JP2002521295A - 蒸気改質による合成ガスの製造方法 - Google Patents
蒸気改質による合成ガスの製造方法Info
- Publication number
- JP2002521295A JP2002521295A JP2000561126A JP2000561126A JP2002521295A JP 2002521295 A JP2002521295 A JP 2002521295A JP 2000561126 A JP2000561126 A JP 2000561126A JP 2000561126 A JP2000561126 A JP 2000561126A JP 2002521295 A JP2002521295 A JP 2002521295A
- Authority
- JP
- Japan
- Prior art keywords
- reactor
- steam reforming
- gas
- effluent
- reforming catalyst
- 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.)
- Pending
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/10—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with stationary catalyst bed
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Abstract
Description
(スチームリフォーミング:steam reforming)することによる合成ガスの製造
に関する。
)に固定されている触媒系に対して使用する。他の物質は、前記系に強度を与え
る支持構造物として作用する。これにより、触媒自身が十分な機械的強度を有し
ていない触媒でも形状の設計が可能となる。本明細書において、前記系は、内壁
に薄膜状の改質触媒が配置された管状物からなる。
物などの適切な形状が含まれる。
造される。
al reforming (ATR))がある。自動熱改質において、バーナー燃焼域(burner co
mbustion zone)では、不足当量の酸素との炎反応によって炭化水素原料が燃焼
し、続いて、蒸気改質触媒の固定床で、部分的に燃焼した供給原料の蒸気改質が
起こる。酸化剤は、空気、濃縮空気又は純粋な酸素であってもよい。
工程と、続いて、部分的に改質された原料を自動熱改質器に通す工程とを組合せ
る方法である。固定床は、燃焼炉(fired furnace)に配置された多数の管状物
で構成されていてもよい。前記組合せは、2工程改質または第1に続く第2改質
と呼ばれ、特に、メタノール及びアンモニアを製造するための合成ガスの製造に
適している。ATRの前に固定床蒸気改質器で起こる改質量をコントロールする
ことによって、メタノール合成に適切な当量の合成ガス、又はアンモニア合成に
適切な水素と窒素との比を有する合成ガスを製造できる。
態で使用する。触媒ペレットは、固定床反応器(改質管)に配置される。改質反
応は、吸熱反応である。従来の改質器では、反応に必要な熱は、通常、改質管の
外側への放射伝熱と対流伝熱との組み合わせによって、管の外部環境から供給さ
れる。熱は、伝導伝熱によって管壁を通して管の内側に伝わり、対流伝熱によっ
て気相に伝わる。最終的に、熱は、対流伝熱によって気相から触媒ペレットに伝
わる。触媒温度は、改質管の同軸位置での管内壁温度より低いが、100℃以上
となり得る。
われることを見出した。触媒への熱輸送は、管内壁からの伝導伝熱によって起こ
る。これは、気相を介する対流伝熱による輸送よりも、より効果的な輸送機構で
ある。結果として、管内壁及び触媒の温度は、ほぼ同一(差は5℃未満)である
。さらに、管の厚みを減少させ、以下に示すように、改質管の内側と外側との温
度差をより小さくすることができる。ゆえに、触媒温度をより高くできるととも
に、管温度をより低くでき、従来の改質管を、触媒作用を有する機材に代えても
、他の条件を全て同じにできる。管の寿命を長引かせるので、管外壁の温度は低
い方が好ましい。反応速度は温度とともに増加し、反応式(3)の平衡を右側へ
移動させて、原料を有効利用できるので、触媒温度は高い方が好ましい。
て小さくなっている。これにより、非典型的な管(例えば、より小さな直径を有
する管)であっても使用でき、許容できる圧力損失を維持できる。管径をより小
さくすることで、結果として、管の寿命を延ばし、高い温度が許容され、管材料
の消費を低減する。
する従来の改質管に比べて、触媒量が低減する。
ならない。これは、供給原料をプレ改質器に通すことによって達成できる。
おいて脱硫され、処理流(process steam)6と混合され、さらに断熱プレ改質
器8に導入される前に加熱される。プレ改質器8からの流出流は、煙道ガス通路
12に配置された熱交換コイルでさらに加熱され、管状改質器14に送られ、こ
こで、メタンから水素、一酸化炭素及び二酸化炭素への変換が起こる。前記流出
ガスは、自動熱改質器16を通り、ここで、酸化剤流18との燃焼が起こる。自
動熱改質器下流からの流出ガス20は、製品の使用目的に応じて処理される。
めの予熱コイル10 2.管状改質器14
水素供給原料を蒸気改質して水素と一酸化炭素とを豊富に含有するガスを調製す
る方法を提供する。この方法は、下記の工程を含む。
、この第1の反応器は、加熱(高温)ガス流と熱伝導関係にある反応器壁に支持
された薄膜状の蒸気改質触媒を有する (b)前記第1の反応器からの流出物を、薄膜状の蒸気改質触媒及び/又は蒸気
改質触媒ペレットを有し、かつ燃料の燃焼によって加熱された後続の管状反応器
に通し、部分的に蒸気改質されたガス流出物及び煙道ガスの加熱ガス流を得る工
程、 (c)前記第2の反応器からの流出物を自動熱改質器に通す工程、及び (d)自動熱改質器から、水素と一酸化炭素とに富む生成物ガスの加熱ガス流
