JP2008194549A - Catalyst for producing hydrogen for fuel cell and dss operation-correspondence fuel cell - Google Patents
Catalyst for producing hydrogen for fuel cell and dss operation-correspondence fuel cell Download PDFInfo
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- JP2008194549A JP2008194549A JP2007029062A JP2007029062A JP2008194549A JP 2008194549 A JP2008194549 A JP 2008194549A JP 2007029062 A JP2007029062 A JP 2007029062A JP 2007029062 A JP2007029062 A JP 2007029062A JP 2008194549 A JP2008194549 A JP 2008194549A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- 239000001257 hydrogen Substances 0.000 title claims abstract description 78
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 78
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000000446 fuel Substances 0.000 title claims abstract description 71
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims description 65
- TVZRAEYQIKYCPH-UHFFFAOYSA-N 3-(trimethylsilyl)propane-1-sulfonic acid Chemical compound C[Si](C)(C)CCCS(O)(=O)=O TVZRAEYQIKYCPH-UHFFFAOYSA-N 0.000 claims description 36
- 239000000470 constituent Substances 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 239000000843 powder Substances 0.000 description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 35
- 239000011572 manganese Substances 0.000 description 31
- 238000005259 measurement Methods 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000002441 X-ray diffraction Methods 0.000 description 17
- 238000000833 X-ray absorption fine structure spectroscopy Methods 0.000 description 15
- 229910002651 NO3 Inorganic materials 0.000 description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 11
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 239000010948 rhodium Substances 0.000 description 8
- 238000000629 steam reforming Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000006057 reforming reaction Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 150000002603 lanthanum Chemical class 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000010025 steaming Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- HBAGRTDVSXKKDO-UHFFFAOYSA-N dioxido(dioxo)manganese lanthanum(3+) Chemical compound [La+3].[La+3].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O HBAGRTDVSXKKDO-UHFFFAOYSA-N 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 241000877463 Lanio Species 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- Y02E60/50—Fuel cells
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
本発明は、燃料供給のＯＮ／ＯＦＦを繰り返すＤＳＳ運転によっても良好に使用可能な燃料電池用水素製造触媒、及びその触媒を備えたＤＳＳ運転対応型燃料電池に関する。 The present invention relates to a hydrogen production catalyst for a fuel cell that can be satisfactorily used even by DSS operation in which fuel supply is repeatedly turned on and off, and a DSS operation-compatible fuel cell including the catalyst.
水素と酸素を燃料とする固体高分子型燃料電池(ＰＥＦＣ)は、低公害で熱効率が高いため、自動車用電源や分散電源等の幅広い分野での動力源として、また、家電製品等の民生用の動力源としての適用が期待されている。この燃料電池に燃料である水素を供給するには幾つかの方法があるが、メタン、プロパン、天然ガス、灯油等の炭化水素を触媒（本願では「水素製造触媒」という。）の存在下で水蒸気改質して水素を製造する方法が一般的に検討されている。 The polymer electrolyte fuel cell (PEFC) that uses hydrogen and oxygen as fuel is low-pollution and high in thermal efficiency, so it can be used as a power source in a wide range of fields such as automobile power supplies and distributed power supplies, and for consumer electronics such as home appliances. Application as a power source is expected. There are several methods for supplying hydrogen as a fuel to the fuel cell, but hydrocarbons such as methane, propane, natural gas, and kerosene are used in the presence of a catalyst (referred to herein as a “hydrogen production catalyst”). A method for producing hydrogen by steam reforming has been generally studied.
こうした水蒸気改質法は、例えばメタンを原料とした場合には、そのメタンを水素製造触媒の存在下で、ＣＨ4＋Ｈ2Ｏ→ＣＯ＋３Ｈ2 の反応により水素を含む改質ガスを得るが、その改質ガスは多量の一酸化炭素を含み、この一酸化炭素は燃料電池の働きを阻害する被毒物質として作用する。そこで、その後に、例えばＣｕ−Ｚｎ等のＣＯ変成触媒の存在下で、ＣＯ＋Ｈ2Ｏ→ＣＯ2＋Ｈ2 の反応により一酸化炭素を二酸化炭素に変換し、さらにその後に、例えばＰｔやＲｕ等のＣＯ除去触媒を有するＣＯ除去触媒の存在下で、ＣＯ＋１／２Ｏ2→ＣＯ の反応により一酸化炭素をさらに除去する方法が検討されている（例えば、特許文献１，２を参照）。
In the steam reforming method, for example, when methane is used as a raw material, a reformed gas containing hydrogen is obtained by a reaction of CH 4 + H 2 O → CO + 3H 2 in the presence of a hydrogen production catalyst. The reformed gas contains a large amount of carbon monoxide, and this carbon monoxide acts as a poisoning substance that inhibits the operation of the fuel cell. Therefore, after that, in the presence of a CO shift catalyst such as Cu—Zn, for example, carbon monoxide is converted into carbon dioxide by a reaction of CO + H 2 O → CO 2 + H 2 , and then, for example, Pt, Ru, etc. A method of further removing carbon monoxide by the reaction of CO + 1 / 2O 2 → CO 2 in the presence of a CO removal catalyst having a CO removal catalyst has been studied (see, for example,
ところで、従来、工業的に利用されている水素の９０％は主にＮｉ／Ａｌ２Ｏ３触媒を用いた水蒸気改質法により連続的に製造されているが、こうしたＮｉ／Ａｌ２Ｏ３触媒は貴金属を含まないため安価であり、実用上極めて有利な触媒である。一方、水素を燃料とする固体高分子型燃料電池（ＰＥＦＣ）は民生用の燃料電池としての実用化が期待されており、そのため、daily start-up and shut-down運転（本願では「ＤＳＳ運転」という。）が伴うことから、水蒸気改質法による水素製造も燃料電池のＤＳＳ運転に対応した安定製造が要求されている。 Meanwhile, conventionally, although 90% of the hydrogen that is industrially used are mainly continuously produced by the steam reforming method using a Ni / Al 2 O 3 catalyst, such Ni / Al 2 O 3 catalyst Is inexpensive because it contains no precious metal and is a very advantageous catalyst for practical use. On the other hand, a polymer electrolyte fuel cell (PEFC) using hydrogen as a fuel is expected to be put to practical use as a consumer fuel cell. Therefore, a daily start-up and shut-down operation (in this application, “DSS operation”) is expected. Therefore, stable production corresponding to the DSS operation of the fuel cell is also required for the hydrogen production by the steam reforming method.
