CN1269724C - 生产富氢和一氧化碳的气体的方法 - Google Patents

生产富氢和一氧化碳的气体的方法 Download PDF

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CN1269724C
CN1269724C CNB981056520A CN98105652A CN1269724C CN 1269724 C CN1269724 C CN 1269724C CN B981056520 A CNB981056520 A CN B981056520A CN 98105652 A CN98105652 A CN 98105652A CN 1269724 C CN1269724 C CN 1269724C
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J·罗斯特鲁普－尼尔森
P·S·克里斯滕森
V·L·汉森
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Abstract

一种在管式反应器中载有蒸汽重整催化剂的情况下，通过烃原料蒸汽重整，生产富氢和一氧化碳的气体的方法，该方法(a)让预重整的烃工艺气体通过在反应器内壁上载有蒸汽重整催化剂薄膜并被燃料燃烧加热的管式反应器，由此获得部分蒸汽重整气流和热烟气；(b)让管式反应器的流出物通过具有蒸汽重整催化剂的固定床反应器；和(c)从固定床反应器排出富一氧化碳和氢的产品气。本发明的方法，其中还包括在步骤(a)前的步骤：让预重整的烃工艺气体通过在反应器内壁上载有蒸汽重整催化剂薄膜的管式反应器，该反应器能与来自随后的步骤(a)的热烟气进行热交换。

Description

生产富氢和一氧化碳的气体的方法
本发明涉及通过烃原料与催化成品接触、蒸汽重整生产合成气。
术语催化成品用来表示一种催化系，该催化系的催化剂层固定在另外物质表面，例如金属表面上，其它物质可用作加强催化系的载体结构。这使催化剂自身形状可设计成不具有充够机械强度。本发明催化剂系所包括的管子其内壁放置重整催化剂薄膜层。
按下列反应(1)-(3)，通过蒸汽重整由烃生产合成气，
Figure C9810565200031
Figure C9810565200033
现有技术蒸汽重整技术是采用呈各种大小形状颗粒的重整催化剂。将催化剂颗粒放置在固定床反应器(重整管)中。重整反应是吸热式的。在普通重整器中，通常是通过对管子外部结合辐射和对流，从管外四周向反应提供的需热量。热量是通过管壁的热传导，传递给管内的，并通过对流传递给气相。最后，通过对流将热由气相传递给催化剂颗粒。催化剂温度可高于100℃，低于上述重整管轴向位置上的管内壁温度。
业已发出，当催化成品用于蒸汽重整过程，热传递更有效。通过管内壁传导，将热传递给催化剂，这是比通过气相对流进行传递的更为有效的一种传递机理。其结果是管内壁和催化剂温度几乎相等(温差低于5℃)。此外，从下面看出，减少管壁厚度，可使重整器管内外壁的温差变小。因而有可能使催化剂温度较高、管道温度较低。当用催化成品管代替普通重整器管子时，所有其他条件均相同。管外壁温度低，是所希望的、因为这可延长管子寿命。催化剂温度高是有利的，因为反应速度随温度而增加并且反应(3)的平衡向右边移动，结果是更好利用原料。
为此，本发明提供一种在管式反应器内载有蒸汽重整催化剂薄膜的情况下，通过对烃原料蒸汽重整，生产富一氧化碳和氢的气体方法，该方法包括下列步骤：
(a)让预重整的烃工艺气体通过在反应器内壁上载有蒸汽重整催化剂薄膜并被燃料燃烧加热的管式反应器，由此获得部分蒸汽重整气流和热烟气；
(b)让管式反应器的流出物通过具有蒸汽重整催化剂的固定床反应器；和
(c)从固定床反应器排出富一氧化碳和氢的产品气。
本发明的方法，其中还包括在步骤(a)前的步骤：让预重整的烃工艺气体通过在反应器内壁上载有蒸汽重整催化剂薄膜的管式反应器，该反应器能与来自随后的步骤(a)的热烟气进行热交换。
催化重整器管的压降大大低于具有相同管径的普通容器。这样有可能采用具有较小直径的反应器，并仍保持可接受的压降。管径较小的结果是使管子寿命增加，并耐更高温度和减少管子材料消耗。
最后，与具有固定床重整催化剂的普通重整器相比，当采用催化成品重整器管子时，可减少催化剂用量。
本发明的方法，其中固定床蒸汽重整催化剂优选是在绝热条件下进行操作的。
本发明的方法，其中固定床蒸汽重整催化剂优选放置在第二管式反应器中。
本发明的方法，其中蒸汽重整催化剂优选包括镍和/或钌。
图1表示合成气生产装置的前-后部分，原料2在装置4中被预热、脱硫、与工艺蒸汽6混合，并在进入绝热式预重整器8之前被进一步加热，由预重整器8流出的流料液物流在烟气管路12中排布的环路中被进一步加热，然后送往管式重整器14。在重整器中甲烷转化为氢、一氧化碳和二氧化碳。管式重整器下游的气流处理取决于产品使用情况。
催化成品可在图1所示的二种设备中使用。
1.在进入管式重整器14前预重整器流料液气流在预热器盘管10中被加热。
2.管式重整器14。
下面列出了当将催化成品使用于上述二种设备时，在图1装置中获得的结果。用作催化成品的催化剂是由Haldor TopsoeA/S购得的R6TR镍蒸汽重整催化剂。将该结果与普通容器作比较。