を回収する工程。
原料を供給するシステムと、反応器自身と、反応器から得られた流出ガスの後処
理及び分析するための機器とからなる。
された長さ1050mmの1/4インチ管からなる。前記触媒は、ハルダートプ
ソーエーエス(Haldor Topsoe A/S)製のRKNRペレット型蒸気改質触媒と同
様の組成を有する。触媒層の厚みは、0.31mmである。触媒作用を有する反
応管は、固体状金属製のケーシング(ケース)内に配置されている。このケーシ
ングは、触媒作用を有する前記反応管を収容し、この管の周りと密接するホール
(孔)を有する。熱電対が配置された多数の溝(milled grooves)が、前記ホー
ルに沿って作製されている。熱電対の一つは、可動性であり、触媒作用を有する
管の壁温度プロファイル(スペクトル)を得ることができる。さらに、熱電対は
、触媒作用を有する帯域への入口及び触媒作用を有する帯域からの出口における
ガス温度を測定できるように、触媒作用を有する管のガス通路に配置されている
。ケーシングを有する反応器は、電熱オーブン中に配置されている。ここでは、
6つの異なる部位で独立して温度操作が行える。
され、そして反応器に導入される前に予備加熱される。反応器からの流出ガス流
は、冷却され、濃縮水がガスから分離され、そしてガスの組成が、ガスクロマト
グラフィーで測定される。
用した場合を想定して低い温度(試験1)で行なわれ、他方は管状反応器に使用
した場合を想定して高い温度(試験2)で行われた。条件を表1に示す。圧力は
両方とも26bar gであった。可動熱電対によって測定された反応器壁の温
度プロファイルを図2に示す。
に関して平衡状態にある。このことは、固定床反応器と同様の転換率が触媒作用
を有する機材においても得られることを示している。
Claims (2)
- 【請求項1】 反応器の壁に薄膜状に備え付けられた蒸気改質触媒の存在下
、炭化水素供給原料を蒸気改質することによって、水素と一酸化炭素とを豊富に
含有するガスを調製する方法であって、下記の工程を含む方法。 (a)必要に応じて、炭化水素供給原料の処理ガスを第1の反応器に通す工程
、この第1の反応器は、加熱ガス流により熱伝導可能な反応器壁に備え付けられ
た薄膜状の蒸気改質触媒を有する (b)前記第1の反応器からの流出物を、薄膜状の蒸気改質触媒及び/又は蒸気
改質触媒ペレットを有し、かつ燃料の燃焼によって加熱される後続の管状反応器
に通し、部分的に蒸気改質されたガス流出物及び煙道ガスの加熱ガス流を得る工
程、 (c)前記第2の反応器からの流出物を自動熱改質器に通す工程、及び (d)自動熱改質器から、水素と一酸化炭素とを豊富に含有する生成物ガスの
加熱ガス流を回収する工程 - 【請求項2】 蒸気改質触媒が、ニッケル及び/又は貴金属を含む請求項1
記載の方法。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP1998/004563 WO2000005168A1 (en) | 1998-07-21 | 1998-07-21 | Synthesis gas production by steam reforming |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2002521295A true JP2002521295A (ja) | 2002-07-16 |
Family
ID=8167013
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2000561126A Pending JP2002521295A (ja) | 1998-07-21 | 1998-07-21 | 蒸気改質による合成ガスの製造方法 |
Country Status (19)
Country | Link |
---|---|
US (1) | US7060118B1 (ja) |
EP (1) | EP1097105B1 (ja) |
JP (1) | JP2002521295A (ja) |
KR (1) | KR100401369B1 (ja) |
CN (1) | CN1117693C (ja) |
AT (1) | ATE225314T1 (ja) |
AU (1) | AU752109B2 (ja) |
BR (1) | BR9815937A (ja) |
CA (1) | CA2337937C (ja) |
CZ (1) | CZ294907B6 (ja) |
DE (1) | DE69808521T2 (ja) |
EA (1) | EA002517B1 (ja) |
ES (1) | ES2185209T3 (ja) |
MX (1) | MXPA01000735A (ja) |
NO (1) | NO328552B1 (ja) |
NZ (1) | NZ509100A (ja) |
PL (1) | PL192266B1 (ja) |
SK (1) | SK285118B6 (ja) |
WO (1) | WO2000005168A1 (ja) |
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JP2005263618A (ja) * | 2004-02-16 | 2005-09-29 | Fuji Electric Holdings Co Ltd | 燃料改質器 |
JP2009084392A (ja) * | 2007-09-28 | 2009-04-23 | Japan Oil Gas & Metals National Corp | 管式リフォーマーの有効熱利用方法 |
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US7320778B2 (en) | 2004-07-21 | 2008-01-22 | Catacel Corp. | High-performance catalyst support |