ＤＳＳ運転対応型燃料電池に水素を供給するためには、水蒸気改質もＤＳＳ運転により行われることになる。そのため、水素製造触媒には、燃料であるメタン等の炭化水素原料が供給される燃料雰囲気と、炭化水素原料が供給されない水蒸気雰囲気とが任意の間隔で繰り返される。こうした場合であっても、上記の安価なＮｉ／Ａｌ２Ｏ３触媒を用いて水素を製造できればよいが、Ｎｉ／Ａｌ２Ｏ３は高温で水蒸気雰囲気下に晒されると、Ｎｉ金属のシンタリングが起こり、活性が低下することがよく知られている（例えば非特許文献１を参照）。 In order to supply hydrogen to the DSS operation compatible fuel cell, steam reforming is also performed by the DSS operation. Therefore, a fuel atmosphere in which a hydrocarbon raw material such as methane as a fuel is supplied to a hydrogen production catalyst and a water vapor atmosphere in which no hydrocarbon raw material is supplied are repeated at an arbitrary interval. Even in such a case, it is sufficient that hydrogen can be produced using the above-described inexpensive Ni / Al 2 O 3 catalyst. However, Ni / Al 2 O 3 is sintered in Ni metal when exposed to a steam atmosphere at a high temperature. It is well known that the activity decreases and the activity decreases (see, for example, Non-Patent Document 1).
そこで現在、固体高分子型燃料電池用の水蒸気改質触媒には、Ｒｕを触媒活性成分としＡｌ２Ｏ３を担体としたものや、ＲｕとＮｉを触媒活性成分としＡｌ２Ｏ３を担体としたものが用いられている（例えば特許文献３を参照）。
しかしながら、貴金属であるＲｕは高価であるため、実用化のためにはＮｉ等の比較的値段の安い卑金属を使うことができると共に、炭化水素原料が供給される燃料雰囲気と、炭化水素原料が供給されない水蒸気雰囲気とが任意の間隔で繰り返される場合であっても安定した触媒性能を発揮できる、ＤＳＳ運転対応型の水素製造触媒が求められている。 However, since Ru, which is a noble metal, is expensive, it is possible to use a relatively inexpensive base metal such as Ni for practical use, as well as a fuel atmosphere to which a hydrocarbon raw material is supplied and a hydrocarbon raw material to be supplied. There is a need for a DSS operation-compatible hydrogen production catalyst that can exhibit stable catalyst performance even when a steam atmosphere that is not performed is repeated at an arbitrary interval.
本発明は、上記課題を解決するためになされたものであって、その目的は、燃料供給のＯＮ／ＯＦＦを繰り返すＤＳＳ運転によっても安定して使用することができる燃料電池用水素製造触媒を提供すること、及び、その水素製造触媒を備えたＤＳＳ運転対応型燃料電池を提供することにある。 The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a hydrogen production catalyst for a fuel cell that can be stably used even by DSS operation in which fuel supply is repeatedly turned on and off. It is another object of the present invention to provide a fuel cell for DSS operation including the hydrogen production catalyst.
上記課題を解決する本発明の第１の観点に係る燃料電池用水素製造触媒は、一般式ＡＢＯ３型で当該ＢがＮｉｘＭｎ（１−ｘ）の組成物からなり、前記ｘが０．７±０．１０であることを特徴とする。 The hydrogen production catalyst for a fuel cell according to the first aspect of the present invention for solving the above-mentioned problems is a composition of the general formula ABO 3 type, wherein B is a composition of Ni x Mn (1-x) , and x is 0.8. It is characterized by 7 ± 0.10.
この発明によれば、上記組成物を燃料電池用水素製造触媒として用いたので、炭化水素原料が供給されない水蒸気雰囲気でも触媒性能を維持することができ、ＤＳＳ運転対応型の燃料電池用水素製造触媒として好ましく用いることができる。さらに、この発明によれば、水素製造触媒が貴金属を主要材料として含んでいないので、触媒コストの低減を図ることができる。 According to the present invention, since the composition is used as a hydrogen production catalyst for a fuel cell, the catalyst performance can be maintained even in a steam atmosphere in which no hydrocarbon raw material is supplied. Can be preferably used. Furthermore, according to the present invention, since the hydrogen production catalyst does not contain a noble metal as a main material, the catalyst cost can be reduced.
また、本発明の第２の観点に係る燃料電池用水素製造触媒は、一般式ＡＢＯ３型で当該ＢがＮｉｘＭ（１−ｘ）の組成物からなり、燃料供給のＯＮ／ＯＦＦを繰り返すＤＳＳ運転対応型の燃料電池用水素製造触媒であって、前記組成物は、ＤＳＳ運転時に、金属Ｎｉがオキシ炭酸化合物に担持されていることを特徴とする。この燃料電池用水素製造触媒において、前記ＭがＭｎであり、前記ｘが０．７±０．１０であることが好ましい。 The fuel cell hydrogen production catalyst according to the second aspect of the present invention is a general formula ABO 3 type, wherein B is composed of Ni x M (1-x) , and the fuel supply is repeatedly turned ON / OFF. A hydrogen production catalyst for a fuel cell that is compatible with DSS operation, wherein the composition is characterized in that metal Ni is supported on an oxycarbonate during DSS operation. In this fuel cell hydrogen production catalyst, the M is preferably Mn and the x is preferably 0.7 ± 0.10.
この発明によれば、上記組成物をＤＳＳ運転対応型の燃料電池用水素製造触媒として用い、その組成物を構成するＮｉがＤＳＳ運転時に金属Ｎｉの状態でオキシ炭酸化合物に担持されているので、炭化水素原料が供給されない水蒸気雰囲気でも触媒性能を維持することができ、ＤＳＳ運転対応型の燃料電池用水素製造触媒として好ましく用いることができる。さらに、この発明によれば、水素製造触媒が貴金属を主要材料として含んでいないので、触媒コストの低減を図ることができる。 According to the present invention, the composition is used as a hydrogen production catalyst for a fuel cell for DSS operation, and Ni constituting the composition is supported on the oxycarbonate compound in the state of metal Ni during the DSS operation. The catalyst performance can be maintained even in a steam atmosphere in which no hydrocarbon raw material is supplied, and it can be preferably used as a hydrogen production catalyst for a fuel cell for DSS operation. Furthermore, according to the present invention, since the hydrogen production catalyst does not contain a noble metal as a main material, the catalyst cost can be reduced.
上記第１及び第２の観点に係る本発明の燃料電池用水素製造触媒において、前記ＡがＬａであることが好ましい。前記組成物を構成するＡ元素は特に限定されないが、この発明によれば、Ａ元素をＬａとすればより好ましい触媒性能を発揮できる。 In the hydrogen production catalyst for a fuel cell of the present invention according to the first and second aspects, it is preferable that the A is La. Although the A element which comprises the said composition is not specifically limited, According to this invention, if A element is set to La, more preferable catalyst performance can be exhibited.
上記第１及び第２の観点に係る本発明の燃料電池用水素製造触媒において、前記ＡがＬａｙＣｅ（１−ｙ）であることが好ましい。前記組成物を構成するＡ元素は特に限定されないが、この発明によれば、Ａ元素をＬａｙＣｅ（１−ｙ）とすればより好ましい触媒性能を発揮できる。 In the fuel cell hydrogen production catalyst according to the first and second aspects of the present invention, it is preferable that the A is La y Ce (1-y) . A element forming the composition is not particularly limited, according to the present invention, the element A La y Ce (1-y) Tosureba can exhibit more preferable catalyst performance.