预热器盘管的目的是在烟气进入管式重整器之前利用烟气的热量预加热工艺气体。烟气可用来预热工艺气体和预热管式重整器(图1中未显示)的燃烧空气，然而，烟气中的热量大于可用于这些目的所需的热量。如果将烟气较大量的热量传递给工艺气体，这将是有利的。这样可减少管式重整器中所需燃料量。由于在设备中传递较少量的热量，这样可减少重整器的尺寸。
普通预热器由于冒甲烷分解形成碳的风险，而受到限制。为此，应规定可接受的管壁温度上限值。在预热器盘管10(如图2所示)的内管壁16上固定一层催化成品，其结果是可减少管壁温度和工艺气体温度。这样使得盘管中传递效率更高而不具有较高管温。
在计算中所采用的预热盘管包括8根管子，其中工艺气体流在该管内流动。烟气在管外流动。流动的型式是横流/并流。图2表示一种管子的布置情况。在表1中概括了具有催化成品和不具有催化成品的二种容器。很显然，与普通容器相比较，催化成品容器的传递效率(热能)较高，为49％。催化成品容器中的催化剂厚度为1.0mm。
表1
  普通情况   催化成品情况
  管子数目   8   8
  总有效管长   51.6m   76.2m
  烟气内/外温度   1057℃/964℃   1057℃/912℃
  工艺气体内/外温度   512℃/650℃   512℃/631℃
  甲烷转化率   0％   8.7％
  传热效率   9.69*106卡/小时   1.44*107卡/小时
有效的管子长度是烟气通道内的管子长度。
普通的管式重整器包括若干根填满催化剂颗粒的管子。工艺气体在管外流动，将管子放置在炉内，通过燃料燃烧将其加热。
在使用催化成品容器的情况下，采用若干根管内壁上具有催化成品层的管子来替代填满催化剂颗粒的管子。催化剂层的厚度为0.25mm。由于催化成品管式重整器中的甲烷转化不如普通容器，为此，应将附加的绝热式重整固定床反应器放置在管式反应器下流。这种反应器称之为后置重整器。在后置重整器中所采用的催化剂是从Halodor TopsoeA/S购得的RKS-2镍蒸汽重整催化剂。
下面表2中概括了这两种容器。从表中看出，与普通容器相比，催化成品容顺中的催化剂消耗减少11.5系数，在管式重整器中的管材消耗减少24％。
表2
  普通容器   催化成品重整器  催化成品容器+后置重整器
  管子数目   276   187
  管长   13m   55m
  催化剂消耗   31.0t   0.63t  2.70t
  管式重整器的管材消耗   153.6t   116.0t
  甲烷转化率   89.0％   80.7％  90.2％
图3表示了本发明方法的流程图。三角形中的数字参考以下表，在该表中，对工艺过程的所有数值进行比较。与普通容器相比，催化成品容器的燃料消耗减少7.4％。
表3
  位置   普通情况   催化成品情况
  1   温度(℃)压力(kg/cm2g)总干流量(Nm3/h)总流量(Nm3/h)组成(干燥摩尔％)H2COCO2CH4   51228.55785114316823.780.7421.1454.34   51228.55785114316823.78O.7421.1454.34
  2   温度(℃)压力(kg/cm2g)总干流量(Nm3/h)总流量(Nm3/h)组成(干燥摩尔％)H2COCO2CH4   65027.55785114316823.780.7421.145434   63127.46739714872034.582.6720.1642.59
  3   温度(℃)压力(kg/cm2g)总干流量(Nm3/h)总流量(Nm3/h)组成(干燥摩尔％)H2COCO2CH4   92524.114153319912168.8520.248.472.44   1O1526.013265319410666.7620.428.244.57
  4   温度(℃)压力(kg/cm2g)总干流量(Nm3/h)总流量(Nm3/h)组成(干燥摩尔％)H2COCO2CH4   在这容器中无后置重整器   93024.414258020000369.0820.358.402.17
  5   T(℃)总流量(Nm3/h)   1057244672   1057234677
  6   T(℃)   964   912
  7   总流量(Nm3/h)   9524   8820

Claims (4)

1.一种在管式反应器中在载有蒸汽重整催化剂薄膜的存在下，通过烃原料的蒸汽重整，生产富一氧化碳和氢的产品气的方法，该方法包括下列步骤：
(a)让预重整的烃工艺气体通过在反应器内壁上载有蒸汽重整催化剂薄膜并被燃料燃烧加热的管式反应器，由此获得部分蒸汽重整气流和热烟气；
(b)让管式反应器的流出物通过具有蒸汽重整催化剂的固定床反应器；和
(c)从固定床反应器排出富一氧化碳和氢的产品气。
2.权利要求1的方法，其中还包括在步骤(a)前的步骤：让预重整的烃工艺气体通过在反应器内壁上载有蒸汽重整催化剂薄膜的管式反应器，该反应器能与来自随后的步骤(a)的热烟气进行热交换。
3.权利要求1的方法，其中固定床蒸汽重整催化剂是在绝热条件下进行操作的。
