CN100379842C - 一种用于烃原料催化蒸汽重整的方法 - Google Patents

一种用于烃原料催化蒸汽重整的方法 Download PDF

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CN100379842C
CN100379842C CNB001222937A CN00122293A CN100379842C CN 100379842 C CN100379842 C CN 100379842C CN B001222937 A CNB001222937 A CN B001222937A CN 00122293 A CN00122293 A CN 00122293A CN 100379842 C CN100379842 C CN 100379842C
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CN1281028A (zh
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T·罗斯特鲁普-尼尔森
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Topsoe AS
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/141—At least two reforming, decomposition or partial oxidation steps in parallel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • C01B2203/143—Three or more reforming, decomposition or partial oxidation steps in series

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)
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Abstract

一种用于烃原料催化蒸汽重整的方法，包括以下步骤：使烃蒸汽混合物与安装在外加热式预重整器内的第一蒸汽重整催化剂接触，外加热式预重整器位于来自燃烧蒸汽重整器的烟道气通道中；并使来自于预重整器的预重整流出物与燃烧蒸汽重整器内的第二蒸汽重整催化剂接触；本方法包括的另一步骤为，使预重整流出物与第三蒸汽重整催化剂接触，第三蒸汽重整催化剂安装在位于外加热式蒸汽重整器上游的烟道气通道的外部。

Description

一种用于烃原料催化蒸汽重整的方法
本发明涉及一种用于烃原料催化蒸汽重整的方法。具体地说，本发明提供一种用于烃原料催化蒸汽重整的改进方法，包括以下步骤：使烃蒸汽混合物与安装在外加热式预重整器壁上并在蒸汽重整中具有活性的催化元件相接触，进行预重整；随后，使来自于预重整器的预重整流出物与燃烧蒸汽重整器内的装载有蒸汽重整催化剂的催化元件整体接触。
在合成气制备中，烃原料预重整是该技术领域公知的。预重整一般用于含有高级烃的烃原料，或者用于提高现有重整炉装置的生产能力。在约为450℃-550℃的温度下，将烃原料工艺气和蒸汽加入预重整器。在预重整器内进行蒸汽重整反应，当以绝热方式进行预重整反应时，工艺气的温度一般是降低的。
在工业合成气制备装置中，预重整后的工艺气随后通过与来自于燃烧重整器的热烟道气进行热交换，再加热到进入燃烧蒸汽重整器所需的入口温度。工业重整器的入口温度通常为600℃-700℃。
EP-855366号欧洲专利公开说明书公开了一种对来自于燃烧蒸汽重整器的烟道气中热能的改进利用方法。在该专利公开的方法中，进入蒸汽重整器的工艺气，在预热器盘管内被部分重整，盘管壁上装有蒸汽重整催化剂薄膜。然后通过在涂有催化剂的壁上进行的吸热蒸汽重整反应，烟道气中的大量有用热能传递给工艺气，并且被其吸收。调整盘管的尺寸和催化剂的量，以增加来自于催化预热器盘管的部分重整工艺气的出口温度，使其达到燃烧蒸汽重整器入口需要的温度。
上述方法的主要缺点是，在催化预热器盘管的长期操作过程中，降低了催化剂的活性，导致盘管的出口温度超过了燃烧蒸汽重整器入口允许的最大气体温度，这是由于工艺气的蒸汽重整量减小，使得对热能的吸收也降低了。因此，盘管壁上的催化剂必须再活化，或用新鲜催化剂来替换。把盘管从烟道气通道中拆下来，更换预热器盘管内的催化剂是困难且昂贵的操作。
本发明的主要目的是通过增加一个易于更换的催化剂设备，补偿预热器盘管内降低的催化剂活性，来提高上述蒸汽重整过程的长期操作性。
根据上述目的，本发明提供一种用于烃原料催化蒸汽重整的方法，包括以下步骤：使烃蒸汽混合物与安装在外加热式预重整器内的第一蒸汽重整催化剂接触，进行预重整；其中外加热式预重整器位于来自燃烧蒸汽重整器的烟道气通道中；并使来自于预重整器的预重整流出物与燃烧蒸汽重整器内的第二蒸汽重整催化剂接触；本方法包括的另一步骤为，使预重整流出物与第三蒸汽重整催化剂接触，第三蒸汽重整催化剂安装在位于外加热式蒸汽重整器上游的烟道气通道的外部。
依照本发明的方法，在长期操作过程中，预重整器内的活性损失，将由在中间重整设备内进行的预重整流出物的蒸汽重整反应予以补偿，中间重整设备位于烟道气通道内的预重整器的出口与燃烧蒸汽重整器入口之间。中间设备在基本绝热的条件下操作，并补偿加热式预重整器内蒸汽重整催化剂或催化元件的蒸汽重整活性降低，以及由此引起的预重整器流出物的温度升高。
除在长期操作中，对工艺气提供需要的温度调节，使之以低于燃烧蒸汽重整器的最大入口温度进入其内之外，中间重整器设备的另一个优点是位于烟道气通道的外部。如上所述，为了补偿预重整器内的活性损失，需要更换或再活化燃烧重整器上游失活的催化剂。在前面已经提到，更换位于烟道气通道中的设备内的催化剂，既耗费时间，操作费用又高。而根据本发明，通过在烟道气外部安装中间催化剂设备，失活的催化剂在中间重整器设备内被更换，更换操作被显著地简化。
中间催化剂设备优选安装于连接预重整器与燃烧蒸汽重整器的管中，并位于烟道气通道的外部。中间设备内的催化剂可以是常用于烃蒸汽重整中的任何形状。为了减小中间设备的压降，催化剂的形状优选采用直管形。
中间催化剂设备内催化剂的尺寸和活性取决于实际工艺布置。
本发明提供的部分技术方案如下：
技术方案1：
一种用于烃原料催化蒸汽重整的方法，包括以下步骤：使烃蒸汽混合物与安装在外加热式预重整器内的第一蒸汽重整催化剂接触，进行预重整；其中外加热式预重整器位于来自燃烧蒸汽重整器的烟道气通道中；并使来自于预重整器的预重整流出物与燃烧蒸汽重整器内的第二蒸汽重整催化剂接触；本方法包括的另一步骤为，使预重整流出物与第三蒸汽重整催化剂接触，第三蒸汽重整催化剂安装在位于外加热式蒸汽重整器上游的烟道气通道的外部。
技术方案2：
如技术方案1所述的方法，其中，第一蒸汽重整催化剂是薄膜催化剂，安装在外加热式预重整器的壁上。
技术方案3：
如技术方案1所述的方法，其中，第三蒸汽重整催化剂是一种整体结构催化剂。