上記第１及び第２の観点に係る本発明の燃料電池用水素製造触媒において、前記組成物が、Ｐｄ、Ｐｔ、Ｒｈ及びＲｕから選ばれるいずれか１以上を含むことが好ましい。この発明によれば、上記組成物にＰｄ、Ｐｔ、Ｒｈ及びＲｕから選ばれるいずれか１以上を含有させることにより、ＤＳＳ運転時における触媒性能をより向上させることができる。なお、これらの元素は、微量含有させるだけでよいので、従来型の触媒に比べてコストの面でも有利である。 In the fuel cell hydrogen production catalyst of the present invention according to the first and second aspects, the composition preferably contains any one or more selected from Pd, Pt, Rh and Ru. According to this invention, the catalyst performance during the DSS operation can be further improved by adding any one or more selected from Pd, Pt, Rh and Ru to the composition. Since these elements only need to be contained in a trace amount, they are advantageous in terms of cost as compared with conventional catalysts.
上記課題を解決する本発明のＤＳＳ運転対応型燃料電池は、上記第１及び第２の観点に係る本発明の燃料電池用水素製造触媒を有する水素製造装置を構成部材として備えることを特徴とする。 The DSS operation-compatible fuel cell of the present invention that solves the above-described problems includes a hydrogen production apparatus having the hydrogen production catalyst for a fuel cell of the present invention according to the first and second aspects as a constituent member. .
この発明によれば、ＤＳＳ運転対応型燃料電池の構成部材として、上記本発明の燃料電池用水素製造触媒を有する水素製造装置を用いたので、コストメリットのあるＤＳＳ運転対応型の燃料電池として好ましく適用できる。 According to the present invention, since the hydrogen production apparatus having the hydrogen production catalyst for a fuel cell of the present invention is used as a constituent member of the DSS operation compatible fuel cell, it is preferable as a DSS operation compatible fuel cell having cost merit. Applicable.
本発明の燃料電池用水素製造触媒によれば、炭化水素原料が供給されない水蒸気雰囲気でも触媒性能を維持することができるので、ＤＳＳ運転対応型の低コストの燃料電池用水素製造触媒として好ましく用いることができる。また、本発明のＤＳＳ運転対応型燃料電池によれば、コストメリットのあるＤＳＳ運転対応型の燃料電池として好ましく適用できる。 According to the fuel cell hydrogen production catalyst of the present invention, the catalyst performance can be maintained even in a steam atmosphere in which no hydrocarbon raw material is supplied. Therefore, the catalyst is preferably used as a low-cost fuel cell hydrogen production catalyst for DSS operation. Can do. Further, the DSS operation compatible fuel cell of the present invention can be preferably applied as a DSS operation compatible fuel cell with cost merit.
以下、本発明の燃料電池用水素製造触媒及びＤＳＳ運転対応型燃料電池について図面を参照しつつ説明する。なお、以下の実施形態と実施例とにより本発明の範囲が限定されるものではなく、以下の構成要素には、技術常識の範囲内で当業者が容易に想定できるものや実質的の同一のもののも含まれる。 Hereinafter, the hydrogen production catalyst for fuel cells and the fuel cell for DSS operation according to the present invention will be described with reference to the drawings. It should be noted that the scope of the present invention is not limited by the following embodiments and examples, and the following constituent elements can be easily assumed by those skilled in the art within the scope of common general technical knowledge, or substantially the same. The thing is also included.
（燃料電池用水素製造触媒）
本発明の燃料電池用水素製造触媒は、燃料供給のＯＮ／ＯＦＦを繰り返すＤＳＳ運転対応型の燃料電池用水素製造触媒として用いられるものであって、一般式ＡＢＯ３型でそのＢがＮｉｘＭ（１−ｘ）の組成物からなるものである。そして、この組成物は、ＤＳＳ運転時に、上記Ｎｉ元素が金属Ｎｉとしてオキシ炭酸化合物に担持された状態になっている。
(Hydrogen production catalyst for fuel cells)
The fuel cell hydrogen production catalyst of the present invention is used as a fuel cell hydrogen production catalyst for DSS operation that repeats ON / OFF of fuel supply, and is a general formula ABO 3 type, where B is Ni x M It consists of the composition of (1-x) . And this composition is in the state by which the said Ni element was carry | supported by the oxycarbonic acid compound as metal Ni at the time of DSS driving | operation.
本発明では、Ｎｉ元素がＤＳＳ運転時に金属Ｎｉとしてオキシ炭酸化合物に担持されているように構成されるので、炭化水素原料が供給されない水蒸気雰囲気を伴うshut-down時においても、Ｎｉ酸化物になって触媒活性が失活することがなく、触媒性能を維持することができるという効果がある。 In the present invention, since the Ni element is configured to be supported on the oxycarbonic acid compound as metal Ni during the DSS operation, it becomes Ni oxide even at the time of shut-down accompanied by a steam atmosphere in which no hydrocarbon raw material is supplied. Thus, there is an effect that the catalyst performance is not deactivated and the catalyst performance can be maintained.
一般式ＡＢＯ３型はペロブスカイト型構造としてよく知られている構造であるが、本発明においては、結晶学的に必ずしもペロブスカイト構造でなくてもよく、組成比としてＡＢＯ３型になっていればよい。 The general formula ABO 3 type is a structure well known as a perovskite structure. However, in the present invention, the perovskite structure is not necessarily crystallographically, and the composition ratio may be ABO 3 type. .
ＡＢＯ３型の組成物において、本願では、Ｂサイトの元素がＮｉｘＭ（１−ｘ）であることに特徴がある。特に好ましい触媒活性を示すＭ元素としては、Ｍｎ（マンガン）を挙げることができる。Ｍｎを構成元素とした場合のＮｉｘＭｎ（１−ｘ）において、炭化水素原料から水素への水蒸気改質反応（例えば、ＣＨ4＋Ｈ2Ｏ→ＣＯ＋３Ｈ2）による変換効率の観点からは、ｘが０．７±０．１０であること、すなわち、ｘが０．６以上０．８以下であることが好ましい。 The ABO 3 type composition is characterized in that the element at the B site is Ni x M (1-x) in the present application. M element (manganese) can be mentioned as an M element exhibiting particularly preferable catalytic activity. In the case of Ni x Mn (1-x) where Mn is a constituent element, from the viewpoint of conversion efficiency by a steam reforming reaction (for example, CH 4 + H 2 O → CO + 3H 2 ) from a hydrocarbon raw material to hydrogen, x Is preferably 0.7 ± 0.10, that is, x is 0.6 or more and 0.8 or less.
ＡＢＯ３型の組成物において、Ａサイトの元素としては、ランタノイド元素（Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｐｍ，Ｓｍ，Ｇｄ，Ｔｂ，Ｄｙ等）や、Ｂａ、Ｓｒ、Ｃａ等のアルカリ土類元素を挙げることができる。この中でも、Ｂサイトの元素をＮｉｘＭｎ（１−ｘ）とした場合においては、Ａサイトの元素としてＬａを好ましく挙げることができ、また、ＬａｙＣｅ（１−ｙ）を好ましく挙げることができる。これらの元素でＡサイトを構成することにより、好ましい触媒性能を発揮させることができる。なお、後述の実験例においては、ＬａｙＣｅ（１−ｙ）においてｙを０．５としたものを例示している。 In the ABO 3 type composition, the elements at the A site include lanthanoid elements (La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, etc.) and alkaline earth elements such as Ba, Sr, Ca, etc. Can be mentioned. Among these, when the element at the B site is Ni x Mn (1-x) , La can be preferably exemplified as the element at the A site, and La y Ce (1-y) can be preferably exemplified. it can. By constituting the A site with these elements, preferable catalytic performance can be exhibited. In the experimental examples described later, an example in which y is 0.5 in La y Ce (1-y) is illustrated.