4.权利要求1的方法，其中蒸汽重整催化剂包括镍和/或钌。
CNB981056520A 1997-01-22 1998-01-22 生产富氢和一氧化碳的气体的方法 Expired - Fee Related CN1269724C (zh)

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Families Citing this family (63)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK173496B1 (da) 1998-07-16 2001-01-02 Topsoe Haldor As Fremgangsmåde til fremstilling af syntesegas ved vanddampreformering under anvendelse af en katalyseret metaloverflade
EP1097105B1 (en) 1998-07-21 2002-10-02 Haldor Topsoe A/S Synthesis gas production by steam reforming
DK173742B1 (da) * 1998-09-01 2001-08-27 Topsoe Haldor As Fremgangsmåde og reaktorsystem til fremstilling af syntesegas
DK173897B1 (da) 1998-09-25 2002-02-04 Topsoe Haldor As Fremgangsmåde til autotermisk reforming af et carbonhydridfødemateriale indeholdende højere carbonhydrider
ATE308482T1 (de) 1999-05-27 2005-11-15 Haldor Topsoe As Synthesegasherstellung durch dampfreformierung
EP1584603A3 (en) * 1999-05-27 2007-06-13 Haldor Topsoe A/S Steam reforming reactor for synthesis gas production
EP1069070B1 (en) * 1999-07-15 2011-11-30 Haldor Topsoe A/S Process for the catalytic steam reforming of a hydrocarbon feedstock
PT1106570E (pt) * 1999-12-02 2013-10-15 Haldor Topsoe As Processo e reactor para realizar reacções catalíticas não adiabáticas
US20040161381A1 (en) * 1999-12-02 2004-08-19 Thomsen Soren Gyde Process and reactor for carrying out non-adiabatic catalytic reactions
WO2002028770A1 (en) 2000-10-02 2002-04-11 Chevron U.S.A. Inc. Process for reducing coke formation in hydrocarbon processing by application of radio frequency electromagnetic radiation
RU2167808C1 (ru) * 2000-10-09 2001-05-27 Пискунов Семен Евсеевич Способ получения синтез-газа
US6890672B2 (en) 2001-06-26 2005-05-10 Idatech, Llc Fuel processor feedstock delivery system
US6818028B2 (en) * 2001-07-18 2004-11-16 Kellogg Brown & Root, Inc. Steam-methane reformer furnace with convection-heated pre-reformer
EP1490296A4 (en) * 2002-02-22 2008-09-10 Chevron Usa Inc METHOD FOR REDUCING METAL-CATALYZED COKE FORMATION IN THE PROCESSING OF CARBON HYDROCARBONS
US20030223926A1 (en) 2002-04-14 2003-12-04 Edlund David J. Steam reforming fuel processor, burner assembly, and methods of operating the same
