CN1105080C - 制备氨合成气的方法和生产装置 - Google Patents

制备氨合成气的方法和生产装置 Download PDF

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CN1105080C
CN1105080C CN98109785A CN98109785A CN1105080C CN 1105080 C CN1105080 C CN 1105080C CN 98109785 A CN98109785 A CN 98109785A CN 98109785 A CN98109785 A CN 98109785A CN 1105080 C CN1105080 C CN 1105080C
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steam
gas
heat exchange
steam reforming
heat
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CN1203186A (zh
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C·L·劳尔森
H·O·斯塔尔
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Topsoe AS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • 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
    • C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
    • 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
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • C01B2203/143—Three or more reforming, decomposition or partial oxidation steps in series
    • 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
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/026—Preparation of ammonia from inorganic compounds

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

从烃原料制备氨合成气的方法和装置，包括在热交换初次蒸汽转化装置和其后的二次转化装置里顺序地初次蒸汽转化和二次蒸汽转化原料，其中将流出的初次蒸汽转化气体流用在初次蒸汽转化气体输入二次转化装置之前的二次转化气体的热产物流采用间接热交换加热。

Description

制备氨合成气的方法和生产装置
技术领域
本申请针对氨合成气的制备。更具体地说，本发明涉及制备这种气体的方法和生产装置，包括在热交换式初次蒸汽转化装置和其后的绝热转化装置里把烃原料顺序地进行初次蒸汽转化和二次蒸汽转化。
背景技术
传统的氨合成气的制备采用在燃烧管式蒸汽转化装置里将天然气或高级烃的烃原料通过与蒸汽转化催化剂接触进行吸热蒸汽转化反应进行。然后将初次转化气体送进二次绝热转化装置里，在二次绝热转化装置里，在气体里的部分氢和剩余的烃在二次转化催化剂存在下用空气或富含氧的气体部分氧化。在上述蒸汽转化反应里，原料与在二次转化阶段中通过加入的空气加到气体里的氮气反应中形成含有氢、一氧化碳和二氧化碳的粗氨合成气从二次转化装置里出来。
用于初次绝热蒸汽转化反应所必须的热量通常由燃料在初次蒸汽转化装置烟道气侧壁内燃烧提供，其中催化剂设置在穿过该转化装置垂直延伸的管子里。在初次转化装置里为了降低燃烧负荷和燃料消耗，也曾经提议通过利用流出来的蒸汽转化气流作为热源提供一部分热量。这样的方法和反应器在美国专利US 5 429809里提出，其中，热量一部分由来自燃料燃烧的热烟道气流提供，一部分由在插管式热交换反应器的热产物流提供。
发明内容
本发明的总目的是在用于从烃原料制备氨合成气的顺序地初次热交换蒸汽转化和二次转化中进一步降低燃烧负荷和燃料消耗。
根据这个总目的，本发明的一个目的是提供从烃原料制备氨合成气的方法，包括在初次热交换蒸汽转化装置里和在随后的二次转化装置里顺序地进行初次和二次催化蒸汽转化原料的阶段，其中将流出的初次蒸汽转化气体流在初次蒸汽转化气体输入二次转化装置之前由二次转化气体的热产物流采用间接热交换加热。
本发明的另一个目的是提供一种用于上述蒸汽转化方法中的生产装置。因此这个生产装置包括，一个连接到二次蒸汽转化装置的初次热交换蒸汽转化装置和设置在二次蒸汽转化装置上游的进料/流出物热交换器，以便将来自初次热交换蒸汽转化装置的蒸汽转化烃原料的流出气流由来自二次蒸汽转化装置的产物流采用间接热交换加热。
附图说明
图1是根据本发明一个特定实施例的工艺的简化的流程图。
具体实施方式
本文中前文和下文所述的术语“热交换蒸汽转化装置”是指一种蒸汽转化装置，其在初次蒸汽转化催化剂的固定床上发生的初次蒸汽转化反应所需要的热量一部分是通过热燃烧气体提供，一部分由通过转化装置的二种与催化床有热交换关系的气体在一次转化气体里所含的热量提供。在这种类型的转化装置里，在转化气体里的热量从一般约800℃的转化温度降至低水平的一般约600℃的出口温度而回收。
在二次蒸汽转化阶段进口的平衡温度是在初次蒸汽转化催化床出口处初次转化气体的温度，一般高于800℃。
然而，在使用没有预热的初次转化气体顺序地进行初次和二次蒸汽转化中的热交换初次蒸汽转化装置时，在二次转化装置进口处的初次转化气体的温度却因为与在初次转化装置里的生成气体的间接热交换而比较低。这导致在二次蒸汽转化阶段原料转化率降低。
为了得到要求的化学计算量的二次转化粗氨合成气的组成和在随后氨合成工艺里所要求的在气体里低的氢含量，在顺序的初次热交换和不预热初次转化气体的二次转化中的初次转化气体的平衡温度必须提高用以补偿在二次转化阶段低的氢原料转化率。
通过把二次转化装置和进料/流出物热交换器创造性地相结合，在热交换转化装置里已经降低于平衡温度的初次蒸汽转化气体的温度通过与来自二次转化装置的热产物流的间接热交换被升高至二次转化装置里所要求的反应温度。这样，通过在进料/流出物热交换器里回收在二次蒸汽转化气体里多余的热量，在初次转化装置里的燃料消耗有利地降低了。与传统的初次-二次蒸汽转化相比，这种方式导致来自蒸汽转化区生成的粗氨合成气出口温度相应较低。
来自转化区的较低的出口温度和在初次转化装置中降低的燃料消耗，导致在转化装置区消耗曲线全面改善。
在以下的说明中将参照附图更详细地说明本发明。
当根据本发明的一个特定实施例的工艺操作时，例如天然气和蒸汽之类的进料2在温度为450℃下被送入初次热交换转化反应器4内。反应器4是一种传统设计的插管式反应器，包括在抗压壳6内的由薄板制的外管8(其出口端封闭并且同心地围绕着一个端部开口的热交换插接内管10)构成的一个或多个反应器管道。
在管8和10之间的空间用初次转化催化剂12填充。
输入的进料2经过外管8和催化剂12，通过和催化剂12接触被初次蒸汽转化。在催化剂12上进行的吸热蒸汽转化反应所需要的热量由热烟道气供给，热烟道气由在底部燃烧器14内燃烧燃料获得，在热烟道气沿着外管8的壁经过时，和在管8内的反应进料呈热传导关系。
补充热量由来自催化剂12的热的初次转化气流16供给，气流16以800℃的出口温度离开催化剂并且通过内管10，在催化剂12内与反应进料气体呈热传导关系。
初次转化的气体16的温度因此下降至600℃。
然后气体16被输送至进料/流出物热交换器18，在这里气体16的温度通过与以975℃的温度的正从二次转化装置22排出的热的二次转化的气体20的间接热交换被升至800℃。二次转化装置22是一个传统设计的绝热转化装置，在这里预热的初次转化气体16在该反应器的顶部用空气24部分氧化，然后通过与在二次转化反应器22底部设置成固定床26的二次转化催化剂相接触而被二次转化。二次转化气体20从反应器的底部以975℃的温度排出，并且通过如上所述的间接热交换被冷却至825℃。