なお、本発明のＡＢＯ３型の水素製造触媒において、その組成物が、Ｐｄ、Ｐｔ、Ｒｈ及びＲｕから選ばれるいずれか１以上を含むことが好ましい。水素製造触媒の総重量に対する前記の元素の含有量は、ＤＳＳ運転時における触媒性能をより高めることができる量を選択する。これらの元素はいずれも貴金属と呼ばれるものであり、コストの点ではやや好ましくないが、本願では含有量が上記範囲であり、主要成分として含まないので、コスト上昇を極力防ぐことができる。なお、上記元素の中でも、特にＰｄを含有させることが触媒活性の点でより好ましい。 In the ABO 3 type hydrogen production catalyst of the present invention, the composition preferably contains any one or more selected from Pd, Pt, Rh and Ru. The content of the element with respect to the total weight of the hydrogen production catalyst is selected so that the catalyst performance during DSS operation can be further improved. All of these elements are called noble metals and are somewhat undesirable in terms of cost. However, in the present application, the content is in the above range and is not included as a main component, so that an increase in cost can be prevented as much as possible. In addition, it is more preferable from the point of catalyst activity to contain Pd especially among the said elements.
以上説明した本発明の水素製造触媒は、ＤＳＳ運転対応型の燃料電池用水素製造触媒として好ましく用いることができる。 The hydrogen production catalyst of the present invention described above can be preferably used as a hydrogen production catalyst for a fuel cell for DSS operation.
（水素製造触媒の製造方法）
上述した水素製造触媒は以下のようにして作製することができる。例えＬａＮｉ0.7Ｍ0.3Ｏ３からなる組成物を作製する場合、例えばメタノール溶媒に、ランタン塩、ニッケル塩、マンガン塩を最終的に上記組成比になるように所定量秤量して投入し、さらにクエン酸やエチレングリコール等の支持塩を所定量秤量して投入した後、所定の温度で重合させてゲル化させ、その後、所定の温度で炭化と焼成を行って前駆物質を作製し、その後さらに焼成することによって、ペロブスカイト型構造又はそれに類似する構造からなるＬａＮｉ0.7Ｍ0.3Ｏ３を作製することができる。
(Method for producing hydrogen production catalyst)
The above-described hydrogen production catalyst can be produced as follows. For example, when preparing a composition composed of LaNi 0.7 M 0.3 O 3 , for example, a lanthanum salt, a nickel salt, and a manganese salt are weighed in a predetermined amount so as to finally have the above composition ratio in a methanol solvent, and further, a quencher is added. A predetermined amount of a supporting salt such as acid or ethylene glycol is weighed and charged, and then polymerized at a predetermined temperature to be gelled, and then carbonized and fired at a predetermined temperature to produce a precursor, and then further calcined. By doing so, LaNi 0.7 M 0.3 O 3 having a perovskite structure or a similar structure can be produced.
なお、Ａサイトに例えばＣｅ（セリウム）を所定の化学量論比で含有させる場合には、Ｌａ塩とＣｅ塩を所定量秤量して加え、また、Ｂサイトに例えばＰｄを所定の化学量論比で含有させる場合には、Ｐｄ塩を所定量秤量して加えることにより調整できる。 For example, when Ce (cerium) is contained in the A site at a predetermined stoichiometric ratio, a predetermined amount of La salt and Ce salt are weighed and added, and for example, Pd is added to the B site at a predetermined stoichiometric amount. When contained in a ratio, it can be adjusted by weighing and adding a predetermined amount of Pd salt.
なお、上記の製造例はその一例であって、必ずしも上記の例に限定されない、 In addition, said manufacture example is the example, Comprising: It is not necessarily limited to said example,
（水素製造装置及び燃料電池）
上述した本発明の水素製造触媒は、水素製造装置内に設けられて、メタン、プロパン、天然ガス、灯油等の炭化水素を水蒸気改質して水素を製造する触媒として用いられる。本発明の水素製造触媒を適用できる水素製造装置の形態は特に限定されず、種々の水素製造装置に好ましく適用可能である。また、こうした水素製造装置を構成部材として備える燃料電池も特に限定されず、各種の形態からなる燃料電池を好ましく適用可能である。本発明の水素製造触媒を適用した水素製造装置や燃料電池は、ＤＳＳ運転対応型の水素製造装置や燃料電池として好ましいものとなり、特にdaily start-up and shut-down運転（ＤＳＳ運転）を伴う民生用の機器や装置に好ましく用いることができる。
(Hydrogen production equipment and fuel cell)
The above-described hydrogen production catalyst of the present invention is provided in a hydrogen production apparatus and used as a catalyst for producing hydrogen by steam reforming hydrocarbons such as methane, propane, natural gas, and kerosene. The form of the hydrogen production apparatus to which the hydrogen production catalyst of the present invention can be applied is not particularly limited, and can be preferably applied to various hydrogen production apparatuses. Moreover, the fuel cell provided with such a hydrogen production apparatus as a constituent member is not particularly limited, and fuel cells having various forms are preferably applicable. A hydrogen production apparatus or fuel cell to which the hydrogen production catalyst of the present invention is applied is preferable as a hydrogen production apparatus or fuel cell compatible with DSS operation, and particularly a consumer product with daily start-up and shut-down operation (DSS operation). It can preferably be used for the apparatus and apparatus for this.
実験例と比較実験例を挙げて本発明の水素製造触媒を更に具体的に説明する。以下の具体例は、本発明の水素製造触媒の一例を挙げたものであり、本発明の範囲が以下の具体例のみに限定されないことは言うまでもない。 The hydrogen production catalyst of the present invention will be described more specifically with reference to experimental examples and comparative experimental examples. The following specific examples are examples of the hydrogen production catalyst of the present invention, and it goes without saying that the scope of the present invention is not limited to the following specific examples.
