JP6304250B2 - リアクタ - Google Patents
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- JP6304250B2 JP6304250B2 JP2015524104A JP2015524104A JP6304250B2 JP 6304250 B2 JP6304250 B2 JP 6304250B2 JP 2015524104 A JP2015524104 A JP 2015524104A JP 2015524104 A JP2015524104 A JP 2015524104A JP 6304250 B2 JP6304250 B2 JP 6304250B2
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- 238000006243 chemical reaction Methods 0.000 claims description 162
- 239000003054 catalyst Substances 0.000 claims description 95
- 239000012530 fluid Substances 0.000 claims description 77
- 238000005192 partition Methods 0.000 claims description 41
- 238000012546 transfer Methods 0.000 claims description 38
- 230000000994 depressogenic effect Effects 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 239000011651 chromium Substances 0.000 description 6
- 238000004891 communication Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000005219 brazing Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000758 substrate Substances 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
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/248—Reactors comprising multiple separated flow channels
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- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
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- B01J2219/00049—Controlling or regulating processes
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- B01J2219/00054—Controlling or regulating the heat exchange system
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Description
図1(a)及び図1(b)は、本実施形態にかかるリアクタ100を説明するための図である。図2(a)は、熱媒体側流路220を説明するための図である。図2(b)は、反応側流路210を説明するための図である。垂直に交わるX軸、Y軸、Z軸は、各図に示すように定義されている。また、図1(a)及び図1(b)中、理解を容易にするために触媒構造体300の記載を省略する。
CH4 + H2O → 3H2 + CO…化学式(1)
CH4 + CO2 → 2H2 + 2CO…化学式(2)
CO + H2O → CO2 + H2…化学式(3)
CO + 3H2 → CH4 + H2O…化学式(4)
(2n+1)H2 + nCO → CnH2n+2 + nH2O…化学式(5)
図3(a)〜図3(d)は、触媒構造体300の具体的な構成を説明するための図である。図3(a)は、触媒構造体300の斜視図である。図3(b)は触媒構造体300の分解斜視図である。図3(c)は触媒構造体300が反応側流路210に設置された際の図3(a)におけるIII(c)−III(c)線のYZ断面図である。図3(d)は比較例の触媒構造体30を説明するための図である。垂直に交わるX軸、Y軸、Z軸を図に示すように定義している。また、図3(a)では、反応流体の流通方向を白抜きの矢印で示す。
続いて、上記触媒構造体300の製造方法について説明する。図4は、触媒構造体300の製造方法の処理の流れを説明するためのフローチャートである。図4に示すように、触媒構造体300の製造方法は、構造体製造工程S110、前処理工程S120、下塗り工程S130、触媒担体形成工程S140、第1焼成工程S150、触媒担持工程S160、第2焼成工程S170を含んで構成される。以下、各工程について詳述する。
構造体製造工程S110では、Fe(鉄)、Cr(クロム)、Al(アルミニウム)、Y(イットリウム)を主成分とする耐熱合金、例えば、Fecralloy(登録商標)等の金属板を波板形状に加工し、溝330を形成する加工を施して、本体部310を作成する。また、Fe(鉄)、Cr(クロム)、Al(アルミニウム)、Y(イットリウム)を主成分とする耐熱合金、例えば、Fecralloy(登録商標)等の金属板に溝370を形成する加工を施して、平板350を作成する。
前処理工程S120では、アセトンを用いて構造体を脱脂し、その後、構造体を予め定められた気体雰囲気下に曝し、予め定められた温度で、予め定められた時間熱処理を行う。これにより、構造体の表面にAl2O3を主成分とする針状の結晶を析出させることができる。
前処理工程S120を行った後、針状の結晶を析出させた構造体を、下塗り剤(例えば、ベーマイト)と、硝酸とを含む懸濁液に浸漬し、その後、懸濁液から引き上げ、余分なスラリーを除去する。そして、懸濁液から引き上げた構造体を乾燥させる。こうして、構造体に下塗り剤が塗布される。
下塗り工程S130を行った後、下塗り剤が塗布された構造体を、触媒の担体(例えば、γ相のAl2O3)と、ベーマイトと、硝酸とを含む懸濁液に浸漬し、その後、懸濁液から引き上げ、余分なスラリーを除去する。そして、懸濁液から引き上げた構造体を乾燥させる。続いて、予め定められた気体雰囲気下に曝し、予め定められた温度で、予め定められた時間熱処理を行う。
触媒担体形成工程S140を行った後、触媒担体が付着した構造体を、予め定められた気体雰囲気下に曝し、予め定められた温度で、予め定められた時間熱処理を行い、触媒担体を焼成する。これにより、構造体の表面に多孔質の触媒担体が形成される。
第1焼成工程S150を行った後、表面に多孔質の触媒担体が形成された構造体を、活性金属(例えば、Ni)の塩が溶解された溶液に浸漬し、その後、溶液から引き上げ、溶液から引き上げた構造体を乾燥させる。
触媒担持工程S160を行った後、触媒が担持された構造体を、予め定められた気体雰囲気下に曝し、予め定められた温度で、予め定められた時間熱処理を行い、触媒を焼成する。これにより、構造体の表面に多孔質の触媒が形成される。
図5は、変形例にかかる触媒構造体400を説明するための図である。垂直に交わるX軸、Y軸、Z軸を図に示すように定義している。また、図5では、反応流体の流通方向を白抜きの矢印で示す。
Claims (7)
- 反応対象としての流体を流通させる反応側流路と、
前記反応側流路を構成する壁部材とは別体に形成され、前記反応側流路内に設置される触媒構造体と、
を備え、
前記触媒構造体は、
隆起した箇所および陥没した箇所が交互に繰り返される板形状に形成され、前記反応側流路内の空間を、前記流体の流通方向に直交する方向に並列した複数の流路に区画する本体部と、
前記本体部に担持され前記流体の反応を促進させる触媒と、
前記本体部における隆起した箇所および陥没した箇所のうちの少なくとも一方に設けられ、前記本体部によって区画された複数の流路のうち、前記本体部における隆起した箇所或いは陥没した箇所を挟む2つの流路を連通する1または複数の溝とを有することを特徴とするリアクタ。 - 前記触媒構造体は、前記本体部における隆起した箇所および陥没した箇所のうちの少なくとも一方に接触する平板をさらに備え、
前記平板は、前記平板における前記本体部の隆起した箇所に接触する箇所および陥没した箇所に接触する箇所のうちの少なくとも一方に設けられ、前記本体部における隆起した箇所或いは陥没した箇所を挟む2つの流路を連通する溝を有することを特徴とする請求項1に記載のリアクタ。 - 前記溝の大きさは、前記本体部によって区画された流路の流路断面積より小さいことを特徴とする請求項1または2に記載のリアクタ。
- 前記反応側流路外から前記流体を加熱または冷却する温度制御部をさらに備えたことを特徴とする請求項1から3のいずれか1項に記載のリアクタ。
- 前記温度制御部は、
伝熱隔壁を介して前記反応側流路と並行して設けられ、前記反応側流路を流通する前記流体と熱交換を行う熱媒体を流通させる熱媒体側流路を含むことを特徴とする請求項4に記載のリアクタ。 - 前記熱媒体は気体であることを特徴とする請求項5に記載のリアクタ。
- 前記反応側流路と、前記熱媒体側流路とが交互に積層されていることを特徴とする請求項5または6に記載のリアクタ。
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