JP2017013049A - 水蒸気改質プロセスに使用される触媒 - Google Patents
水蒸気改質プロセスに使用される触媒 Download PDFInfo
- Publication number
- JP2017013049A JP2017013049A JP2016117687A JP2016117687A JP2017013049A JP 2017013049 A JP2017013049 A JP 2017013049A JP 2016117687 A JP2016117687 A JP 2016117687A JP 2016117687 A JP2016117687 A JP 2016117687A JP 2017013049 A JP2017013049 A JP 2017013049A
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- Prior art keywords
- catalyst
- support
- metal
- particulate
- alumina
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 54
- 230000004048 modification Effects 0.000 title 1
- 238000012986 modification Methods 0.000 title 1
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 18
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 15
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 14
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 13
- 229910052737 gold Inorganic materials 0.000 claims abstract description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 238000000465 moulding Methods 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000002344 surface layer Substances 0.000 claims abstract description 5
- 238000005507 spraying Methods 0.000 claims abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 26
- 239000010410 layer Substances 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 238000000629 steam reforming Methods 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 17
- 238000002407 reforming Methods 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- -1 magnesium aluminate Chemical class 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000008188 pellet Substances 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 239000003345 natural gas Substances 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 244000075898 Lantana strigocamara Species 0.000 claims 1
- 150000004645 aluminates Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 1
- 239000010419 fine particle Substances 0.000 abstract description 7
- 238000002715 modification method Methods 0.000 abstract 1
- 238000006011 modification reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000002736 metal compounds Chemical class 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 241000003832 Lantana Species 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000002453 autothermal reforming Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000007756 Akebia quinata Nutrition 0.000 description 1
- 240000008027 Akebia quinata Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000001193 catalytic steam reforming Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling 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
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000001991 steam methane reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002700 tablet coating Substances 0.000 description 1
- 238000009492 tablet coating Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B01J23/83—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 rare earths or actinides
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Abstract
【解決手段】水蒸気改質方法において、工程(i)〜(iii)を含む方法により調製される触媒を用いる方法。(i)Ni、Cu、Pt、Pd、Rh、Ru又はAuから選択される1以上の触媒金属含む微粒子触媒化合物を含有するスラリーをパンコーター内で成形支持体表面に噴霧し、表面層に触媒金属を有する被覆成形支持材を形成する工程、(ii)被覆成形支持材を乾燥させ、任意で焼成して触媒前駆体を形成する工程、(iii)触媒前駆体の金属(単数又は複数)を任意で低級酸化状態に還元し触媒を形成する工程
【選択図】なし
Description
(i)Ni、Cu、Pt、Pd、Rh、Ru及びAuからなる群より選択される1または複数の触媒金属を含む微粒子触媒化合物含有スラリーを、パンコーター内で成形支持体の表面に噴霧し、被覆成形支持体を形成する工程
(ii)被覆成形支持材を乾燥させ任意で焼成し、表面層に触媒金属を有する触媒前駆体を形成する工程、及び
(iii)触媒前駆体の金属(単数又は複数)を任意で低級酸化状態まで還元し、触媒を形成する工程。
