JP5405569B2 - 触媒部分酸化改質 - Google Patents
触媒部分酸化改質 Download PDFInfo
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Description
Claims (26)
- 第1の炭化水素の一部を部分燃焼させるのに十分な条件で、酸化剤及び1種又は複数の第1の触媒の存在下で、前記第1の炭化水素を部分酸化することにより、二酸化炭素、燃焼していない第1の炭化水素、及び熱を提供するステップと;
触媒部分酸化(CPOX)反応器中で、前記部分酸化する工程で発生した熱の少なくとも一部、及び1種又は複数の第1の触媒の存在下で、前記燃焼していない第1の炭化水素の少なくとも一部を改質することにより、水素、一酸化炭素、及び二酸化炭素を含む第1の合成ガスを提供するステップと;
水蒸気、及び1種又は複数の第2の触媒の存在下で、前記第1の合成ガスからの熱を第2の炭化水素に間接的に交換して、前記第2の炭化水素の少なくとも一部を改質することにより、水素、一酸化炭素、及び二酸化炭素を含む第2の合成ガスを提供するステップと;
前記第1の合成ガス、前記第2の合成ガス、又はこれらの混合物中の一酸化炭素の少なくとも一部を二酸化炭素に対して反応させることにより、乾燥ベースで5モル%以下の一酸化炭素を含む変換済み合成ガスを提供するステップと;
を含み、
前記第1の合成ガスは、CPOX反応器から出たとき及びいかなる更なる処理または混合の前に、乾燥ベースで30モル%〜乾燥ベースで70モル%の水素、乾燥ベースで5モル%〜乾燥ベースで35モル%の一酸化炭素、及び、乾燥ベースで5モル%〜25モル%の二酸化炭素を含む、
合成ガスを生成するための方法。 - 水蒸気及び1種又は複数の第2の触媒の存在下で、前記第1の合成ガスからの熱を前記第2の炭化水素に間接的に交換する前に、熱伝達媒体を用いた直接熱交換、間接熱交換、又はその両方によって、前記第1の合成ガスを冷却するステップをさらに含む、請求項1に記載の方法。
- 前記第1の合成ガスの少なくとも一部、及び前記第2の合成ガスの少なくとも一部を混合することにより、合成ガス生成物を提供するステップをさらに含む、請求項1に記載の方法。
- 前記水素の少なくとも一部を、前記変換済み合成ガスから分離することにより、水素生成物を提供するステップと
をさらに含む、請求項1に記載の方法。 - 1種又は複数の第3の触媒の存在下、前記水素生成物の少なくとも一部を窒素と反応させることにより、アンモニア生成物を提供するステップをさらに含む、請求項4に記載の方法。
- 前記アンモニア生成物の少なくとも一部を1種又は複数の反応物に反応させることにより、1種又は複数のアンモニア誘導体を提供するステップをさらに含む、請求項5に記載の方法。
- 前記二酸化炭素の少なくとも一部を前記変換済み合成ガスから分離することにより、水素、一酸化炭素、及び二酸化炭素を含む第1の水素生成物を提供するステップと;
前記第1の水素生成物中の一酸化炭素及び二酸化炭素の少なくとも一部を反応させることにより、水素、メタン、及び水を含む第2の水素生成物を提供するステップと;
1種又は複数の第3の触媒の存在下、前記第2の水素生成物の少なくとも一部を窒素と反応させることにより、アンモニア生成物を提供するステップとを
さらに含む、請求項1に記載の方法。 - 前記アンモニア生成物の少なくとも一部と1種又は複数の反応物とを反応させることにより、1種又は複数のアンモニア誘導体を提供するステップをさらに含む、請求項7に記載の方法。
- 前記二酸化炭素の少なくとも一部を前記変換済み合成ガスから分離することにより、水素、一酸化炭素、及び二酸化炭素を含む第1の水素生成物を提供するステップと;
前記第1の水素生成物中の一酸化炭素及び二酸化炭素の少なくとも一部を反応させることにより、水素、メタン、及び水を含む第2の水素生成物を提供するステップと;
前記水の少なくとも一部を前記第2の水素生成物から分離することにより、乾燥水素生成物を提供するステップと;
1種又は複数の第3の触媒の存在下、前記乾燥水素生成物の少なくとも一部を窒素と反応させることにより、アンモニア生成物を提供するステップと
をさらに含む、請求項1に記載の方法。 - 前記アンモニア生成物の少なくとも一部を1種又は複数の反応物と反応させることにより、1種又は複数のアンモニア誘導体を提供するステップをさらに含む、請求項9に記載の方法。
- 前記二酸化炭素の少なくとも一部を前記変換済み合成ガスから分離することにより、水素、一酸化炭素、及び二酸化炭素を含む第1の水素生成物を提供するステップと;
前記第1の水素生成物中の一酸化炭素及び二酸化炭素の少なくとも一部を反応させることにより、水素、メタン、及び水を含む第2の水素生成物を提供するステップと;
前記水の少なくとも一部を前記第2の水素生成物から分離することにより、乾燥水素生成物を提供するステップと;
前記乾燥水素生成物の少なくとも一部を精製することにより、水素を含む第4の水素生成物を提供するステップであって、任意の残留ガスの少なくとも一部を分離する操作を含み、前記残留ガスが、一酸化炭素、二酸化炭素、水、及び不活性物質の1種又は複数を含む上記ステップと
をさらに含む、請求項1に記載の方法。 - 前記二酸化炭素の少なくとも一部を前記変換済み合成ガスから分離することにより、水素、一酸化炭素、及び二酸化炭素を含む第1の水素生成物を提供するステップと;
前記第1の水素生成物中の一酸化炭素及び二酸化炭素の少なくとも一部を反応させることにより、水素、メタン、及び水を含む第2の水素生成物を提供するステップと;
前記メタン及び水の少なくとも一部を前記第2の水素生成物から分離することにより、乾燥水素生成物を提供するステップと;
前記乾燥水素生成物の少なくとも一部を精製することにより、約2.7から約3.3のモル比で水素及び窒素を含む精製済み水素生成物を提供するステップであって、任意の残留ガスの少なくとも一部及び過剰な窒素を分離する操作を含み、前記残留ガスが、一酸化炭素、二酸化炭素、水、及び不活性物質の1種又は複数を含み、前記酸化剤が、空気、過剰な空気、窒素に富む空気、又はこれらの混合物を含む上記ステップと
をさらに含む、請求項1に記載の方法。 - 前記1種又は複数の第1の触媒、第2の触媒、又はその両方が、2種以上の触媒を含む、請求項1に記載の方法。
