JP6025603B2 - Coシフト反応装置及びcoシフト変換方法 - Google Patents
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- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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Description
CO + H2O → CO2 + H2 ・・・(1)
前記COシフト触媒として、前記COシフト反応部の前流部に、第1温度領域を有するNi−Mo系触媒が配置され、前記COシフト反応部の後流部に、第2温度領域を有する耐久性の高いCOシフト触媒が配置されてなることが好適である。
また、前記COシフト反応部は、その好適な形態で、直列に複数配列されてなることができる。
前記COシフト反応部間において、未反応のガスを循環するラインを更に備えることができる。
前記COシフト反応部におけるシフト反応後のガスを、第1温度領域の温度に冷却する熱交換部を更に備えることができる。
前記Ni−Mo系触媒は、モリブデン(Mo)を主成分とすると共に、ニッケル(Ni)を副成分とする活性成分と、前記活性成分を担持するチタン(Ti)、ジルコニウム(Zr)及びセリウム(Ce)の酸化物のいずれか一種又は二種以上を担体とするものであることが好適である。
高温領域において耐久性の高いCOシフト触媒は、Co−Mo系触媒であることが好適である。
低温領域において耐久性の高いCOシフト触媒は、Ni−Mo系触媒であることが好適である。
前記第1温度領域は、150〜300℃の範囲であり、前記第2温度領域は、300〜500℃の範囲であることが好適である。
前記接触させる工程は、前記ガス化ガスを、第1温度領域を有するNi−Mo系触媒と接触させた後、第2温度領域を有する耐久性の高いCOシフト触媒と接触させることを含むことができる。
前記耐久性の高いCOシフト触媒と接触させたガス化ガスを、再度前記Ni−Mo系触媒と接触させる工程を更に含むことができる。
前記耐久性の高いCOシフト触媒と接触させたガス化ガスを、第1温度領域の温度に冷却する工程を更に含むことができる。
図1に、本発明に係るCOシフト反応装置の一実施の形態を示す。
本発明のCOシフト反応装置を用いて、COシフト反応を行った。具体的には、COシフト反応部の前流部にNi−Mo系触媒を、後流部にCo−Mo系触媒をそれぞれ充填し、COシフト反応部の前流部からガス化ガスを供給した。評価は、ガス化ガス中に含まれるCOのCO2への変換率(CO転化率)を算出することにより行った。CO転化率は83%であった。
COシフト反応器と、冷却器とを備えるCOシフト反応部を2段具備したCOシフト反応装置を用いて、COシフト反応を行った。COシフト反応部内には、Co−Mo系触媒を充填した。評価は、実施例1と同様に行った。CO転化率は78%であった。
11 COシフト反応部の前流部
12 COシフト反応部の後流部
21 第1COシフト反応部
21a 第1COシフト反応部の前流部
21b 第1COシフト反応部の後流部
22 第2COシフト反応部
22a 第2COシフト反応部の前流部
22b 第2COシフト反応部の後流部
23 循環ライン
24 濃度計
25 熱交換部
A ガス流れ方向
C、C1、C2 平衡転化率曲線
G1、G2、G3、G4、G5、G6、G7 グラフ
H 高温側
L 低温側
Claims (11)
- 互いに活性温度領域の異なるCOシフト触媒が、ガス流れ方向に対して複数配置されるCOシフト反応部を備え、
前記COシフト触媒として、前記COシフト反応部の前流部に、第1温度領域を有するNi−Mo系触媒が配置され、前記COシフト反応部の後流部に、第2温度領域を有する耐久性の高いCOシフト触媒が配置されてなる、COシフト反応装置。 - 前記COシフト反応部が、直列に複数配列されてなる、請求項1に記載のCOシフト反応装置。
- 前記COシフト反応部間において、未反応のガスを循環するラインを更に備える、請求項2に記載のCOシフト反応装置。
- 前記COシフト反応部におけるシフト反応後のガスを、第1温度領域の温度に冷却する熱交換部を更に備える、請求項2又は3に記載のCOシフト反応装置。
- 前記Ni−Mo系触媒が、モリブデン(Mo)を主成分とすると共に、ニッケル(Ni)を副成分とする活性成分と、前記活性成分を担持するチタン(Ti)、ジルコニウム(Zr)及びセリウム(Ce)の酸化物のいずれか一種又は二種以上を担体とするものである、請求項1〜4のいずれかに記載のCOシフト反応装置。
- 前記耐久性の高いCOシフト触媒が、Co−Mo系触媒である、請求項1〜5のいずれかに記載のCOシフト反応装置。
- 前記耐久性の高いCOシフト触媒が、Ni−Mo系触媒である、請求項1〜5のいずれかに記載のCOシフト反応装置。
- 前記第1温度領域が、150〜300℃の範囲であり、前記第2温度領域が、300〜500℃の範囲である、請求項1〜7のいずれかに記載のCOシフト反応装置。
- 石炭をガス化したガス(ガス化ガス)に含まれるCOをCO2に変換するCOシフト変換方法であって、
前記ガス化ガスを、ガス流れ方向に対して複数配置された、互いに耐久性が高く、温度領域の異なるCOシフト触媒と接触させる工程を含み、
前記接触させる工程が、前記ガス化ガスを、第1温度領域を有するNi−Mo系触媒と接触させた後、第2温度領域を有する耐久性の高いCOシフト触媒と接触させることを含む、COシフト変換方法。 - 前記耐久性の高いCOシフト触媒と接触させたガス化ガスを、再度前記Ni−Mo系触媒と接触させる工程を更に含む、請求項9に記載のCOシフト変換方法。
- 前記耐久性の高いCOシフト触媒と接触させたガス化ガスを、第1温度領域の温度に冷却する工程を更に含む、請求項9又は10に記載のCOシフト変換方法。
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JP2013032109A JP6025603B2 (ja) | 2013-02-21 | 2013-02-21 | Coシフト反応装置及びcoシフト変換方法 |
EP14754509.9A EP2960318B8 (en) | 2013-02-21 | 2014-02-18 | Co shift reaction device and co shift conversion method |
AU2014219864A AU2014219864B2 (en) | 2013-02-21 | 2014-02-18 | CO shift reaction device and CO shift conversion method |
PCT/JP2014/053718 WO2014129440A1 (ja) | 2013-02-21 | 2014-02-18 | Coシフト反応装置及びcoシフト変換方法 |