CH4+H2O⇔CO+3H2
"CH2"+H2O→CO+2H2
("CH2"はメタンより高級の炭化水素、例えば200℃までの温度で沸騰する通常は気体の炭化水素及び通常は液体の炭化水素を表す。)一酸化炭素を用いた類似の反応が別途又は水蒸気反応と共に行われうる。
CH4+CO2→2CO+2H2
"CH2"+CO2→2CO+H2
メタノールは以下の式に従い水蒸気と反応する。
CH3OH+H2O→CO2+3H2
2%Rh/30%Ce0.75Zr0.25O2−70%Al2O3の粉末(470g)をミネラル除去水に分散させて45%の固体スラリーを作った。これを350rpmで8分間粉砕し、2.2ミクロンのD50を得た。酢酸を加えて478gのウォッシュコートのpHを6.7(天然)から4.0に調節し、Dipseral P3アルミナ(Sasol)を加え(21.5g)、次いでSilverson(約3000rpmで20分)のハイシアヘッドで混合した。 ミネラル除去水(150ml)に溶解させてあったKollicoat IR(17.6g(8%wrt触媒)を加えると、ウォッシュコートの最終重量は705gであった。このウォッシュコート388gをパンコーター内で1L(1180g)のアルファアルミナのクローバーの葉形の錠剤に適用した。コーティングのパラメーターは以下のとおりであった。T入り口(50℃)、パン回転数(20rpm)、ポンプ回転数(18rpm)、パン減圧(−30Pa)。コーティングには29分かかった。生成物を500℃で2時間焼成した。得られた触媒層の厚みは100〜150ミクロンであった。
図1は、成形アルファアルミナの芯部に触媒外層を含む触媒を有する触媒前駆体を表す。
実施例1の被覆ペレットのメタン水蒸気改質活性を試験した。ペレット24個と非被覆ペレット24個を1”径×2.2”長の反応管に配置した。水蒸気−メタン改質を1大気圧で水蒸気:炭素比3.25で実施した。
図2は、Rh−硝酸塩溶液を用いて一般的な初期湿式含浸法で調製した0.2%Rh/CaAl2O4触媒と上記のパンコート触媒(2Rh/CZA)を比較している。初期湿式触媒ではRhが支持体の表面全体に500マイクロメートルまでの深さで分散しているが、パンコーターで調製された被覆触媒はRh含有外層を有する。Rhローディング0.15%のパンコート触媒は、メタン転換において、Rh含有量が比較含浸触媒よりも有意に低かったにもかかわらず、調査した温度範囲全域で比較含浸触媒よりも優れていた。
Claims (27)
- 水蒸気改質プロセスでの使用に適した触媒を調製する方法であって、
(i)Ni、Cu、Pt、Pd、Rh、Ru及びAuからなる群より選択される1または複数の触媒金属を含む微粒子触媒化合物含有スラリーをパンコーター内で成形支持体表面に噴霧し、該触媒金属を表面層内に有する被覆成形支持材を形成する工程と、
(ii)該被覆成形支持材を乾燥させ任意で焼成し触媒前駆体を形成する工程と、
(iii)該触媒前駆体の金属を低級酸化状態に任意で還元し触媒を形成する工程
を含む方法。 - 該微粒子触媒化合物の該触媒金属が、Niを、任意でPt、Pd、Rh、Ru及びAuの1又は複数と共に含む、請求項1に記載の方法。
- 該微粒子触媒化合物の該触媒金属が、Ptを、任意でPd、Rh、Ru及びAuと共に含み、好ましくはPtをRhと共に含む、請求項1に記載の方法。
- 該微粒子触媒化合物の該触媒金属がRhからなる、請求項1に記載の方法。
- 該微粒子触媒化合物が、触媒活性金属の酸化物、水酸化物又は炭酸塩を含む、請求項1から4のいずれか一項に記載の方法。
- 該微粒子触媒化合物が、微粒子触媒支持材の表面に分散したNi、Cu、Pt、Pd、Rh、Ru及びAuからなる群より選択される1または複数の金属を含む、請求項1から5のいずれか一項に記載の方法。
- 該微粒子触媒支持材が、アルミナ、チタニア若しくはジルコニア、酸化亜鉛、ランタナ、マグネシア、セリア、アルミン酸金属及びこれらの混合物からなる群より選択される、請求項6に記載の方法。
- 微粒子触媒支持材が、アルミナ及び/又は安定化ジルコニアを含む、請求項6又は請求項7に記載の方法。
- 1または複数の中間層が該成形支持体と該触媒表面層の間に適用される、請求項1から8のいずれか一項に記載の方法。
- 該成形支持体が、成形品、ペレット又は顆粒を含む、請求項1から9のいずれか一項に記載の方法。
- 成形支持体が、1mmから50mmの長さと1mmから25mmの断面幅又は径を有する、請求項1から10のいずれか一項に記載の方法。
- 該成形支持体ユニットが、多穴ペレット、又は円形、裂片状又は溝付きの断面を有する成形品である、請求項1から11のいずれか一項に記載の方法。
- 該成形支持体が、アルミナ、セリア、マグネシア、チタニア若しくはジルコニア、アルミン酸カルシウム若しくはアルミン酸マグネシウム及びこれらの混合物からなる群より選択される支持酸化物を含む耐火酸化物である、請求項1から12のいずれか一項に記載の方法。
- 該成形支持体が、アルミン酸カルシウム若しくはアルミン酸マグネシウム又はアルファアルミナである、請求項1から13のいずれか一項に記載の方法。
- 該支持体が30〜60℃の範囲の温度で被覆される、請求項1から14のいずれか一項に記載の方法。
- スラリーの固体含有量が1〜60重量%の範囲である、請求項1から15のいずれか一項に記載の方法。
- 乾燥材料中の触媒活性金属を含有する層の厚みが、5から250μmの範囲である、請求項1から16のいずれか一項に記載の方法。
- ポリエチレングラフトコポリマーがスラリーに含まれる、請求項1から17のいずれか一項に記載の方法。
- 乾燥被覆支持材が焼成される、請求項1から18のいずれか一項に記載の方法。
- 該乾燥又は焼成被覆支持材が還元される、請求項1から19のいずれか一項に記載の方法。
- 還元が、水素含有ガスを、200〜600℃の範囲の温度で1から24時間、大気圧又は約25バールまでのより高い圧力で触媒上を通過させることにより実施される、請求項20に記載の方法。
- 該還元触媒が不動態化される、請求項20又は請求項21に記載の方法。
- 請求項1から22のいずれか一項の方法により得られうる触媒。
- 請求項23に記載の触媒又は請求項1から22のいずれか一項の方法により得られうる触媒を用いて水蒸気改質反応を実施する、方法。
- 炭化水素を水蒸気改質することを含む、請求項24に記載の方法。
- 該炭化水素が天然ガス、ナフサ、液体燃料又はガス化器排水である、請求項25に記載の方法。
- 該改質プロセスに酸素が含まれる、請求項25又は請求項26に記載の方法。
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US20140005042A1 (en) | 2014-01-02 |
JP5955868B2 (ja) | 2016-07-20 |
JP2014507274A (ja) | 2014-03-27 |
US9511351B2 (en) | 2016-12-06 |
BR112013020271B1 (pt) | 2019-11-05 |
EP2675561A1 (en) | 2013-12-25 |
BR112013020271B8 (pt) | 2019-12-10 |
CN106362735B (zh) | 2019-07-02 |
BR112013020271A2 (pt) | 2016-10-18 |
EP2675561B1 (en) | 2019-10-02 |
CN103442803A (zh) | 2013-12-11 |
RU2013142164A (ru) | 2015-03-27 |
RU2580548C2 (ru) | 2016-04-10 |
GB201102502D0 (en) | 2011-03-30 |
CN106362735A (zh) | 2017-02-01 |
JP6247344B2 (ja) | 2017-12-13 |
WO2012110781A1 (en) | 2012-08-23 |
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