar ratio of Co: Fe from 0.25 to 9.
Example 7. Preparation of a supported iron-cobalt oxide catalyst 2 M solution of cobalt and iron nitrates was prepared by dissolving equal molar cobalt and iron nitrates in de-ionized water. 2 ml of the resulting solution was introduced into a 100 ml beaker containing 3 g of molecular sieves (Yakuri Pure Chemicals Co. LTD, Osaka, Japan). The cobalt and iron ions impregnated molecular sieves were dried in an oven at 100 degree C for 1 hour, and consecutively heated on a hot plate with a maximum temperature setting for 1 hour.
Example 8. Hydrogen generation experiments
Hydrogen generation experiments were carried out to measure a flow rate of hydrogen. Several metal oxide and mixed-metal oxide samples were employed. The experiment was carried out by adding 20 ml of a sodium borohydride solution containing
16 wt. % NaBH4, 3.5 wt. % NaOH, and 80.5 wt. % of Dl water to a reaction vessel containing a certain amount (0.01 -0.3 g) of metal or mixed-metal oxide powder samples.
The hydrogen flow rate was measured using a mass flow controller interfaced with a personal computer. FIGS. 2-6 shows a graph of the hydrogen flow rates of the various metal oxide catalysts.
The plots of hydrogen flow rate vs. time of various metal oxide catalysts are shown in FIG.S 2-5. In the case of Co3Fe2-oxide catalyst prepared using a glycine- nitrate process according to the present invention, the hydrogen flow rate hit a peak of -50000 ml/min-g without temperature control (see FIG. 2). On the other hand, the CoFe4-oxide produced from a microwave assisted thermal oxidation process revealed the maximum hydrogen flow rate of 3065 ml/min-g (see FIG. 3), but its activation commenced immediately. The maximum hydrogen flow rates of Fe-oxide samples are 2193 and 2473 ml/min-g for partially sintered Fe-Oxide (microwave heating) and sintered Fe-Oxide (microwave heating + additional heating at 1150 degree C), respectively (see FIGS 4-5). Although it seemed that additional thermal treatments did not make big differences on the hydrogen flow rates, sintered catalysts are more favorable in terms of convenience of use and mechanical strength. In the system of the Co-Fe oxides prepared from a glycine-nitrate process, decreasing the amount of Fe contents elevated the maximum hydrogen flow rates, but it remained constant after the molar ratio of Co/Fe of 1.5 (see FIG. 6). The hydrogen flow rate may depend on concentration of sodium borohydride, the particle size and amount of the catalysts, compositions of hetero metals and so on. Maximum hydrogen flow rates of various mixed metal oxides are summarized in Table 1. Unlike a Co-Fe oxide system, Fe- or Co-oxide coupled with zinc oxide had no catalytic activity on hydrogen generation. Other metal oxides coupled with Co-oxides are relatively weak catalytic activities on hydrogen generation.
TABLE 1. Maximum Hydrogen Flow Rate (ml/min-g) of Coupled Metal Oxide Catalysts
INDUSTRIALAPPLICABILITY
Hydrogen can be manufactured efficiently and economically by using the metal oxide catalyst for hydrogen generation of the present invention.
Claims
CLAIMS 1. A hydrogen generation catalyst comprising one or more metal oxides.
2. The hydrogen generation catalyst of claim 1 , wherein metal oxide comprises one or more transition metal oxides.
3. The hydrogen generation catalyst of claim 1 , wherein metal oxide comprises one or more transition metal oxides coupled with one or more non-transition metal oxides.
4. The transition metal oxide of claim 2, wherein transition metal comprises Sc, T, V, Cr, Mn, Fe, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and mixtures thereof.
5. The hydrogen generation catalyst of claim 1 , wherein metal oxide comprises at least oxides of metal elements having Fe, Co, Cu, Ni, Ru, Rh or mixtures thereof.
6. The non-transition metal oxide of claim 3, wherein non-transition metal comprises Li, Na, Sr, K, Rb Cs, Fr, Mg, Ca, Sr, Ba, Ra, Al, Si, Fe, Ga, In, Sn, Pb or mixtures thereof.
7. The hydrogen generation catalyst of claim 1 , wherein metal oxides have mono, multiple oxidation states, or mixtures thereof.
8. The hydrogen generation catalyst of claim 1 , wherein metal oxide is Co-Fe oxide having a molar ratio of Co to Fe in the range of 0.001 to 1000.
9. The hydrogen generation catalyst of claim 1 , wherein metal oxide has an unsupported form.
10. The hydrogen generation catalyst of claim 9 in the form of powder, chip, disk, rod, wire, mesh, bead, monolith, strip with porosity, or strip without porosity.
11. The hydrogen generation catalyst of claim 1 , which in contact to a support.
12. The hydrogen generation catalyst of claim 11 , wherein the support is selected from the group consisting of: metals, ceramics, polymers, glass, fibers, fabrics, textiles, wovens, nonwovens, fibers, alloys, zeolites, molecular sieves, ion exchange resins, graphite, metal oxide, metal carbide, metal boride, metal nitride, and mixtures thereof.
13. A method of making the hydrogen generation catalyst of claim 1 from a metal source comprising oxidations of the metal in a temperature of about 200 to about 1200 degrees centigrade in the air or ozone.
14. The method according to claim 13, wherein the oxidation may be thermal oxidation, hydrothermal oxidation, or steam oxidation.
15. The method according to claim 13, wherein the oxidizing and sintering of the metal oxide prepared from a metal source are carried out in a microwave oven, an electric high temperature furnace, an electric heating oven, a heat gun, a hot plate, or a combination thereof.