- 前記第1の炭化水素及び前記第2の炭化水素が、1種又は複数のC1〜C20炭化水素を含む、請求項1に記載の方法。
- 前記第1の炭化水素及び前記第2の炭化水素が、天然ガス、脱硫天然ガス、メタン、脱硫メタン、又はこれらの混合物を含む、請求項1に記載の方法。
- 前記第1の炭化水素及び前記第2の炭化水素が異なる、請求項1に記載の方法。
- 前記第1の合成ガスの少なくとも一部、及び前記第2の合成ガスの少なくとも一部を混合することにより、合成ガス生成物を提供するステップをさらに含み、
合成ガス生成物が、乾燥ベースで50モル%〜乾燥ベースで70モル%の水素、乾燥ベースで20モル%〜乾燥ベースで35モル%の一酸化炭素、及び、乾燥ベースで5モル%〜25モル%の二酸化炭素を含む、請求項1に記載の方法。 - 前記第1の合成ガスが、乾燥ベースで少なくとも5モル%〜25モル%の範囲の二酸化炭素濃度を有する、請求項1に記載の方法。
- 前記第1の合成ガスが、乾燥ベースで少なくとも7モル%〜25モル%の範囲の二酸化炭素濃度を有する、請求項1に記載の方法。
- 前記第1の合成ガスからの熱を第2の炭化水素に間接的に交換することが、前記第1の合成ガスと前記第2の合成ガスとの間の接触を防止することをさらに含み;そして、前記方法が、第1の合成ガス生成物及び第2の合成ガス生成物を回収することをさらに含む、請求項1に記載の方法。
- 第1の炭化水素の少なくとも一部を部分燃焼させるのに十分な条件で、第1の反応ゾーンで酸化剤及び1種又は複数の第1の触媒の存在下、前記第1の炭化水素を部分酸化することにより、二酸化炭素、燃焼していない第1の炭化水素、及び熱を提供するステップと;
触媒部分酸化(CPOX)反応器中で、前記部分酸化する工程で発生した熱の少なくとも一部、及び1種又は複数の第1の触媒の存在下で、第1の反応ゾーンで前記燃焼していない炭化水素を少なくとも部分的に改質することにより、水素、一酸化炭素、及び二酸化炭素を含む第1の合成ガスを提供するステップと;
水蒸気及び1種又は複数の第2の触媒の存在下、第2の反応ゾーンで前記第1の合成ガスからの熱を第2の炭化水素に間接的に交換して、前記第2の炭化水素の少なくとも一部を改質することにより、水素、一酸化炭素、及び二酸化炭素を含む第2の合成ガスを提供するステップと
前記第1の合成ガス、前記第2の合成ガス、又はこれらの混合物中の一酸化炭素の少なくとも一部を二酸化炭素に対して反応させることにより、乾燥ベースで5モル%以下の一酸化炭素を含む変換済み合成ガスを提供するステップと;
を含み、
前記第1の合成ガスは、CPOX反応器から出たとき及びいかなる更なる処理または混合の前に、乾燥ベースで30モル%〜乾燥ベースで70モル%の水素、乾燥ベースで5モル%〜乾燥ベースで35モル%の一酸化炭素、及び、乾燥ベースで5モル%〜25モル%の二酸化炭素を含む、
合成ガスを生成するための方法。 - 前記第1の合成ガスからの熱を前記第2の炭化水素に間接的に交換する前に、熱伝達媒体を用いる直接熱交換、間接熱交換、又はその両方によって、前記第1の合成ガスを冷却するステップをさらに含む、請求項21に記載の方法。
- 1種又は複数の第1の触媒、第2の触媒、又はその両方が、2種以上の触媒を含む、請求項21に記載の方法。
- 前記第1の反応ゾーン、前記第2の反応ゾーン、又はその両方が、2つ以上の触媒含有床を含む、請求項21に記載の方法。
- 前記第2の反応ゾーンが、1つ又は複数のチューブを含み、そのそれぞれが前記第2の触媒を含有する、請求項21に記載の方法。
- 前記第1の合成ガスからの熱を第2の炭化水素に間接的に交換することが、前記第1の合成ガスと前記第2の合成ガスとの間の接触を防止することをさらに含み;そして、前記方法が、第1の合成ガス生成物及び第2の合成ガス生成物を回収することをさらに含む、請求項21に記載の方法。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102602141B1 (ko) | 2021-10-06 | 2023-11-14 | 두산에너빌리티 주식회사 | 복합 개질기 |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8273139B2 (en) * | 2003-03-16 | 2012-09-25 | Kellogg Brown & Root Llc | Catalytic partial oxidation reforming |
US20100035193A1 (en) * | 2008-08-08 | 2010-02-11 | Ze-Gen, Inc. | Method and system for fuel gas combustion, and burner for use therein |
US9083020B2 (en) * | 2009-09-04 | 2015-07-14 | Lg Fuel Cell Systems Inc. | Reducing gas generators and methods for generating reducing gas |
US8636922B2 (en) * | 2010-06-30 | 2014-01-28 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process for recovering hydrogen and carbon dioxide from a syngas stream |
US8535638B2 (en) | 2010-11-11 | 2013-09-17 | Air Liquide Large Industries U.S. | Process for recovering hydrogen and carbon dioxide |
WO2012084135A1 (en) * | 2010-12-22 | 2012-06-28 | Haldor Topsøe A/S | Process for reforming hydrocarbon |
US20120291482A1 (en) * | 2011-05-18 | 2012-11-22 | Air Liquide Large Industries U.S. Lp | Process For Recovering Hydrogen And Carbon Dioxide |