（実験例１）
１００ｍｌのメタノール溶媒中に以下のモル比となるように秤量した各塩を投入して溶解し、その後、約１３０℃で重合させてゲル化させ、その後、約３３０℃・大気雰囲気で炭化させ、次いで、約５００℃・大気雰囲気で５時間の焼成を行って、前駆物質を作製した。その後さらに、約１０００℃・大気雰囲気で１５時間焼成することによって、ペロブスカイト型構造又はそれに類似する構造からなるＬａＮｉxＭｎ(1-X)Ｏ３の触媒粉末を７種作製した。
(Experimental example 1)
Each salt weighed in the following molar ratio in 100 ml of methanol solvent is added and dissolved, then polymerized and gelled at about 130 ° C., and then carbonized at about 330 ° C. in an air atmosphere, Next, firing was performed at about 500 ° C. in an air atmosphere for 5 hours to prepare a precursor. Then further by calcining for 15 hours at about 1000 ° C. · air atmosphere, and the catalyst powder of LaNi x Mn (1-X)
・硝酸ランタン・６水和物…１（単位：モル比。以下同じ。）
・硝酸ニッケル・６水和物…０、０．２、０．３、０．５、０．７、０．８、１．０
・硝酸マンガン・６水和物…１．０、０．８、０．７、０．５、０．３、０．２、０
・クエン酸…１０
・エチレングリコール…４０
なお、上記のうち、硝酸ニッケルと硝酸マンガンのモル比は、ＮｉxＭｎ(1-X)のｘと（１−ｘ）とが合計で１．０（モル比）になるように調整した。
-Lanthanum nitrate hexahydrate ... 1 (unit: molar ratio; the same applies hereinafter)
Nickel nitrate hexahydrate: 0, 0.2, 0.3, 0.5, 0.7, 0.8, 1.0
Manganese nitrate hexahydrate: 1.0, 0.8, 0.7, 0.5, 0.3, 0.2, 0
・ Citric acid ... 10
・ Ethylene glycol ... 40
In addition, among the above, the molar ratio of nickel nitrate and manganese nitrate was adjusted so that x and (1-x) of Ni x Mn (1-X) were 1.0 (molar ratio) in total.
（実験例２）
作製手順は実験例１と同様であるが、ＬａＮｉ0.7Ｍｎ0.3Ｏ３にＰｄ元素を導入した組成物を作製した。具体的には、ＬａＮｉ0.7Ｍｎ0.3Ｏ３にＰｄ元素をモル比で０．００５と０．０００５導入して、ＬａＮｉ0.7Ｍｎ0.3Ｏ３Ｐｄ０．００５とＬａＮｉ0.7Ｍｎ0.3Ｏ３Ｐｄ０．０００５となるように組成物を作製した。Ｐｄ元素としては、硝酸パラジウム水溶液を用い、ランタン塩等と共に溶解し、実験例１と同様にして、前記組成物からなる触媒粉末を作製した。
(Experimental example 2)
The production procedure was the same as in Experimental Example 1, but a composition in which Pd element was introduced into LaNi 0.7 Mn 0.3 O 3 was produced. Specifically, Pd element is introduced into LaNi 0.7 Mn 0.3 O 3 in a molar ratio of 0.005 and 0.0005, and LaNi 0.7 Mn 0.3 O 3 Pd 0.005 and LaNi 0.7 Mn 0.3 O 3 Pd 0.0005 are introduced. A composition was prepared so that As the Pd element, an aqueous palladium nitrate solution was used and dissolved together with a lanthanum salt or the like, and a catalyst powder made of the above composition was prepared in the same manner as in Experimental Example 1.
（実験例３）
作製手順は実験例１と同様であるが、ＬａＮｉ0.7Ｍｎ0.3Ｏ３にＲｈ元素を導入した組成物を作製した。具体的には、ＬａＮｉ0.7Ｍｎ0.3Ｏ３にＲｈ元素をモル比で０．００５と０．０００５導入して、ＬａＮｉ0.7Ｍｎ0.3Ｏ３Ｒｈ０．００５とＬａＮｉ0.7Ｍｎ0.3Ｏ３Ｒｈ０．０００５となるように組成物を作製した。Ｒｈ元素としては、（硝酸ロジウム水溶液）を用い、ランタン塩等と共に溶解し、実験例１と同様にして、前記組成物からなる触媒粉末を作製した。
(Experimental example 3)
The production procedure was the same as in Experimental Example 1, but a composition in which Rh element was introduced into LaNi 0.7 Mn 0.3 O 3 was produced. Specifically, 0.005 and 0.0005 introduced in a molar ratio of Rh element LaNi 0.7 Mn 0.3 O 3, LaNi 0.7 Mn 0.3
（実験例４）
作製手順は実験例１と同様であるが、ＡサイトにＣｅ元素を導入した組成物を作製した。具体的には、ＡサイトにＣｅ元素をモル比で０．５導入して、Ｌａ0.5Ｃｅ0.5Ｎｉ0.7Ｍｎ0.3Ｏ３となるように組成物を作製した。Ｃｅ元素としては、（硝酸セリウム）を用い、ランタン塩等と共に溶解し、実験例１と同様にして、前記組成物からなる触媒粉末を作製した。
(Experimental example 4)
The production procedure was the same as in Experimental Example 1, but a composition in which Ce element was introduced into the A site was produced. Specifically, 0.5 mol of Ce element was introduced into the A site at a molar ratio to prepare a composition so that La 0.5 Ce 0.5 Ni 0.7 Mn 0.3 O 3 was obtained. As the Ce element, (cerium nitrate) was used and dissolved together with a lanthanum salt and the like, and a catalyst powder made of the above composition was produced in the same manner as in Experimental Example 1.
（比較実験例１）
作製手順は実験例１と同様であるが、ＬａＮｉ0.7Ｍｎ0.3Ｏ３を基準とし、そのＢサイトのＭｎの代わりに、Ａｌ（硝酸塩），Ｃｏ（硝酸塩），Ｃｒ（硝酸塩），Ｆｅ（硝酸塩），Ｔｉ（チタニウムテトライソプロポキシド）を導入した組成物を作製し、それ以外は実験例１と同様にして、各種の組成物からなる触媒粉末を作製した。
(Comparative Experimental Example 1)
The production procedure is the same as in Experimental Example 1, but using LaNi 0.7 Mn 0.3 O 3 as a reference, instead of Mn at the B site, Al (nitrate), Co (nitrate), Cr (nitrate), Fe (nitrate) , Ti (titanium tetraisopropoxide) was prepared, and catalyst powders composed of various compositions were prepared in the same manner as in Experimental Example 1 except that.
（比較実験例２）
作製手順は実験例１と同様であるが、Ｂサイトにさらに他の元素を導入した組成物を作製した。具体的には、Ｂサイトに「Ｂ」元素をモル比で０．１導入して、ＬａＮｉ0.7Ｍｎ0.2Ｂ0.1Ｏ３となるように組成物を作製した。Ｂ元素としては、Ａｌ（硝酸塩），Ｃｏ（硝酸塩），Ｃｒ（硝酸塩），Ｆｅ（硝酸塩），Ｔｉ（チタニウムテトライソプロポキシド）を用い、それぞれの塩をランタン塩等と共に溶解し、実験例１と同様にして、各種の組成物からなる触媒粉末を作製した。
(Comparative Experiment Example 2)
The production procedure was the same as in Experimental Example 1, but a composition in which another element was further introduced into the B site was produced. Specifically, 0.1 composition of “B” element was introduced into the B site at a molar ratio to prepare a composition so that LaNi 0.7 Mn 0.2 B 0.1 O 3 was obtained. As the element B, Al (nitrate), Co (nitrate), Cr (nitrate), Fe (nitrate), Ti (titanium tetraisopropoxide) are used, and each salt is dissolved together with a lanthanum salt. In the same manner, catalyst powders composed of various compositions were prepared.