Claims (4)

1.一种用于烃原料催化蒸汽重整的方法，包括以下步骤：使烃蒸汽混合物与安装在外加热式预重整器内的第一蒸汽重整催化剂接触，进行预重整；其中外加热式预重整器位于来自燃烧蒸汽重整器的烟道气通道中；并使来自于预重整器的预重整流出物与燃烧蒸汽重整器内的第二蒸汽重整催化剂接触；本方法包括的另一步骤为，使预重整流出物与第三蒸汽重整催化剂接触，第三蒸汽重整催化剂安装在位于外加热式蒸汽重整器上游的烟道气通道的外部。
2.如权利要求1所述的方法，其中，第一蒸汽重整催化剂是薄膜催化剂，安装在外加热式预重整器的壁上。
3.如权利要求1所述的方法，其中，第三蒸汽重整催化剂是一种整体结构催化剂。
4.如权利要求1所述的方法，包括以下步骤：使烃蒸汽混合物与安装在外加热式预重整器壁上并在蒸汽重整中具有活性的催化元件相接触，进行预重整；随后，使来自于预重整器的预重整流出物与燃烧蒸汽重整器内的装载有蒸汽重整催化剂的催化元件整体接触。
CNB001222937A 1999-07-15 2000-07-15 一种用于烃原料催化蒸汽重整的方法 Expired - Fee Related CN100379842C (zh)

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EP1069070B1 (en) 2011-11-30
AU769747B2 (en) 2004-02-05
CA2313762A1 (en) 2001-01-15
AU4863500A (en) 2001-01-18
CA2313762C (en) 2009-09-01
KR100444428B1 (ko) 2004-08-16
KR20010061919A (ko) 2001-07-07
ES2375102T3 (es) 2012-02-24
TWI223643B (en) 2004-11-11
CN1281028A (zh) 2001-01-24
RU2263627C2 (ru) 2005-11-10
EP1069070A3 (en) 2003-01-29
NZ505785A (en) 2001-12-21
EP1069070A2 (en) 2001-01-17
JP2001064001A (ja) 2001-03-13

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