ES2405587T3 (es) 2002-09-26 2013-05-31 Haldor Topsoe A/S Procedimiento y aparato para la preparación de gas de síntesis
EP1413547A1 (en) 2002-09-26 2004-04-28 Haldor Topsoe A/S Process for the production of synthesis gas
EP1403217A1 (en) 2002-09-26 2004-03-31 Haldor Topsoe A/S Process and apparatus for the preparation of synthesis gas
CA2410927A1 (fr) * 2002-11-05 2004-05-05 Michel Petitclerc Reacteur a chauffage electrique pour le reformage en phase gazeuse
ES2381105T3 (es) * 2003-02-05 2012-05-23 Haldor Topsoe A/S Procedimiento para el tratamiento de gas de síntesis
BRPI0407751A (pt) * 2003-02-24 2006-02-14 Texaco Development Corp processador de combustìvel e método para a reforma a vapor de um combustìvel de hidrocarbonetos contendo enxofre, e, aparelho e método para a geração de eletricidade
US7427388B2 (en) * 2004-03-19 2008-09-23 Air Products And Chemicals, Inc. Process for improving prereforming and reforming of natural gas containing higher hydrocarbons along with methane
US7892511B2 (en) 2004-07-02 2011-02-22 Kellogg Brown & Root Llc Pseudoisothermal ammonia process
US7320778B2 (en) * 2004-07-21 2008-01-22 Catacel Corp. High-performance catalyst support
US7472936B2 (en) * 2005-04-14 2009-01-06 Catacel Corp. Tool for insertion and removal of a catalytic reactor cartridge
US7565743B2 (en) * 2005-04-14 2009-07-28 Catacel Corp. Method for insertion and removal of a catalytic reactor cartridge
US20060230613A1 (en) * 2005-04-14 2006-10-19 Catacel Corporation Catalytic reactor cartridge
US7682580B2 (en) * 2005-05-19 2010-03-23 Catacel Corp. Catalytic reactor having radial leaves
US7632322B2 (en) * 2005-06-07 2009-12-15 Idatech, Llc Hydrogen-producing fuel processing assemblies, heating assemblies, and methods of operating the same
US7504048B2 (en) * 2005-06-14 2009-03-17 Air Products And Chemicals, Inc. Axial convective reformer
US7501102B2 (en) * 2005-07-28 2009-03-10 Catacel Corp. Reactor having improved heat transfer
US7588738B2 (en) * 2005-08-23 2009-09-15 Exxonmobil Chemical Patents Inc. Series catalyst beds
JP4724029B2 (ja) * 2006-03-27 2011-07-13 アイシン精機株式会社 改質装置の運転停止方法
US7629067B2 (en) * 2006-05-22 2009-12-08 Idatech, Llc Hydrogen-producing fuel processing systems and fuel cell systems with a liquid leak detection system