（比較実験例３）
作製手順は実験例４と同様であるが、ＡサイトにＣｅ元素の代わりに他の元素を導入した組成物を作製した。Ａ元素としては、Ｄｙ（硝酸塩），Ｎｄ（硝酸塩），Ｐｒ（硝酸塩），Ｓｍ（硝酸塩），Ｓｒ（硝酸塩）を用い、それぞれの塩をランタン塩等と共に溶解し、実験例４と同様にして、各種の組成物からなる触媒粉末を作製した。
(Comparative Experiment 3)
The preparation procedure was the same as in Experimental Example 4, but a composition was prepared in which other elements were introduced into the A site instead of the Ce element. As element A, Dy (nitrate), Nd (nitrate), Pr (nitrate), Sm (nitrate), Sr (nitrate) are used, and each salt is dissolved together with a lanthanum salt or the like. Catalyst powders composed of various compositions were prepared.
（触媒活性測定）
図１は、上記実験例と上記比較実験例で得られた触媒粉末の触媒活性を測定する装置を示す模式図である。図１に示すように、触媒活性測定装置は、直径１０ｍｍの石英ガラス製の反応管内に充填した触媒粉末を石英ウールとケイ砂とで両側から挟み、その部分を所定の温度で加熱可能になるように構成した。また、触媒粉末に接触するように熱電対を配置し、加熱時の温度を測定できるよう構成した。図１に示す触媒活性測定装置の上方にガス導入口を設け、下方にガス導出口を設けた。
(Catalyst activity measurement)
FIG. 1 is a schematic diagram showing an apparatus for measuring the catalytic activity of catalyst powders obtained in the experimental example and the comparative experimental example. As shown in FIG. 1, the catalytic activity measuring apparatus sandwiches a catalyst powder filled in a quartz glass reaction tube having a diameter of 10 mm from both sides with quartz wool and silica sand, and can heat the portion at a predetermined temperature. It was configured as follows. In addition, a thermocouple was disposed so as to come into contact with the catalyst powder so that the temperature during heating could be measured. A gas inlet is provided above the catalyst activity measuring apparatus shown in FIG. 1, and a gas outlet is provided below.
触媒活性測定は、上記実験例と上記比較実験例で得られた触媒粉末を粒径０．５μｍ以下に粉砕したものを０．１ｇ秤量し、石英ガラス製の反応管に充填し、２０％Ｈ２／Ｎ２を２００ｍｌ／ｍｉｎで流通させながら７００℃で１時間水素還元を行った。このとき、ＧＨＳＶ（原料ガス供給速度を見掛け触媒体積で除した値）は、２００÷（１／６０）÷０．１＝１２００００ｍｌ／ｈ／ｇとなる。その後、Ｎ２を１６０ｍｌ／ｍｉｎでパージした後、Ｎ２、ＣＨ４、Ｈ２Ｏをそれぞれ流量４１．７ｍｌ／ｍｉｎ、８３．３ｍｌ／ｍｉｎ、２５０ｍｌ／ｍｉｎで流通させ、７００℃で改質反応を行った。このとき、ＧＨＳＶは、３７５÷（１／６０）÷０．１＝２２５０００ｍｌ／ｈ／ｇとなる。出口ガスの定量は、Ｎ２を内部標準ガスとしたガスクロマトグラフィーによって行い、改質反応後の定常活性状態でのＣＨ４転化率を測定した。図２は、定常活性を測定する際のプロファイルである。この実験では、ＧＨＳＶを２２５０００で行っており、通常のＧＨＳＶの数千レベルのものに比べ、かなりの加速試験で行った結果で評価している。 The catalytic activity was measured by weighing 0.1 g of the powdered catalyst powder obtained in the above experimental example and the above comparative experimental example to a particle size of 0.5 μm or less, and filling it into a reaction tube made of quartz glass. Hydrogen reduction was performed at 700 ° C. for 1 hour while flowing 2 / N 2 at 200 ml / min. At this time, GHSV (a value obtained by dividing the raw material gas supply rate by the apparent catalyst volume) is 200 ÷ (1/60) ÷ 0.1 = 120,000 ml / h / g. After purging N 2 at 160 ml / min, N 2 , CH 4 , and H 2 O were passed at flow rates of 41.7 ml / min, 83.3 ml / min, and 250 ml / min, respectively, and the reforming reaction was performed at 700 ° C. Went. At this time, GHSV is 375 / (1/60) /0.1=225000 ml / h / g. The quantification of the outlet gas was performed by gas chromatography using N 2 as an internal standard gas, and the CH 4 conversion rate in the steady active state after the reforming reaction was measured. FIG. 2 is a profile for measuring steady-state activity. In this experiment, GHSV is performed at 225,000, and the evaluation is based on the result of a considerable acceleration test compared to a normal GHSV of several thousand levels.
（ＤＳＳ運転試験）
前記の触媒活性測定と同様、上記実験例と上記比較実験例で得られた触媒粉末を粒径０．５μｍ以下に粉砕したものを前記同様の改質反応を行い、定常活性状態でのＣＨ４転化能を確認した。その後、２００℃まで１０Ｋ／ｍｉｎで降温する際に所定の温度（以下、「スチーミング温度」という。）で原燃料であるＣＨ４を供給停止することによってｓｈｕｔ−ｄｏｗｎを行い、続いて７００℃まで１０Ｋ／ｍｉｎで昇温する際にスチーミング温度でＣＨ４を供給開始することによってｓｔａｒｔ−ｕｐを行った。その後、ＣＨ４転化能が定常活性を示すまで反応を行った後に、ｓｔａｒｔ−ｕｐとｓｈｕｔ−ｄｏｗｎとを繰り返すＤＳＳ運転試を行った。なお、この実験例では、スチーミング温度を６００℃とした。
(DSS operation test)
Similar to the measurement of the catalytic activity, the catalyst powders obtained in the above experimental example and the comparative experimental example were pulverized to a particle size of 0.5 μm or less and subjected to the same reforming reaction to obtain CH 4 in a steady active state. The conversion ability was confirmed. Thereafter, when the temperature is lowered to 200 ° C. at 10 K / min, shut-down is performed by stopping supply of CH 4 as a raw fuel at a predetermined temperature (hereinafter referred to as “steaming temperature”), followed by 700 ° C. The start-up was performed by starting the supply of CH 4 at the steaming temperature when the temperature was raised to 10 K / min. Thereafter, after the reaction was performed until the CH 4 conversion ability showed a steady activity, a DSS operation test was repeated in which start-up and shut-down were repeated. In this experimental example, the steaming temperature was 600 ° C.
（ＸＲＤ回折測定及びＸＡＦＳ測定）
実験に供した触媒粉末の結晶構造は、Ｘ線回析装置（理学社製、型式：ＲＩＮＴ−Ｕｌｔｉｍａ III）によって測定した。なお、各実験例と各比較実験例で作製された触媒粉末は、測定されたＸＲＤパターンから、単一のペロブスカイト型によく似た複合酸化物であることが同定された。ＸＡＦＳ測定は、化合物の定性的な情報を精度よく測定できる測定手段であり、ここでは、Ｘ線吸収微細構造（X-ray absorption fine structure）測定装置（高エネルギー加速器研究機構内フォトンファクトリーＢＬ１２Ｃ）によって測定した。
(XRD diffraction measurement and XAFS measurement)
The crystal structure of the catalyst powder subjected to the experiment was measured with an X-ray diffraction apparatus (manufactured by Rigaku Corporation, model: RINT-Ultima III). In addition, it was identified from the measured XRD pattern that the catalyst powder produced in each experimental example and each comparative experimental example was a complex oxide that closely resembled a single perovskite type. XAFS measurement is a measurement means capable of measuring qualitative information of a compound with high accuracy. Here, an X-ray absorption fine structure measurement device (photon factory BL12C in the High Energy Accelerator Research Organization) is used. It was measured.