DE102011113699A1 (de) * | 2011-09-20 | 2013-03-21 | Lurgi Gmbh | Verfahren zur Herstellung von Synthesegas |
US9388980B2 (en) | 2011-12-15 | 2016-07-12 | Kellogg Brown + Root LLC | Systems and methods for gasifying a hydrocarbon feedstock |
WO2013095130A1 (en) * | 2011-12-19 | 2013-06-27 | Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center | Process for producing ammonia and urea |
MX364235B (es) | 2012-06-27 | 2019-04-17 | Grannus Llc | Produccion de poligeneracion de polvo y fertilizador a traves de captura de emisiones. |
WO2016016251A1 (en) * | 2014-07-29 | 2016-02-04 | Eni S.P.A. | Integrated sct-cpo/sr process for producing synthesis gas |
CA3007124A1 (en) | 2015-12-04 | 2017-06-08 | Grannus, Llc | Polygeneration production of hydrogen for use in various industrial processes |
AU2017356668B2 (en) | 2016-11-09 | 2023-04-20 | 8 Rivers Capital, Llc | Systems and methods for power production with integrated production of hydrogen |
CN110382667A (zh) | 2016-12-23 | 2019-10-25 | 碳工程有限公司 | 从稀薄的二氧化碳源合成燃料的方法和系统 |
US11142832B2 (en) | 2017-02-09 | 2021-10-12 | Battelle Energy Alliance, Llc | Methods and systems for syngas production and for efficient, flexible energy generation |
US10870810B2 (en) | 2017-07-20 | 2020-12-22 | Proteum Energy, Llc | Method and system for converting associated gas |
CN110799452B (zh) | 2017-07-25 | 2023-08-01 | 托普索公司 | 用于制备合成气的方法 |
EP3658493B1 (en) | 2017-07-25 | 2023-08-30 | Topsoe A/S | Process for the co-production of methanol and ammonia |
CA3069817A1 (en) | 2017-07-25 | 2019-01-31 | Haldor Topsoe A/S | Method for the preparation of ammonia synthesis gas |
CN107416863B (zh) * | 2017-08-01 | 2020-01-07 | 中盐安徽红四方新能源科技有限公司 | 磷酸铁生产的废水制备工业级铵盐的方法 |
CN114538376B (zh) | 2017-11-09 | 2024-07-30 | 八河流资产有限责任公司 | 用于生产和分离氢气和二氧化碳的系统和方法 |
DE102018210921A1 (de) * | 2018-07-03 | 2019-08-14 | Thyssenkrupp Ag | Vermeidung von VOC und HAP Emissionen aus dem Entgaser von Synthesegas verarbeitenden Anlagen |
BG112796A (bg) * | 2018-09-03 | 2020-04-15 | Тодор ТОДОРОВ | Получаване на сингаз за производство на водород, чрез паров реформинг на въглеводороди с прилагане на процес на пълно горене на поток горивни газове в автотермичен реформинг |
AU2020292848A1 (en) | 2019-06-13 | 2022-02-03 | 8 Rivers Capital, Llc | Power production with cogeneration of further products |
EP4433414A1 (en) | 2021-11-18 | 2024-09-25 | 8 Rivers Capital, LLC | Apparatus for hydrogen production |
Family Cites Families (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2896927A (en) * | 1956-09-26 | 1959-07-28 | Texaco Inc | Gas and liquid contacting apparatus |
GB944059A (en) | 1960-12-29 | 1963-12-11 | Exxon Research Engineering Co | Process for the production of ammonia synthesis feed gas |
US3920717A (en) * | 1973-03-26 | 1975-11-18 | Texaco Development Corp | Production of methanol |
