JP2011167595A - 水素製造用改質触媒及びその製造方法、並びに該触媒を用いた水素製造方法 - Google Patents
水素製造用改質触媒及びその製造方法、並びに該触媒を用いた水素製造方法 Download PDFInfo
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- JP2011167595A JP2011167595A JP2010031459A JP2010031459A JP2011167595A JP 2011167595 A JP2011167595 A JP 2011167595A JP 2010031459 A JP2010031459 A JP 2010031459A JP 2010031459 A JP2010031459 A JP 2010031459A JP 2011167595 A JP2011167595 A JP 2011167595A
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- catalyst
- hydrogen production
- reforming
- hydrogen
- reaction
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 139
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 139
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 109
- 238000002407 reforming Methods 0.000 title claims abstract description 91
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- 238000000629 steam reforming Methods 0.000 claims abstract description 50
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 47
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 41
- 239000002131 composite material Substances 0.000 claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 239000002904 solvent Substances 0.000 description 5
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- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- VAROLYSFQDGFMV-UHFFFAOYSA-K di(octanoyloxy)alumanyl octanoate Chemical compound [Al+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O VAROLYSFQDGFMV-UHFFFAOYSA-K 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000005324 oxide salts Chemical class 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- KGRJUMGAEQQVFK-UHFFFAOYSA-L platinum(2+);dibromide Chemical compound Br[Pt]Br KGRJUMGAEQQVFK-UHFFFAOYSA-L 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- GVIIRWAJDFKJMJ-UHFFFAOYSA-N propan-2-yl 3-oxobutanoate Chemical compound CC(C)OC(=O)CC(C)=O GVIIRWAJDFKJMJ-UHFFFAOYSA-N 0.000 description 1
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical compound [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 description 1
- MMRXYMKDBFSWJR-UHFFFAOYSA-K rhodium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Rh+3] MMRXYMKDBFSWJR-UHFFFAOYSA-K 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
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- CFTHARXEQHJSEH-UHFFFAOYSA-N silicon tetraiodide Chemical compound I[Si](I)(I)I CFTHARXEQHJSEH-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JKUYRAMKJLMYLO-UHFFFAOYSA-N tert-butyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC(C)(C)C JKUYRAMKJLMYLO-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910002001 transition metal nitrate Inorganic materials 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- UNKOLEUDCQIVBV-UHFFFAOYSA-N tris(2-ethylhexanoyloxy)silyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)O[Si](OC(=O)C(CC)CCCC)(OC(=O)C(CC)CCCC)OC(=O)C(CC)CCCC UNKOLEUDCQIVBV-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 description 1
Images
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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
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Abstract
【解決手段】ジルコニウムを含有する無機複合酸化物担体に、活性金属成分としてルテニウム、ロジウム、白金から選ばれる少なくとも1種の貴金属、および助触媒成分としてニッケル、コバルトから選ばれる少なくとも1種の遷移金属を含有し、比表面積が310m2/g以上で、前記貴金属が分散度60%以上で前記無機複合酸化物担体中に分散されていることを特徴とする水素製造用改質触媒である。
【選択図】図1
Description
ジルコニウムと、ジルコニウム以外の金属を1種以上含む複合酸化物前駆体、および活性金属成分を含む活性金属前駆体を、有機多座配位子を用いて溶解させて均一溶液を調製する工程と、
助触媒成分を含む助触媒前駆体の水溶液を前記均一溶液に加えて加水分解させ、加水分解生成物を得る工程と、
酸素存在下、400〜800℃で、前記加水分解生成物を焼成する工程と
を含むことを特徴とする。
<実施例1(触媒A)>
