CN1098699A - 用于制备含有一氧化碳的混合气的管式加热器 - Google Patents

用于制备含有一氧化碳的混合气的管式加热器 Download PDF

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CN1098699A
CN1098699A CN94107964A CN94107964A CN1098699A CN 1098699 A CN1098699 A CN 1098699A CN 94107964 A CN94107964 A CN 94107964A CN 94107964 A CN94107964 A CN 94107964A CN 1098699 A CN1098699 A CN 1098699A
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output terminal
pipe
carbon monoxide
synthesis gas
tubular heater
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CN1037504C (zh
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弗雷德里希·霍曼
维尔纳·罗尔
汉斯·冈特·莫尔罗特尔
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GEA Group AG
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    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J19/14Production of inert gas mixtures; Use of inert gases in general
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical 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
    • B01J8/06Chemical 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
    • B01J8/062Chemical 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 being installed in a furnace
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    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/38Production 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
    • C01B3/384Production 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 the catalyst being continuously externally heated
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00477Controlling the temperature by thermal insulation means
    • B01J2208/00495Controlling the temperature by thermal insulation means using insulating materials or refractories
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
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    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0816Heating by flames
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0866Methods of heating the process for making hydrogen or synthesis gas by combination of different heating methods
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0872Methods of cooling
    • C01B2203/0883Methods of cooling by indirect heat exchange
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235Hydrocarbons
    • C01B2203/1241Natural gas or methane

Abstract

一种管式加热器包含多个管,该管设置在燃烧室 中并装有催化剂。主要包含氢气、一氧化碳和二氧化 碳的合成气体在所述管中制备。在所述管的输出端 的外表面上由于金属粉状腐蚀有形成碳化物的风 险。为防止这种腐蚀,一种基本上没有一氧化碳的气 态或汽化的保护流体被供应到管的输出端的周围区 域。