PL14754509T PL2960318T3 (pl) | 2013-02-21 | 2014-02-18 | Urządzenie do reakcji konwersji co i sposób konwersji co |
US14/768,909 US10000378B2 (en) | 2013-02-21 | 2014-02-18 | Carbon monoxide shift reaction apparatus and carbon monoxide shift conversion method |
CN201480020405.XA CN105102593B (zh) | 2013-02-21 | 2014-02-18 | Co变换反应装置和co变换转化方法 |
DK14754509.9T DK2960318T3 (en) | 2013-02-21 | 2014-02-18 | CO-SHIFT REACTION AND CO-SHIFT CONVERSION PROCEDURE |
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US3128163A (en) | 1960-05-21 | 1964-04-07 | Metallgesellschaft Ag | Method of carrying out exothermic catalytic carbon monoxide-steam gas reactions |
US3850841A (en) | 1969-11-10 | 1974-11-26 | Exxon Research Engineering Co | Shift process for new catalyst |
US4021366A (en) * | 1975-06-30 | 1977-05-03 | Texaco Inc. | Production of hydrogen-rich gas |
JPS606986B2 (ja) * | 1982-02-03 | 1985-02-21 | 大阪瓦斯株式会社 | 都市ガスの製造方法 |
JP2526404B2 (ja) * | 1993-10-15 | 1996-08-21 | 工業技術院長 | 触媒反応方法 |
US6019954A (en) * | 1994-12-16 | 2000-02-01 | China Petro-Chemical Corp | Catalyst and process for the conversion of carbon monoxide |
GB9720353D0 (en) | 1997-09-25 | 1997-11-26 | Johnson Matthey Plc | Hydrogen purification |
US6576203B2 (en) | 1998-06-29 | 2003-06-10 | Ngk Insulators, Ltd. | Reformer |
JP2000007302A (ja) * | 1998-06-29 | 2000-01-11 | Ngk Insulators Ltd | 改質反応装置 |
US7160343B2 (en) * | 2003-05-16 | 2007-01-09 | General Motors Corporation | Systems and methods for carbon monoxide clean-up |
US7618558B2 (en) * | 2005-04-15 | 2009-11-17 | Haldor Topsoe A/S | Process for cleaning gases from gasification units |
CN101050390B (zh) | 2007-04-27 | 2011-04-27 | 中国石化集团宁波工程有限公司 | 一种与粉煤气化配套的co变换工艺 |
CN101412932B (zh) * | 2008-11-28 | 2011-06-01 | 青岛联信化学有限公司 | 一种制取甲醇合成气的耐硫变换工艺 |
CA2756138A1 (en) * | 2009-03-30 | 2010-10-07 | Shell Internationale Research Maatschappij B.V. | Process for producing purified synthesis gas |
DE112009004645T5 (de) * | 2009-04-10 | 2012-08-09 | Mitsubishi Heavy Industries, Ltd. | Co-shift-katalysator, co-shift-reaktor und verfahren zur aufreinigung von in gas umgewandeltes gas |
WO2011105501A1 (ja) * | 2010-02-24 | 2011-09-01 | 三菱重工業株式会社 | Coシフト触媒、coシフト反応装置及びガス化ガスの精製方法 |
JP5535990B2 (ja) * | 2010-08-27 | 2014-07-02 | 株式会社日立製作所 | シフト触媒、ガス精製方法及び設備 |
JP5733974B2 (ja) | 2010-12-20 | 2015-06-10 | 三菱重工業株式会社 | Coシフト変換システム及び方法、石炭ガス化発電プラント |
JP5514133B2 (ja) | 2011-02-08 | 2014-06-04 | 株式会社日立製作所 | Co2の回収方法及びco2の回収装置 |
UA112362C2 (uk) * | 2012-06-26 | 2016-08-25 | Ламмус Текнолоджі Інк. | Двоступінчаста газифікація з подвійним охолодженням |
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EP2960318A4 (en) | 2016-02-17 |
AU2014219864B2 (en) | 2017-03-30 |
EP2960318B1 (en) | 2018-09-12 |
JP2014162803A (ja) | 2014-09-08 |
PL2960318T3 (pl) | 2019-07-31 |
US10000378B2 (en) | 2018-06-19 |
CN105102593B (zh) | 2017-08-25 |
US20160002032A1 (en) | 2016-01-07 |
CN105102593A (zh) | 2015-11-25 |
AU2014219864A1 (en) | 2015-09-10 |
WO2014129440A1 (ja) | 2014-08-28 |
EP2960318B8 (en) | 2018-10-24 |
DK2960318T3 (en) | 2019-01-07 |
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