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US7565743B2 (en) | 2005-04-14 | 2009-07-28 | Catacel Corp. | Method for insertion and removal of a catalytic reactor cartridge |
US7682580B2 (en) | 2005-05-19 | 2010-03-23 | Catacel Corp. | Catalytic reactor having radial leaves |
US7501102B2 (en) | 2005-07-28 | 2009-03-10 | Catacel Corp. | Reactor having improved heat transfer |
US20070104641A1 (en) * | 2005-11-08 | 2007-05-10 | Ahmed M M | Method of controlling oxygen addition to a steam methane reformer |
WO2007081016A1 (ja) * | 2006-01-13 | 2007-07-19 | Matsushita Electric Industrial Co., Ltd. | 水素生成装置、燃料電池システム及びそれらの運転方法 |
US7829035B2 (en) | 2006-01-19 | 2010-11-09 | Massachusetts Institute Of Technology | Oxidation catalyst |
CN101321690B (zh) * | 2006-04-05 | 2012-03-14 | 花王株式会社 | 反应器 |
DE102006023248C5 (de) | 2006-05-18 | 2018-01-25 | Air Liquide Global E&C Solutions Germany Gmbh | Verfahren und Anlage zur Herstellung von Synthesegas |
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US20090184293A1 (en) * | 2008-01-18 | 2009-07-23 | Han Pat A | Process for reforming hydrocarbons |
US7850944B2 (en) * | 2008-03-17 | 2010-12-14 | Air Products And Chemicals, Inc. | Steam-hydrocarbon reforming method with limited steam export |
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TWI412172B (zh) * | 2010-11-05 | 2013-10-11 | Ind Tech Res Inst | 燃料重組裝置及其方法 |
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WO2016016257A1 (en) | 2014-07-29 | 2016-02-04 | Eni S.P.A. | Integrated sct-cpo/pox process for producing synthesis gas |
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US11059719B2 (en) | 2016-04-26 | 2021-07-13 | Haldor Topsøe A/S | Process for producing hydrogen or syngas by methanol cracking |
WO2020174056A1 (en) * | 2019-02-28 | 2020-09-03 | Haldor Topsøe A/S | Chemical plant with a reforming section and a process for producing a chemical product |
US11472700B2 (en) * | 2019-12-27 | 2022-10-18 | Saudi Arabian Oil Company | Catalyst and process for thermo-neutral reforming of petroleum-based liquid hydrocarbons |
CN112265962B (zh) * | 2020-10-30 | 2022-03-04 | 庄焱法 | 一种电气协同供热重整反应系统 |
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DK173496B1 (da) * | 1998-07-16 | 2001-01-02 | Topsoe Haldor As | Fremgangsmåde til fremstilling af syntesegas ved vanddampreformering under anvendelse af en katalyseret metaloverflade |
-
1998
- 1998-07-21 EA EA200100134A patent/EA002517B1/ru not_active IP Right Cessation
- 1998-07-21 JP JP2000561126A patent/JP2002521295A/ja active Pending
- 1998-07-21 EP EP98942587A patent/EP1097105B1/en not_active Expired - Lifetime
- 1998-07-21 WO PCT/EP1998/004563 patent/WO2000005168A1/en active IP Right Grant