Description

本发明涉及一种管式加热器,该加热器用于烃类的催化裂解以便制备一种未处理的合成气体,该合成气体主要包含氢气、一氧化碳和二氧化碳,该加热器包含多个管,该管设置在燃烧室中并装有催化剂。
这种管式加热器是已知的并被用于例如天然气的催化裂解以制备合成气体,该合成气体被用来例如甲醇的合成。在管中通常保持1至20巴的范围的压力,在管的输出端处未处理的合成气体的温度在700~1000℃之间。已经发现,管的输出端受到腐蚀作用,这导致碳化物(金属粉尘)的形成从而引起金属材料的损坏。
本发明的目的是有效地保护管的输出端,该输出端以及其邻接区域对金属粉状腐蚀是敏感的。在上文第一段所描述的这种管式加热器中,根据本发明,这个问题是这样解决的,即设置这样一装置,其用于供应基本上不含一氧化碳的气态或汽化的保护流体到达至少一些管的输出端的外表面上,所述输出端位于燃烧室的外边,并且未处理的合成气体从其中流过。所述保护流体防止含有一氧化碳的合成气体的腐蚀作用,特别是在围绕管的输出端的敏感区域。根据一氧化碳的含量发生金属粉状腐蚀的温度区域是大约500~850℃之间。
至少在一些管的输出端的外边设置有用于容纳保护流的腔室,该腔室通常邻接一耐火衬,该耐火衬环绕着管的输出端。
也就是说,本发明提出一种管式加热器,其由于烃类的催化裂解以便制备一种未处理的合成气体,该合成气体主要包含氢气、一氧化碳、二氧化碳,所述加热器包含多个管,该管设置在燃烧室中并装有催化剂,其特征在于,所述加热器还设置有用于供应气态或汽化的保护流体的装置,该保护流体中基本没有一氧化碳并到达至少一些管的输出端的外表面,所述输出端位于燃烧室的外边,未处理的合成气体从该输出端流过。
在至少一些管的输出端的外边设置有一腔室,该腔室用于容纳保护流体。
至少在一些管的输出端设置有耐火衬。
保护流体通过一管线供应,该管线沿着连接管延伸一定的距离,在该管中合成气体被引导,保护流体与所述管的外表面相接触。
下面参照附图对根据本发明的管式加热器的设计进行详细说明。这些附图是:
图1是表示管式加热器的水平剖面示意图。
图2是表示管的输出端的大比例的纵剖面图。
一耐火的外壳1包含一燃烧室2,在燃烧室2中,多个竖直管3从外边被加热。加热是由多个燃烧器4完成的,该燃烧器4被供给例如天然气等燃料。一种包含烃类和蒸汽的混合气通过供给线5供应到管3中,并在管3中的催化剂的作用下在管3中反应,该催化剂包含例如镍催化剂。一种未处理的合成制品就这样制备而成,该合成制品之要包含氢气、一氧化碳和二氧化碳。在700~1000℃最好至少在800℃时,合成气体在管中向下流去并由输出端3a流出进到收集管线6中。
已经发现,输出端3a的外表面和其周围对金属粉状腐蚀是特别敏感的,这将由于碳化物的形成而引起金属的损坏。该碳化物是由于一氧化碳的分解反应而形成的,
该反应在500~850℃的范围内是特别剧烈的。在这范围的温度通常出现在输出端3a的外表面和其周围。
收集管线6的内表面具有耐火衬6a,耐火衬6a也围绕着管3的输出端3a。因为耐火衬具有一定的孔隙率,合成气体必须被料想到的扩散通过耐火衬,在相对低的温度合成气体到达输出端3a的上表面,那么上边提到的腐蚀就会发生。
为了保护输出端3a和其最靠近的周围抵抗腐蚀作用导致碳化物的形成,每一输出端均设置有一供应管线7,来自主管线8的气态或汽化的保护流体通过该供应管线7。保护流体可以包含例如氢气、水蒸汽。氮气或二氧化碳气。
从图2可以明显地看出保护流体是怎样被引导通过供应管线7进入到腔室9,该腔室9设置在收集管线6的喇叭口状的放大部10内,放大部10在其顶端10a与管3焊在一起。保护流体防止输出端3a的外表面和放大部10的内表面上的金属粉状腐蚀。
收集管线6的耐火衬6a环绕着管3的输出端3a。耐火衬例如可由夯实的混合物构成并且是稍微多孔的,因而保护流体能够由腔室9中扩散出并穿过衬,最后在收集管线6中与合成气体一起被排出。
从图1和图2很明显地看出,来自主管线8的管线7引导保护流体向下延伸一定的距离并与连接管3的外表面相接触,因此,管3里边的热气被用来以间接的热交换形式加热管线7中的保护流体,当保护流体进入到腔室9时,其温度升高了。保护流体的这种加热防止了邻接于输出端3a的热应力。

Claims (4)

1、一种管式加热器,其由于烃类的催化裂解以便制备一种未处理的合成气体,该合成气体主要包含氢气、一氧化碳、二氧化碳,所述加热器包含多个管,该管设置在燃烧室中并装有催化剂,其特征在于,所述加热器还设置有用于供应气态或汽化的保护流体的装置,该保护流体中基本没有一氧化碳并到达至少一些管的输出端的外表面,所述输出端位于燃烧室的外边,未处理的合成气体从该输出端流过。
2、根据权利要求1所述的管式加热器,其特征在于,在至少一些管的输出端的外边设置有一腔室,该腔室用于容纳保护流体。
3、根据权利要求1或2所述的管式加热器,其特征在于,至少在一些管的输出端设置有耐火衬。
4、根据权利要求1至3之一所述的管式加热器,其特征在于,保护流体通过一管线供应,该管线沿着连接管延伸一定的距离,在该管中合成气体被引导,保护流体与所述管的外表面相接触。
CN94107964A 1993-08-13 1994-07-27 用于制备含有一氧化碳的混合气的管式加热器 Expired - Lifetime CN1037504C (zh)

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EP0638514B1 (de) 1997-04-02
DE4327176C1 (de) 1995-01-26
SA94140510B1 (ar) 2005-05-04
CA2129303A1 (en) 1995-02-14
ATE151056T1 (de) 1997-04-15
US5490974A (en) 1996-02-13
EP0638514A1 (de) 1995-02-15
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RU94038428A (ru) 1996-06-10
AU7022294A (en) 1995-02-23
MY124300A (en) 2006-06-30
NZ260957A (en) 1995-09-26
CN1037504C (zh) 1998-02-25
RU2102310C1 (ru) 1998-01-20
CA2129303C (en) 2003-12-09

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