US3929429A (en) * | 1974-09-26 | 1975-12-30 | Texaco Inc | Fuel gas from solid carbonaceous fuels |
US4081253A (en) * | 1976-12-10 | 1978-03-28 | Texaco Development Corporation | Production of purified synthesis gas and carbon monoxide |
JPS58194707A (ja) * | 1982-05-07 | 1983-11-12 | Masaya Kuno | 炭化水素のガス化方法 |
GB2163449B (en) | 1984-07-18 | 1988-06-02 | Shell Int Research | Production of gas mixtures containing hydrogen and carbon monoxide |
DE3521304A1 (de) | 1985-06-13 | 1986-12-18 | Linde Ag, 6200 Wiesbaden | Verfahren zur erzeugung eines synthesegases |
US5011625A (en) * | 1989-12-11 | 1991-04-30 | The M. W. Kellogg Company | Autothermal steam reforming process |
US5122299A (en) * | 1989-12-11 | 1992-06-16 | The M. W. Kellogg Company | Autothermal steam reforming process |
JPH04310501A (ja) * | 1991-04-03 | 1992-11-02 | Mw Kellogg Co | 自己熱式スチーム改質プロセス |
JPH04313339A (ja) * | 1991-04-12 | 1992-11-05 | Toyo Eng Corp | 触媒燃焼を利用した部分酸化改質反応器 |
US5362454A (en) * | 1993-06-28 | 1994-11-08 | The M. W. Kellogg Company | High temperature heat exchanger |
US5358696A (en) * | 1993-12-01 | 1994-10-25 | Texaco Inc. | Production of H2 -rich gas |
MY131526A (en) * | 1993-12-27 | 2007-08-30 | Shell Int Research | A process for the preparation of carbon monoxide and/or hydrogen |
US5720901A (en) * | 1993-12-27 | 1998-02-24 | Shell Oil Company | Process for the catalytic partial oxidation of hydrocarbons |
US5496859A (en) * | 1995-01-28 | 1996-03-05 | Texaco Inc. | Gasification process combined with steam methane reforming to produce syngas suitable for methanol production |
US5523483A (en) * | 1995-06-16 | 1996-06-04 | The M. W. Kellogg Company | Integrated urea/ammonia process |
DE19625093A1 (de) * | 1996-06-24 | 1998-01-02 | Bayer Ag | Verfahren zur Gewinnung von Kohlenmonoxid und Wasserstoff |
US6005011A (en) * | 1998-05-06 | 1999-12-21 | The M. W. Kellogg Company | Process for converting gas to liquids |
DK173742B1 (da) * | 1998-09-01 | 2001-08-27 | Topsoe Haldor As | Fremgangsmåde og reaktorsystem til fremstilling af syntesegas |
US6726850B1 (en) * | 2000-01-14 | 2004-04-27 | Sebastian C. Reyes | Catalytic partial oxidation using staged oxygen addition |
JP3543717B2 (ja) * | 2000-02-18 | 2004-07-21 | 日産自動車株式会社 | 触媒燃焼器 |
EP1188713A3 (en) * | 2000-09-18 | 2003-06-25 | Haldor Topsoe A/S | Production of hydrogen and carbon monoxide containing synthesis gas by partial oxidation |
NL1016848C2 (nl) * | 2000-12-11 | 2002-06-13 | Continental Engineering B V | Werkwijze en inrichting voor de bereiding van ammoniak. |
JP2002308604A (ja) * | 2001-04-10 | 2002-10-23 | Toyota Motor Corp | 燃料改質装置 |
WO2003002459A1 (en) * | 2001-06-28 | 2003-01-09 | Fluor Corporation | Improved ammonia plant configurations and methods |