- 1998-07-21 SK SK34-2001A patent/SK285118B6/sk not_active IP Right Cessation
- 1998-07-21 DE DE69808521T patent/DE69808521T2/de not_active Expired - Lifetime
- 1998-07-21 BR BR9815937-2A patent/BR9815937A/pt not_active IP Right Cessation
- 1998-07-21 PL PL345848A patent/PL192266B1/pl unknown
- 1998-07-21 MX MXPA01000735A patent/MXPA01000735A/es unknown
- 1998-07-21 AT AT98942587T patent/ATE225314T1/de active
- 1998-07-21 ES ES98942587T patent/ES2185209T3/es not_active Expired - Lifetime
- 1998-07-21 CZ CZ20004929A patent/CZ294907B6/cs not_active IP Right Cessation
- 1998-07-21 US US09/743,528 patent/US7060118B1/en not_active Expired - Fee Related
- 1998-07-21 NZ NZ509100A patent/NZ509100A/xx not_active IP Right Cessation
- 1998-07-21 KR KR10-2001-7000912A patent/KR100401369B1/ko not_active IP Right Cessation
- 1998-07-21 CN CN98814142A patent/CN1117693C/zh not_active Expired - Fee Related
- 1998-07-21 CA CA002337937A patent/CA2337937C/en not_active Expired - Fee Related
- 1998-07-21 AU AU90672/98A patent/AU752109B2/en not_active Ceased
-
2000
- 2000-12-29 NO NO20006711A patent/NO328552B1/no not_active IP Right Cessation
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005263618A (ja) * | 2004-02-16 | 2005-09-29 | Fuji Electric Holdings Co Ltd | 燃料改質器 |
JP2009084392A (ja) * | 2007-09-28 | 2009-04-23 | Japan Oil Gas & Metals National Corp | 管式リフォーマーの有効熱利用方法 |
US8338495B2 (en) | 2007-09-28 | 2012-12-25 | Japan Oil, Gas And Metals National Corporation | Method for efficient use of heat from tubular reformer |
Also Published As
Publication number | Publication date |
---|---|
NO20006711D0 (no) | 2000-12-29 |
EP1097105B1 (en) | 2002-10-02 |
PL192266B1 (pl) | 2006-09-29 |
NO328552B1 (no) | 2010-03-15 |
SK342001A3 (en) | 2001-09-11 |
WO2000005168A1 (en) | 2000-02-03 |
US7060118B1 (en) | 2006-06-13 |
KR20010106413A (ko) | 2001-11-29 |
CN1304380A (zh) | 2001-07-18 |
MXPA01000735A (es) | 2002-04-08 |
EP1097105A1 (en) | 2001-05-09 |
NZ509100A (en) | 2002-09-27 |
ATE225314T1 (de) | 2002-10-15 |
ES2185209T3 (es) | 2003-04-16 |
KR100401369B1 (ko) | 2003-10-17 |
EA200100134A1 (ru) | 2001-08-27 |
AU752109B2 (en) | 2002-09-05 |
CZ294907B6 (cs) | 2005-04-13 |
BR9815937A (pt) | 2001-02-28 |
CA2337937A1 (en) | 2000-02-03 |
PL345848A1 (en) | 2002-01-14 |
EA002517B1 (ru) | 2002-06-27 |
CN1117693C (zh) | 2003-08-13 |
CA2337937C (en) | 2004-10-26 |
NO20006711L (no) | 2001-03-21 |
AU9067298A (en) | 2000-02-14 |
CZ20004929A3 (en) | 2001-05-16 |
DE69808521D1 (de) | 2002-11-07 |
SK285118B6 (sk) | 2006-06-01 |
DE69808521T2 (de) | 2003-01-30 |
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