アルミニウムイソプロポキシド490gと、ジルコニウム(IV)テトライソプロポキシド(イソプロパノール付加体)186gを、2−メチル−2,4−ペンタンジオール720gに脱水雰囲気下で均一に溶解させ、110℃で生成するイソプロパノールを蒸留除去しながら4時間反応蒸留を行った後、三塩化ルテニウム3.51gを加えて減圧下でイソプロパノールを除去した後、硝酸コバルト(II)六水和物1.54gおよび硝酸ランタン六水和物13.2gを水500gに溶解させた水溶液を加えて80℃で24時間加水分解を行った。加水分解後に得られた沈殿物を130℃で24時間ゲル化反応を行い、得られたゲルを95℃で真空減圧乾燥した後、130℃で16時間乾燥、引き続き酸素存在下600℃で3時間焼成を実施し、ヒドラジン炭酸塩水溶液を用いて40℃で液相還元処理を行った後、150℃で10時間乾燥して得られた触媒粉を成形器に入れて、4kgf/cm2で5分間プレス成形したものを粉砕して、16〜24メッシュの大きさに篩い分けしたものを回収して、触媒Aを得た。
実施例1の方法において、三塩化ルテニウムの代わりにルテニウム(III)2,4−ペンタンジオネート3.65gを使用した以外は実施例1と同様の方法で調製し、触媒Bを得た。
アルミニウムイソプロポキシド490gと、ジルコニウム(IV)テトライソプロポキシド(イソプロパノール付加体)186gを、2−メチル−2,4−ペンタンジオール720gに脱水雰囲気下で均一に溶解させ、110℃で生成するイソプロパノールを蒸留除去しながら4時間反応蒸留を行った後、減圧下でイソプロパノールを除去した後、水500gを加えて80℃で加水分解を行った。加水分解後に得られた白色沈殿物を130℃でゲル化反応を行い、得られた白色のゲルを95℃で真空減圧乾燥した後、600℃で焼成して、担体C 175gを得た。得られた担体C 125gに、硝酸ランタン六水和物13.2gが溶解した水溶液180mlをポアフィリング法により含浸した後、110℃で16時間乾燥、引き続き酸素存在下600℃で3時間焼成を実施した。得られたランタン含有担体に、三塩化ルテニウム3.51gと硝酸コバルト(II)六水和物1.54gが溶解した水溶液180mlをポアフィリング法で含浸した後、150℃で16時間乾燥した。得られた触媒にヒドラジン炭酸塩水溶液を用いて40℃で液相還元処理を行い、150℃で10時間乾燥し、得られた触媒粉を成形器に入れて、4kgf/cm2で5分間プレス成形したものを粉砕して、16〜24メッシュの大きさに篩い分けしたものを回収して、触媒Cを得た。
2mm径のアルミナ担体D(比表面積120m2/g、細孔容積0.36ml/g)415gに、塩化ジルコニウム(IV)34gを水に溶かして全量をポアフィリング法により含浸した後、110℃で16時間乾燥、引き続き酸素存在下650℃で3時間焼成を実施して得られたジルコニウム含有担体に、三塩化ルテニウム17.5gと硝酸コバルト(II)六水和物10.2gが溶解した水溶液150mlをポアフィリング法で含浸した後、150℃で16時間乾燥した。得られた触媒にヒドラジン炭酸塩水溶液を用いて40℃に加温して液相還元処理を行い、液相から取り出して150℃で10時間乾燥し、触媒Dを得た。
実施例2の方法において、アルミニウムイソプロポキシドの使用量を600gとし、ジルコニウム(IV)テトライソプロポキシド(イソプロパノール付加体)を使用しない以外は実施例2と同様の方法で調製し、触媒Eを得た。
V50:測定温度50(℃)におけるCO吸着量(ml)
W:触媒の試料量(g)
P:測定時の圧力(kPa)
t:測定温度(℃)
JIS 1号灯油を市販のコバルト−モリブデン系脱硫触媒を用いてLHSV=1.0h-1、370℃、水素/油=500Nm3/m3、圧力5MPaの条件で370℃の水素化脱硫処理を行い、引き続き市販の酸化亜鉛吸着剤を用いてLHSV=1.0h-1、350℃、圧力5MPaの条件で吸着処理を行い、脱硫灯油を得た。これらのJIS 1号灯油及び脱硫灯油の性状を表2に示す。
T120 水タンク
EV110 原料気化器
EV120 水気化器
M130 混合器
R140 改質器
A150 分析計
S160 気液分離器
T170 液回収タンク
Claims (7)
- ジルコニウムを含有する無機複合酸化物担体に、活性金属成分としてルテニウム、ロジウム、白金から選ばれる少なくとも1種の貴金属、および助触媒成分としてニッケル、コバルトから選ばれる少なくとも1種の遷移金属を含有し、比表面積が310m2/g以上で、前記貴金属が分散度60%以上で前記無機複合酸化物担体中に分散されていることを特徴とする水素製造用改質触媒。
- 前記無機複合酸化物担体がアルミナを含み、かつ該アルミナの結晶子径が3nm以下であることを特徴とする、請求項1に記載の水素製造用改質触媒。
- ジルコニウムと、ジルコニウム以外の金属を1種以上含む複合酸化物前駆体、および活性金属成分を含む活性金属前駆体を、有機多座配位子を用いて溶解させて均一溶液を調製する工程と、
助触媒成分を含む助触媒前駆体の水溶液を前記均一溶液に加えて加水分解させ、加水分解生成物を得る工程と、
酸素存在下、400〜800℃で、前記加水分解生成物を焼成する工程と
を含むことを特徴とする請求項1又は2に記載の水素製造用改質触媒の製造方法。 - 前記有機多座配位子が、ポリオール、アセトアセテート、ポリカルボン酸から選ばれる少なくとも1種を含むことを特徴とする、請求項3に記載の水素製造用改質触媒の製造方法。
- 前記有機多座配位子が、炭素数5以上のジオールを含むことを特徴とする請求項4に記載の水素製造用改質触媒の製造方法。
- 請求項1又は2に記載の水素製造用改質触媒を具備する改質部に水素製造用燃料油とスチームを供給し、該改質部の触媒層の入口温度を520℃以下として水蒸気改質反応を行い、水素を含有する生成物を得ることを特徴とする水素製造方法。
- 前記水素製造用燃料油が灯油留分であることを特徴とする、請求項6に記載の水素製造方法。
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JP2013202568A (ja) * | 2012-03-29 | 2013-10-07 | Jx Nippon Oil & Energy Corp | 水素の製造方法 |
WO2019069058A1 (en) * | 2017-10-05 | 2019-04-11 | Petróleo Brasileiro S. A. - Petrobras | PROCESS FOR PREPARING A PRE-REFORMING CATALYST HAVING STEAM PASSING DEACTIVATION RESISTANCE IN THE ABSENCE OF A REDUCING AGENT, AND PRE-REFORMING CATALYST |
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JP2013202568A (ja) * | 2012-03-29 | 2013-10-07 | Jx Nippon Oil & Energy Corp | 水素の製造方法 |
WO2019069058A1 (en) * | 2017-10-05 | 2019-04-11 | Petróleo Brasileiro S. A. - Petrobras | PROCESS FOR PREPARING A PRE-REFORMING CATALYST HAVING STEAM PASSING DEACTIVATION RESISTANCE IN THE ABSENCE OF A REDUCING AGENT, AND PRE-REFORMING CATALYST |
US11794168B2 (en) | 2017-10-05 | 2023-10-24 | Petróleo Brasileiro S.A.—Petrobras | Process for preparing a pre-reforming catalyst having resistance to deactivation by passage of steam in the absence of a reducing agent, and a pre-reforming catalyst |
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