US7501078B2 (en) * 2007-01-10 2009-03-10 Air Products And Chemicals, Inc. Process for generating synthesis gas using catalyzed structured packing
US7771585B2 (en) 2007-03-09 2010-08-10 Southern Company Method and apparatus for the separation of a gas-solids mixture in a circulating fluidized bed reactor
US7850944B2 (en) * 2008-03-17 2010-12-14 Air Products And Chemicals, Inc. Steam-hydrocarbon reforming method with limited steam export
US20100147749A1 (en) * 2008-12-11 2010-06-17 American Air Liquide, Inc. Multi-Metallic Catalysts For Pre-Reforming Reactions
US9561476B2 (en) 2010-12-15 2017-02-07 Praxair Technology, Inc. Catalyst containing oxygen transport membrane
CN103011077B (zh) * 2011-09-27 2016-04-06 中国科学院宁波材料技术与工程研究所 一种催化重整制氢方法与催化装置
EP2791082B1 (en) 2011-12-15 2021-01-20 Praxair Technology, Inc. Method of producing composite oxygen transport membrane
US9486735B2 (en) 2011-12-15 2016-11-08 Praxair Technology, Inc. Composite oxygen transport membrane
WO2014100376A1 (en) 2012-12-19 2014-06-26 Praxair Technology, Inc. Method for sealing an oxygen transport membrane assembly
US9453644B2 (en) 2012-12-28 2016-09-27 Praxair Technology, Inc. Oxygen transport membrane based advanced power cycle with low pressure synthesis gas slip stream
US9611144B2 (en) 2013-04-26 2017-04-04 Praxair Technology, Inc. Method and system for producing a synthesis gas in an oxygen transport membrane based reforming system that is free of metal dusting corrosion
US9212113B2 (en) 2013-04-26 2015-12-15 Praxair Technology, Inc. Method and system for producing a synthesis gas using an oxygen transport membrane based reforming system with secondary reforming and auxiliary heat source
US9938145B2 (en) 2013-04-26 2018-04-10 Praxair Technology, Inc. Method and system for adjusting synthesis gas module in an oxygen transport membrane based reforming system
US9296671B2 (en) 2013-04-26 2016-03-29 Praxair Technology, Inc. Method and system for producing methanol using an integrated oxygen transport membrane based reforming system
MX2016004495A (es) 2013-10-07 2016-06-16 Praxair Technology Inc Reactor ceramico de conversion de conjunto de membranas de transporte de oxigeno.