16. A method of making the metal oxide catalyst of claim 1 from a metal compound comprising decomposing the metal compound by heating.
17. The method according to claim 16, wherein the metal compound is metal fluoride, metal chloride, metal bromide, metal iodide, metal nitrate, metal carbonate, metal hydroxide, metal borate, metal acetate, metal oxalate, or an organometallic compound.
18. The method according to claim 16, comprising a pyrolysis process and a glycine nitrate process in air.
19. A process of hydrogen generation using the hydrogen generation catalyst of claim 1 , comprising contacting the metal oxide catalyst with a solution comprising metal borohydride, a base, and proton donor solvent.
20. The process of hydrogen generation of claim 19, wherein the metal borohydride is selected from the group consisting of: lithium borohydride, sodium borohydride, potassium borohydride, ammonium borohydride, tetramethyl ammonium borohydride, and mixtures thereof.
21. The process of hydrogen generation of claim 19, wherein the base is selected from the group consisting of: lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium sulfide, sodium zincate, sodium gallate, sodium silicate, and mixtures thereof.
22. The process of hydrogen generation of claim 19, wherein the proton donor solvent is selected from the group consisting of: water, alcohol, ethylene glycol, glycerol, methanol, ethanol, isopropanol, isobutanol, propanol, propanediol, butanol, and mixtures thereof.
23. A process of hydrogen generation using the hydrogen generation catalyst of claim 1 , comprising contacting proton donor solvent with a solid mixture comprising metal borohydride and metal oxide catalysts according to claim 1.
24. A method of regenerating deactivated metal oxide catalyst for hydrogen generation comprising:
(a) sonicating the deactivated catalyst in solvent; (b) washing the catalyst with solvent; and
(c) heating the catalyst at about 200 - 1200 degree C.
25. The method according to claim 24, wherein the heating is accomplished by a microwave oven, a high temperature furnace, an electric heating oven, a heat gun, a hot plate, or a combination thereof.
26. The method according to claim 24, wherein the solvent is deionized water.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06769101A EP1896178A4 (en) | 2005-06-29 | 2006-06-29 | Metal oxide catalyst for hydrogen generation and method of producing the same |
| JP2008518048A JP4818358B2 (en) | 2005-06-29 | 2006-06-29 | Metal oxide catalyst for hydrogen production and method for producing the same |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/160,571 | 2005-06-29 | ||
| US11/160,571 US7309479B2 (en) | 2005-06-29 | 2005-06-29 | Cobalt oxide catalysts |
| US11/162,108 US7566440B2 (en) | 2005-06-29 | 2005-08-29 | Metal oxide catalysts |
| US11/162,108 | 2005-08-29 |
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| WO2007001164A1 true WO2007001164A1 (en) | 2007-01-04 |
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| PCT/KR2006/002532 WO2007001164A1 (en) | 2005-06-29 | 2006-06-29 | Metal oxide catalyst for hydrogen generation and method of producing the same |
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|---|---|
| EP (1) | EP1896178A4 (en) |
| KR (1) | KR100724555B1 (en) |
| WO (1) | WO2007001164A1 (en) |
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| EP2168188A1 (en) * | 2007-05-18 | 2010-03-31 | Enerfuel, Inc. | Hydrogen production from borohydrides and glycerol |
| US10435343B2 (en) | 2016-04-13 | 2019-10-08 | Northwestern University | Efficient catalytic greenhouse gas-free hydrogen and aldehyde formation from alcohols |
| CN110586116A (en) * | 2019-09-25 | 2019-12-20 | 广西师范大学 | MoO of hydrogen evolution electrocatalyst2-Ni/CC composite material and preparation method thereof |
| CN110639542A (en) * | 2019-09-06 | 2020-01-03 | 华南理工大学 | In-situ hybridization room-temperature formaldehyde removal catalyst, composite gel, and preparation method and application thereof |
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| CN115403008A (en) * | 2022-09-16 | 2022-11-29 | 重庆大学 | MgH 2 -Co 3 V 2 O 8 Composite hydrogen storage material and preparation method thereof |
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| JP2010527893A (en) * | 2007-05-18 | 2010-08-19 | エナフューエル インコーポレイテッド | Production of hydrogen from borohydride and glycerol |
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| US8609054B2 (en) | 2007-05-18 | 2013-12-17 | Enerfuel, Inc. | Hydrogen production from borohydrides and glycerol |
| US10435343B2 (en) | 2016-04-13 | 2019-10-08 | Northwestern University | Efficient catalytic greenhouse gas-free hydrogen and aldehyde formation from alcohols |
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| CN110586116A (en) * | 2019-09-25 | 2019-12-20 | 广西师范大学 | MoO of hydrogen evolution electrocatalyst2-Ni/CC composite material and preparation method thereof |
| CN110586116B (en) * | 2019-09-25 | 2021-08-17 | 广西师范大学 | MoO of hydrogen evolution electrocatalyst2-Ni/CC composite material and preparation method thereof |
| CN113477252A (en) * | 2021-06-30 | 2021-10-08 | 常州大学 | Preparation method and application of composite porous catalyst simultaneously containing titanium and other transition metals |
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Also Published As
| Publication number | Publication date |
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| EP1896178A1 (en) | 2008-03-12 |
| KR100724555B1 (en) | 2007-06-04 |
| KR20070001831A (en) | 2007-01-04 |
| EP1896178A4 (en) | 2011-10-05 |
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