Claims (2)

1、从烃原料制备氨合成气的方法，包括在初次热交换蒸汽转化装置里和在随后的二次转化装置里顺序地进行初次和二次催化蒸汽转化原料的阶段，其中初次蒸汽转化反应中所需要的热量一部分通过热燃烧气体提供，一部分由初次转化气流里所含的热量提供，通过使流出的初次蒸汽转化气体流与从二次转化装置排出的热的二次转化气体进行间接热交换而将该初次蒸汽转化气流加热，然后将初次蒸汽转化气体输入二次转化装置。
2、用于权利要求1的蒸汽转化方法中的处理装置，该处理装置包括，一个初次热交换蒸汽转化装置，与其连接的二次蒸汽转化装置，和设置在二次蒸汽转化装置上游的进料/流出物热交换器，以进行初次转化气流与烃原料流的热传导，提供补充的热量；并进行初次蒸汽转化气体流与二次转化装置的热产物流之间的间接热交换。
CN98109785A 1997-05-05 1998-05-04 制备氨合成气的方法和生产装置 Expired - Fee Related CN1105080C (zh)

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DK199700510A DK173052B1 (da) 1997-05-05 1997-05-05 Fremgangsmåde til fremstilling af ammoniak syntesegas
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EP (1) EP0876993B1 (zh)
JP (1) JPH111303A (zh)
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AT (1) ATE400527T1 (zh)
DE (1) DE69839685D1 (zh)
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EA (1) EA000777B1 (zh)
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UA53630C2 (uk) 2003-02-17
KR19980086722A (ko) 1998-12-05
DE69839685D1 (de) 2008-08-21
ATE400527T1 (de) 2008-07-15
DK51097A (da) 1998-11-06
DK173052B1 (da) 1999-12-06
EA199800356A1 (ru) 1998-12-24
CN1203186A (zh) 1998-12-30
EP0876993A1 (en) 1998-11-11
US6077459A (en) 2000-06-20
TW513385B (en) 2002-12-11
JPH111303A (ja) 1999-01-06
EA000777B1 (ru) 2000-04-24

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