CN1268481A - 自热催化蒸汽转化的方法 - Google Patents

自热催化蒸汽转化的方法 Download PDF

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CN1268481A
CN1268481A CN00106514A CN00106514A CN1268481A CN 1268481 A CN1268481 A CN 1268481A CN 00106514 A CN00106514 A CN 00106514A CN 00106514 A CN00106514 A CN 00106514A CN 1268481 A CN1268481 A CN 1268481A
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steam reforming
catalyzer
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CN1129552C (zh
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K·阿斯伯格-彼得森
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Topsoe AS
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • C01B3/32Production 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
    • C01B3/382Multi-step processes
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02Preparation of oxygen
    • C01B13/0229Purification or separation processes
    • C01B13/0248Physical processing only
    • C01B13/0251Physical processing only by making use of membranes
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14Details of the flowsheet
    • C01B2203/142At least two reforming, decomposition or partial oxidation steps in series
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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
    • C01B2203/80Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
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    • C01B2210/0046Nitrogen

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Abstract

一种由烃原料制备氢和/或一氧化碳富气的方法,它包括:采用一种由膜渗透供给的氧化剂对烃原料进行部分氧化,并在一种放置在该膜渗透侧的蒸汽转化催化剂存在下对原料进行蒸汽转化,其中催化剂的蒸汽转化活性在至少一个催化剂床的入口区域是减低的。

Description

自热催化蒸汽转化的方法
本发明涉及烃原料的自热催化蒸汽转化。特别地,本发明是关于已知自热催化蒸汽转化工艺的改进,其中的氧化剂是通过一种膜向反应过程气体提供的。
采用带有致密可传导氧的陶瓷膜的反应器来生产合成气,对本领域技术人员来说是已知的(例如,WO 98/48921)。
合成气在膜反应器中的生产,是通过采用由膜的氧化剂一侧传送的氧气而进行的。合成气的形成可用下列的三个反应式表示:
在上述方法中,气体的入口温度通常在500-800℃之间。在膜的合成气一侧的压力范围为常压-90巴,空气一侧的压力范围为常压-26巴。
甲烷蒸汽转化和转移反应通常在反应器出口处是接近平衡的。
在本发明之前,已知的膜自热催化蒸汽转化方法的改善,是通过控制反应器中的温度梯度,同时在自热反应器的至少一个顶端部位采用一种具有低的蒸汽转化活性或不具有蒸汽转化活性的催化剂而实现的。
因此,本发明是一种由烃原料制备氢和/或一氧化碳富气的方法,它包括:采用一种由膜渗透提供的氧化剂对烃原料进行部分氧化,并在一种放置在该膜渗透侧的蒸汽转化催化剂存在下对原料进行蒸汽转化,其中催化剂的蒸汽转化活性在催化剂床的至少一个入口区域是减活的。
自热膜蒸汽转化的原理如图1所示。
含有烃类物质(在图1和下文中,是以甲烷为例)的原料4在膜6的渗透侧6a处进入反应器2。位于膜这侧的室内装填有蒸汽转化催化剂和/或部分氧化催化剂8。在进料入口处,相对于催化剂床中其它部位的催化剂活性来说,处于顶层8a的催化剂活性是减活的。催化剂除了以固定方式放置外,它也可直接载荷在膜的渗透侧(图中未画出)。
含氧蒸汽10(在图1和下文中,是以空气为例)在膜的另一侧进入反应器。合适的具有传送氧能力的膜材料,对本领域人员来说是公知的。如果氧离子呈可移动的形式,则电子可以相反的方向通过膜,从而可保证电中性。氧流量以一种复杂的方式取决于氧分压的压力差。
假定催化剂在顶层8a不具有蒸汽转化活性,则该催化剂就是作为一种氧化催化剂使用的。
因而,可以获得下列的优点:
·反应器的机械设计变得较简单;
·在较低的物料和/或氧化剂入口温度下的操作成为可能,从而降低热交换面积,减少燃料的消耗;
·所需要的膜面积变小。
对于本领域技术人员来说,用于氢或烃类氧化的催化剂是公知的。具有减低转化活性的蒸汽转化催化剂,可通过采用减低数量的具有催化性能的物质浸渍载体物质和/或添加促进剂以减低具有催化活性物质的活性。这些催化剂的制备方法和具有减低的蒸汽转化活性的催化剂,对本领域的技术人员来说,也是已知的。
还有一个优点是,具有减低活性的催化剂,可在较低的蒸汽/炭比值下进行无炭操作,这是通过向催化剂中添加促进剂以提高抗炭性能和减低催化剂的蒸汽转化活性而实现的。
如果对具有膜供给氧的已知催化自热蒸汽转化炉进行操作,则原料气的蒸汽转化平衡温度,低于原料气通常的反应器入口温度。当原料气与催化剂接触时,蒸汽转化反应立即就会进行。由于蒸汽转化反应是强烈的吸热反应,与气体入口温度相比,可以观察到气体和催化剂温度的降低。
流过膜的氧流量随着温度而增加,在低于某一温度(T0)下,氧流量基本为零。
因此,在带有具有高的蒸汽转化活性催化剂的反应器中,流过单位面积膜的氧流量将要降低。这会出现下列二种后果的一种:
a)反应器内的温度降低到某一水平,当低于这一水平时流过膜的氧流量可忽略。避免这种情形的唯一办法就是提高原料入口温度。
b)与处于原料气体温度的氧流量相比,氧流量是降低的。根据本发明的方法,在反应器的入口部位,采用具有减低的或零蒸汽转化活性的催化剂进行操作,温度的降低可以消除或者变得很不显著。因此,由于氧是在较高(平均)温度下流过膜的,所以,其温度可降低到接近T0的水平,或者可降低膜的面积。

Claims (5)

1.一种由烃原料制备氢和/或一氧化碳富气的方法,它包括:采用一种由膜渗透供给的氧化剂对烃原料进行部分氧化,并在一种放置在该膜渗透侧的蒸汽转化催化剂存在下对原料进行蒸汽转化,其中催化剂的蒸汽转化活性在催化剂床的至少一个入口区域是减低的。
2.权利要求1的方法,其中所述入口区域的蒸汽转化催化活性减低至零。
3.权利要求2的方法,其中所述入口区域催化剂在烃原料的氧化步骤中具有活性。
4.根据权利要求1的方法,其中的催化剂是设置在固定床上的。
5.根据权利要求1的方法,其中的催化剂是由该膜承载的。
CN00106514A 1999-03-05 2000-03-05 自热催化蒸汽转化的方法 Expired - Fee Related CN1129552C (zh)

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US6338833B1 (en) 2002-01-15
ATE266601T1 (de) 2004-05-15
RU2248931C2 (ru) 2005-03-27
ES2218012T3 (es) 2004-11-16
EP1035072B1 (en) 2004-05-12
EP1035072A1 (en) 2000-09-13
CN1129552C (zh) 2003-12-03
NO328246B1 (no) 2010-01-18
NO20001114L (no) 2000-09-06
ZA200001107B (en) 2000-09-06
JP2000256001A (ja) 2000-09-19
NO20001114D0 (no) 2000-03-03
CA2299940A1 (en) 2000-09-05
JP4541484B2 (ja) 2010-09-08
DE60010550D1 (de) 2004-06-17
DE60010550T2 (de) 2005-05-12

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