CN105593162B (zh) 2013-10-08 2018-09-07 普莱克斯技术有限公司 用于在基于氧输送膜的反应器中的温度控制的系统和方法
CN105764842B (zh) 2013-12-02 2018-06-05 普莱克斯技术有限公司 使用具有二段转化的基于氧转运膜的重整系统生产氢气的方法和系统
CN105980666B (zh) 2014-02-12 2019-04-09 普莱克斯技术有限公司 用于生成电力的基于氧传输膜反应器的方法和系统
US20170021322A1 (en) 2014-04-02 2017-01-26 Haldor Topsøes A/S Pseudo-isothermal reactor
US10822234B2 (en) 2014-04-16 2020-11-03 Praxair Technology, Inc. Method and system for oxygen transport membrane enhanced integrated gasifier combined cycle (IGCC)
WO2016057164A1 (en) 2014-10-07 2016-04-14 Praxair Technology, Inc Composite oxygen ion transport membrane
US10441922B2 (en) 2015-06-29 2019-10-15 Praxair Technology, Inc. Dual function composite oxygen transport membrane
US10118823B2 (en) 2015-12-15 2018-11-06 Praxair Technology, Inc. Method of thermally-stabilizing an oxygen transport membrane-based reforming system
US9938146B2 (en) 2015-12-28 2018-04-10 Praxair Technology, Inc. High aspect ratio catalytic reactor and catalyst inserts therefor
WO2017172238A1 (en) 2016-04-01 2017-10-05 Praxair Technology, Inc. Catalyst-containing oxygen transport membrane
WO2018208373A1 (en) * 2017-05-09 2018-11-15 Exxonmobil Chemical Patents Inc. Linear alpha olefin process using temperature control in oligomerization reactor
WO2019226435A1 (en) 2018-05-21 2019-11-28 Praxair Technology, Inc. Otm syngas panel with gas heated reformer
US20230415118A1 (en) 2020-11-19 2023-12-28 L'Air Liguide Société Anonyme pour I'Etude et I'Exploitation des Procédés Georges Claude Reforming reactor comprising reformer tubes with enlarged outer surface area and structured catalyst
EP4155259A1 (de) 2021-09-22 2023-03-29 L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren zum herstellen von synthesegas mit reduziertem dampfexport

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1008667A (en) * 1972-06-30 1977-04-19 Foster Wheeler Corporation Catalytic steam reforming
US4079017A (en) * 1976-11-19 1978-03-14 Pullman Incorporated Parallel steam reformers to provide low energy process
EP0049967A1 (en) * 1980-10-14 1982-04-21 Imperial Chemical Industries Plc Ammonia production process
US4844837A (en) * 1982-09-30 1989-07-04 Engelhard Corporation Catalytic partial oxidation process
DE3480192D1 (en) * 1983-03-25 1989-11-23 Ici Plc Steam reforming
GB8308343D0 (en) * 1983-03-25 1983-05-05 Ici Plc Steam reforming
GB8309359D0 (en) * 1983-04-06 1983-05-11 Ici Plc Synthesis gas
DK165946C (da) * 1985-03-21 1993-07-05 Haldor Topsoe As Reformingproces under varmeudveksling og reaktor dertil
GB8728882D0 (en) * 1987-12-10 1988-01-27 Ici Plc Hydrogen
EP0334540B1 (en) * 1988-03-24 1993-10-20 Imperial Chemical Industries Plc Two-step steam-reforming process
JP2607644B2 (ja) * 1988-10-27 1997-05-07 三菱重工業株式会社 メタノール改質方法
GB9000389D0 (en) * 1990-01-08 1990-03-07 Ici Plc Steam reforming
DK167864B1 (da) * 1990-02-02 1993-12-27 Topsoe Haldor As Fremgangsmaade og reaktorsystem til reforming af carbonhydrider under varmeveksling
EP0522744B1 (en) * 1991-07-09 1997-08-13 Imperial Chemical Industries Plc Synthesis gas production
US5429809A (en) * 1991-09-23 1995-07-04 Haldor Topsoe A/S Process and reactor for carrying out non-adiabatic catalytic reactions
JPH05155602A (ja) * 1991-12-09 1993-06-22 Sekiyu Sangyo Kasseika Center 薄型水蒸気改質反応器
JPH05186203A (ja) * 1992-01-07 1993-07-27 Toshiba Corp 水蒸気改質用触媒エレメント
FR2696168B1 (fr) * 1992-09-25 1994-12-09 Inst Francais Du Petrole Procédé et dispositif de fabrication de gaz de synthèse et utilisation associée.
JPH06219705A (ja) * 1993-01-22 1994-08-09 Mitsubishi Electric Corp 燃料改質装置
MY131526A (en) * 1993-12-27 2007-08-30 Shell Int Research A process for the preparation of carbon monoxide and/or hydrogen

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