（触媒活性測定結果）
図３は、実験例１で得られたＬａＮｉxＭｎ(1-X)Ｏ３の触媒粉末を改質反応させた後のＣＨ４転化率の測定結果を示すグラフである。Ｂサイトを構成するＮｉのモル比が約０．７のとき極大値を示しているのが確認され、その±１０％程度が好ましい範囲であることが推察された。なお、各実験例と各比較実験例では、通常の実用態様に比べてかなり高いＧＨＳＶで行った加速試験を行っているので、測定されたＣＨ４転化率の実測値はやや低い値を示しているが、実用態様のＧＨＳＶで行った測定では十分に高いＣＨ４転化率が見込まれる。一方、比較実験例１で得られた触媒粉末についても同様に測定したが、実験例１で得られたような触媒活性は得られなかった。また、Ｂサイトにさらに他の元素を導入した比較実験例２で得られた触媒粉末についても同様に測定したが、実験例１で得られたような触媒活性は得られなかった。
(Catalyst activity measurement results)
FIG. 3 is a graph showing the measurement results of the CH 4 conversion after the reforming reaction of the LaNi x Mn (1-X) O 3 catalyst powder obtained in Experimental Example 1. It was confirmed that the maximum value was shown when the molar ratio of Ni constituting the B site was about 0.7, and it was estimated that about ± 10% was a preferable range. In each experimental example and each comparative experimental example, an acceleration test performed at a considerably higher GHSV than that in a normal practical mode is performed. Therefore, the measured value of the measured CH 4 conversion rate is slightly lower. However, a sufficiently high CH 4 conversion rate is expected in the measurement performed with the practical GHSV. On the other hand, the catalyst powder obtained in Comparative Experimental Example 1 was also measured in the same manner, but the catalytic activity as obtained in Experimental Example 1 was not obtained. Further, the catalyst powder obtained in Comparative Experimental Example 2 in which another element was further introduced into the B site was measured in the same manner, but the catalytic activity as obtained in Experimental Example 1 was not obtained.
実験例２〜３で得られた触媒粉末は貴金属を僅かに含有させたＬａＮｉ0.7Ｍｎ0.3Ｏ３の触媒粉末であるが、この触媒粉末を改質反応させた後のＣＨ４転化率の測定結果については、いずれも５〜７％の変化率が確認された。測定されたＣＨ４転化率の実測値はやや低い値を示しているが、実用態様のＧＨＳＶで行った測定では十分に高いＣＨ４転化率が見込まれる。 The catalyst powders obtained in Experimental Examples 2 to 3 are LaNi 0.7 Mn 0.3 O 3 catalyst powder slightly containing a noble metal, and the measurement results of the CH 4 conversion rate after reforming reaction of this catalyst powder. For all, a change rate of 5 to 7% was confirmed. Although the measured value of the measured CH 4 conversion rate is somewhat low, a sufficiently high CH 4 conversion rate is expected in the measurement performed with the practical GHSV.
実験例４で得られた触媒粉末はＡサイトにＣｅ元素を導入したＬａ0.5Ｃｅ0.5Ｎｉ0.7Ｍｎ0.3Ｏ３の触媒粉末であるが、この触媒粉末を改質反応させた後のＣＨ４転化率の測定結果については、約４％程度の変化率が確認された。測定されたＣＨ４転化率の実測値はやや低い値を示しているが、実用態様のＧＨＳＶで行った測定では十分に高いＣＨ４転化率が見込まれる。一方、Ｃｅ元素に変えて他の元素を導入した比較実験例３で得られた触媒粉末についても同様に測定したが、実験例４で得られたような触媒活性は得られなかった。 The catalyst powder obtained in Experimental Example 4 is a La 0.5 Ce 0.5 Ni 0.7 Mn 0.3 O 3 catalyst powder in which Ce element is introduced at the A site. The CH 4 conversion rate after the catalyst powder is subjected to a reforming reaction. As for the measurement results, a change rate of about 4% was confirmed. Although the measured value of the measured CH 4 conversion rate is somewhat low, a sufficiently high CH 4 conversion rate is expected in the measurement performed with the practical GHSV. On the other hand, the catalyst powder obtained in Comparative Experimental Example 3 in which another element was introduced instead of Ce element was measured in the same manner, but the catalytic activity as obtained in Experimental Example 4 was not obtained.
（ＤＳＳ運転試験結果）
実験例１で作製したＬａＮｉ0.7Ｍｎ0.3Ｏ３からなる触媒粉末を用いてＤＳＳ運転試験を行った。図４は、ＬａＮｉ0.7Ｍｎ0.3Ｏ３を水素還元する前のＳＥＭ写真とＸ線回折結果とＸＡＦＳ測定結果とを示しており、図５は、ＬａＮｉ0.7Ｍｎ0.3Ｏ３を水素還元した後のＳＥＭ写真とＸ線回折結果とＸＡＦＳ測定結果とを示しており、図６は、スチーミング温度後における触媒粉末のＳＥＭ写真とＸ線回折結果とＸＡＦＳ測定結果とを示しており、図７は、失活した後における触媒粉末のＳＥＭ写真とＸ線回折結果とＸＡＦＳ測定結果とを示しており、図８は、再焼成して再生した後における触媒粉末のＳＥＭ写真とＸ線回折結果とＸＡＦＳ測定結果とを示している。
(DSS operation test results)
A DSS operation test was conducted using the catalyst powder made of LaNi 0.7 Mn 0.3 O 3 prepared in Experimental Example 1. FIG. 4 shows an SEM photograph, X-ray diffraction results and XAFS measurement results before hydrogen reduction of LaNi 0.7 Mn 0.3 O 3 , and FIG. 5 shows SEM after LaNi 0.7 Mn 0.3 O 3 hydrogen reduction. Fig. 6 shows a photograph, an X-ray diffraction result and an XAFS measurement result. Fig. 6 shows an SEM photo, an X-ray diffraction result and an XAFS measurement result of the catalyst powder after the steaming temperature. FIG. 8 shows an SEM photograph, an X-ray diffraction result and an XAFS measurement result of the catalyst powder after activation, and FIG. 8 shows an SEM photograph, an X-ray diffraction result and an XAFS measurement result of the catalyst powder after recalcination and regeneration. It shows.