US6855272B2 (en) | 2001-07-18 | 2005-02-15 | Kellogg Brown & Root, Inc. | Low pressure drop reforming exchanger |
JP4773641B2 (ja) * | 2001-07-19 | 2011-09-14 | 三菱重工業株式会社 | メタノールの製造方法 |
US20030162846A1 (en) * | 2002-02-25 | 2003-08-28 | Wang Shoou-L | Process and apparatus for the production of synthesis gas |
JP4209625B2 (ja) * | 2002-04-09 | 2009-01-14 | 新日本石油株式会社 | オートサーマルリフォーミング改質器およびそれを用いたオートサーマルリフォーミング方法 |
US6936238B2 (en) * | 2002-09-06 | 2005-08-30 | General Motors Corporation | Compact partial oxidation/steam reactor with integrated air preheater, fuel and water vaporizer |
GB0225961D0 (en) * | 2002-11-07 | 2002-12-11 | Johnson Matthey Plc | Production of hydrocarbons |
CA2504206A1 (en) * | 2002-11-11 | 2004-05-27 | Conocophillips Company | Stabilized alumina supports, catalysts made therefrom, and their use in partial oxidation |
GB0301323D0 (en) * | 2003-01-21 | 2003-02-19 | Johnson Matthey Plc | Methanol synthesis |
US7125913B2 (en) * | 2003-03-14 | 2006-10-24 | Conocophillips Company | Partial oxidation reactors and syngas coolers using nickel-containing components |
US6958363B2 (en) * | 2003-03-15 | 2005-10-25 | Conocophillips Company | Hydrogen use in a GTL plant |
US7138001B2 (en) * | 2003-03-16 | 2006-11-21 | Kellogg Brown & Root Llc | Partial oxidation reformer-reforming exchanger arrangement for hydrogen production |
US8273139B2 (en) * | 2003-03-16 | 2012-09-25 | Kellogg Brown & Root Llc | Catalytic partial oxidation reforming |
CA2507922C (en) * | 2003-03-18 | 2012-08-14 | Kellogg Brown & Root, Inc. | Autothermal reformer-reforming exchanger arrangement for hydrogen production |
US7261751B2 (en) * | 2004-08-06 | 2007-08-28 | Conocophillips Company | Synthesis gas process comprising partial oxidation using controlled and optimized temperature profile |
DE102005021500A1 (de) * | 2005-05-10 | 2006-11-16 | Uhde Gmbh | Verfahren zur Aufheizung eines Dampf-/Erdgasgemisches im Bereich eines Gassammelrohres nach einem Primärreformer |
US7485767B2 (en) * | 2005-06-29 | 2009-02-03 | Exxonmobil Chemical Patents Inc. | Production of synthesis gas blends for conversion to methanol or Fischer-Tropsch liquids |
US20070129450A1 (en) * | 2005-11-18 | 2007-06-07 | Barnicki Scott D | Process for producing variable syngas compositions |
JP5065605B2 (ja) * | 2006-03-02 | 2012-11-07 | Jx日鉱日石エネルギー株式会社 | 水素製造装置および燃料電池システム並びにその運転方法 |
US8152874B2 (en) * | 2006-06-19 | 2012-04-10 | Siemens Energy, Inc. | Systems and methods for integration of gasification and reforming processes |
-
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- 2008-07-18 US US12/175,639 patent/US8273139B2/en not_active Expired - Lifetime
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- 2009-06-29 BR BRPI0914822A patent/BRPI0914822A2/pt not_active IP Right Cessation
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