図４に示すように、水素還元前の触媒粉末は、ＸＲＤパターンからＬａＮｉ0.7Ｍｎ0.3Ｏ3の存在が同定され、さらに、ＸＡＦＳ測定結果からも、ＮｉＯや金属Ｎｉが存在しないことが確認された。また、図５に示すように、水素還元後の触媒粉末は、ＸＲＤパターンから酸化ランタン（Ｌａ2Ｏ3）と金属Ｎｉの存在が同定され、さらに、ＸＡＦＳ測定結果からは、金属Ｎｉの存在とＮｉＯの不存在が確認された。また、図６に示すように、スチーミング温度後においても触媒活性を有する触媒粉末は、ＸＲＤパターンからオキシ炭酸ランタン（Ｌａ2Ｏ2ＣＯ3）と金属Ｎｉとマンガン酸ランタン（ＬａＭｎＯ3）との存在が同定され、さらに、ＸＡＦＳ測定結果からは、金属Ｎｉの存在とＮｉＯの不存在が確認された。また、図７に示すように、失活した後の触媒粉末は、ＸＲＤパターンからニッケル酸ランタン（ＬａＮｉＯ3）とマンガン酸ランタン（ＬａＭｎＯ3）との存在が同定され、さらに、ＸＡＦＳ測定結果からは、金属Ｎｉの不存在とＮｉＯの存在が確認された。また、図８に示すように、再生された触媒粉末は、図６と同様、ＸＲＤパターンからニッケル酸ランタン（ＬａＮｉＯ3）とマンガン酸ランタン（ＬａＭｎＯ3）との存在が同定され、さらに、ＸＡＦＳ測定結果からは、金属Ｎｉの不存在とＮｉＯの存在が確認された。 As shown in FIG. 4, in the catalyst powder before hydrogen reduction, the presence of LaNi 0.7 Mn 0.3 O 3 was identified from the XRD pattern, and further XAFS measurement results confirmed that NiO and metallic Ni were not present. . Further, as shown in FIG. 5, in the catalyst powder after hydrogen reduction, the presence of lanthanum oxide (La 2 O 3 ) and metal Ni was identified from the XRD pattern. Further, from the XAFS measurement results, the presence of metal Ni was confirmed. The absence of NiO was confirmed. Further, as shown in FIG. 6, the catalyst powder having catalytic activity even after the steaming temperature is obtained from the XRD pattern of lanthanum oxycarbonate (La 2 O 2 CO 3 ), metal Ni, and lanthanum manganate (LaMnO 3 ). The presence was identified, and the XAFS measurement results confirmed the presence of metallic Ni and the absence of NiO. Further, as shown in FIG. 7, the catalyst powder after deactivation was identified from the XRD pattern as to the presence of lanthanum nickelate (LaNiO 3 ) and lanthanum manganate (LaMnO 3 ). The absence of metallic Ni and the presence of NiO were confirmed. In addition, as shown in FIG. 8, the regenerated catalyst powder was identified for the presence of lanthanum nickelate (LaNiO 3 ) and lanthanum manganate (LaMnO 3 ) from the XRD pattern as in FIG. The results confirmed the absence of metallic Ni and the presence of NiO.
この結果が示すように、一般式ＡＢＯ３型でそのＢサイトがＮｉｘＭ（１−ｘ）の組成物からなる触媒粉末においては、ＤＳＳ運転時に、金属Ｎｉがオキシ炭酸ランタン（Ｌａ2Ｏ2ＣＯ3）に担持された状態になっていることによって、触媒活性を示していると考えられる。したがって、こうした金属Ｎｉがオキシ炭酸化合物上に担持されているように、Ａサイトの元素やＢサイトの元素を選択することができれば、安価で安定した触媒粉末とすることができると考えられる。なお、本願では、好ましい実験例としてＬａＮｉxＭｎ(1-X)Ｏ３組成物を挙げることができ、さらにその組成物に僅かな貴金属を添加した場合も同様の効果が得られることがわかった。
As shown by this result, in the catalyst powder having the general formula ABO 3 type and the B site of Ni x M (1-x) , the metal Ni is lanthanum oxycarbonate (La 2 O 2) during the DSS operation. It is considered that the catalyst activity is shown by being in a state of being supported on CO 3 ). Therefore, it is considered that an inexpensive and stable catalyst powder can be obtained if an A-site element or a B-site element can be selected such that such metal Ni is supported on an oxycarbonic acid compound. In the present application, there may be mentioned LaNi x Mn (1-X)
Claims (6)
前記組成物は、ＤＳＳ運転時に、金属Ｎｉがオキシ炭酸化合物に担持されていることを特徴とする燃料電池用水素製造触媒。 A fuel cell hydrogen production catalyst of general formula ABO 3 type, wherein B is composed of a composition of Ni x M (1-x) , and repeats ON / OFF of fuel supply,
The composition is a hydrogen production catalyst for a fuel cell, characterized in that metal Ni is supported on an oxycarbonate during DSS operation.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2018165228A (en) * | 2017-03-28 | 2018-10-25 | 京セラ株式会社 | Hydrogen generating cell, concentration-type hydrogen generating cell, and hydrogen production apparatus |
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| JPS4869783A (en) * | 1971-12-24 | 1973-09-21 | ||
| JPH02207843A (en) * | 1989-02-09 | 1990-08-17 | Sekiyu Sangyo Katsuseika Center | Production of steam reforming catalyst and hydrogen for fuel cell |
| JPH08229390A (en) * | 1995-02-24 | 1996-09-10 | Tokin Corp | Production of powder for lanthanum-manganese oxide catalyst |
| JP2002126529A (en) * | 2000-10-18 | 2002-05-08 | Japan National Oil Corp | Method for preparing reforming catalyst |
| JP2004000900A (en) * | 2002-03-25 | 2004-01-08 | Nippon Steel Corp | Catalyst for reforming hydrocarbon and method for reforming hydrocarbon |
| JP2005254076A (en) * | 2004-03-09 | 2005-09-22 | Kyushu Electric Power Co Inc | Reforming catalyst composition |
| JP2005262070A (en) * | 2004-03-18 | 2005-09-29 | Hitachi Ltd | Catalyst for production of hydrogen |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4869783A (en) * | 1971-12-24 | 1973-09-21 | ||
| JPH02207843A (en) * | 1989-02-09 | 1990-08-17 | Sekiyu Sangyo Katsuseika Center | Production of steam reforming catalyst and hydrogen for fuel cell |
| JPH08229390A (en) * | 1995-02-24 | 1996-09-10 | Tokin Corp | Production of powder for lanthanum-manganese oxide catalyst |
| JP2002126529A (en) * | 2000-10-18 | 2002-05-08 | Japan National Oil Corp | Method for preparing reforming catalyst |
| JP2004000900A (en) * | 2002-03-25 | 2004-01-08 | Nippon Steel Corp | Catalyst for reforming hydrocarbon and method for reforming hydrocarbon |
| JP2005254076A (en) * | 2004-03-09 | 2005-09-22 | Kyushu Electric Power Co Inc | Reforming catalyst composition |
| JP2005262070A (en) * | 2004-03-18 | 2005-09-29 | Hitachi Ltd | Catalyst for production of hydrogen |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2018165228A (en) * | 2017-03-28 | 2018-10-25 | 京セラ株式会社 | Hydrogen generating cell, concentration-type hydrogen generating cell, and hydrogen production apparatus |
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| JP4848294B2 (en) | 2011-12-28 |
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