CN1181023C - 甲醇合成工艺和设备 - Google Patents

甲醇合成工艺和设备 Download PDF

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CN1181023C
CN1181023C CNB008125058A CN00812505A CN1181023C CN 1181023 C CN1181023 C CN 1181023C CN B008125058 A CNB008125058 A CN B008125058A CN 00812505 A CN00812505 A CN 00812505A CN 1181023 C CN1181023 C CN 1181023C
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methanol reactor
methanol
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gas
synthesis
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H-J
H-J·巴尼施
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ThyssenKrupp Industrial Solutions AG
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    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516Multisteps
    • C07C29/1518Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • 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
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/152Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the reactor used
    • 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
    • B01J2208/00026Controlling or regulating the heat exchange system
    • B01J2208/00035Controlling or regulating the heat exchange system involving measured parameters
    • B01J2208/00044Temperature measurement
    • B01J2208/00061Temperature measurement of the reactants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00008Controlling the process
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    • B01J2208/00106Controlling the temperature by indirect heat exchange
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    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00168Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00256Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles in a heat exchanger for the heat exchange medium separate from the reactor
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    • 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
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00265Part of all of the reactants being heated or cooled outside the reactor while recycling
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

由氢、一氧化碳和二氧化碳在压力下合成甲醇的工艺,包括至少一个含有至少一个催化剂填充的甲醇反应器的合成步骤,其中在多个步骤时设置至少一个使用压缩机的步骤,和实施该工艺的设备,它们能够克服已知的缺点,特别是提供节省热交换器面积和/或在尤其考虑到变化的催化剂活性情况下提高收率的可能性。按照该工艺,在至少一个合成步骤中特定用于催化剂填充的甲醇反应器中的气体混合物直接在加入所述甲醇反应器之前在一个另外的微调加热器中加热。相应设备的特色是在至少一个合成步骤中设计一个微调加热器(5)用于加热直接加载到甲醇反应器(60)的气体混合物。

Description

甲醇合成工艺和设备
本发明涉及由氢、一氧化碳和二氧化碳在压力下合成甲醇的工艺,包括至少一个含有至少一个催化剂填充的甲醇反应器的合成步骤,其中在多个步骤时设置至少一个使用压缩机的步骤和所有的合成步骤设置用于甲醇的自有产物出口和自有气/气热交换器用于将离开甲醇反应器的气体混合物的热量传递给预设用于甲醇反应器中的气体混合物,以及涉及一种相应设备。
已知有一系列的催化法甲醇合成工艺或设备,其中对溶液的填充度这里作为例子可提到DE-2117060,DE-2529591,DE-3220995,DE-3518362,US-2904575和DE-4100632。
从WO97/31707已知一种方法,其中一个微调加热器安排在相应的气/气热交换器之前,从而后者的温差变小并因此增大了它的面积。这样的面积扩大应通过本发明阻止。在WO97/31707中也描述了一种技术,其中热交换器整合到反应器中,这必须要求一个另外的热交换器,因为否则的话反应条件会不稳定。
在申请人的DE-4028750中使用一个炉子(在那里为6)用于在绝热反应器入口处达到必需的反应温度和在蒸镏中作为蒸煮器(那里为11)的间接加热器。在那里,只有反应器的一少部分反应热用于反应入口气体的加热。蒸煮器在那里仅用于驱动后面的蒸镏反应。
在申请人的DE-4004862中描述了一个另外的热交换器,但在那里仅用作起动(Anfahr)热交换器,然而它的应用并没有带有缩小其它热交换器面积的后果。
如在DE-4100632中所述,有利的是使用含有反应器的多个合成步骤,浓缩它们产生的甲醇,与合成气体分离并在每个单个反应器之后作为单独的甲醇产物流抽出。在离开反应器的甲醇/合成气体混合物冷却时,经济的是将释放的热至少部分地用于借助气/气热交换器事先温热进入各个反应器的进料流。
在多年的操作中发现的缺点是,通常用于甲醇反应器中的催化剂物质其活性随着时间会发生变化,需要越来越高的反应器温度以达到最佳的收率,但在反应器进气区后面的区域一段时间后无法再达到这么高的反应器温度。由于反应转化率降低,产生的甲醇和在甲醇反应器冷却时常作为同步产物(Koppelprodukt)生成的蒸汽都变少。
本发明的目的是,克服所述的缺点,特别是创造节约热交换器面积和/和在特别注意到变化的催化剂活性情况下提高收率。
本发明的目的可这样达到,提供一种由氢、一氧化碳和二氧化碳在压力下合成甲醇的工艺,包括至少一个含有至少一个催化剂填充的甲醇反应器的合成步骤,其中在多个步骤时设置至少一个使用压缩机的步骤和所有的合成步骤设置用于甲醇的自有产物出口和自有气/气热交换器用于将离开甲醇反应器的气体混合物的热量传递给预设用于甲醇反应器中的气体混合物,其中设计为,在至少一个合成步骤中特定用于填充有催化剂的甲醇反应器中的气体混合物直接在加入上述的甲醇反应器之前在一个另外的微调加热器中加热。
本发明的实施方案尤其在于:
——确定用于填充有催化剂的反应器中的气体混合物在通过一个另外的微调加热器加热之后测量其温度,
——该另外的微调加热器的热输入可进行调节,和
——该另外的微调加热器用外来介质例如蒸汽来加热。
这种设计方式的主要优点在于,将从反应器出来的流体逆着进入的流体冷却的气/气热交换器尺寸明显变小。还意外地显示出,在催化剂活性变差时可通过进一步调节反应器入口温度一直得到最佳产率。
由于例如蒸汽加热的微调加热器的热传递性能比气/气热交换器好得多和也因为需要的安全储备件本身可属于微调加热器,“局部地(unter demStrich)”甚至节省了投资成本。此外表明,在微调加热器中的催化剂寿命期间使用的蒸汽量对于由于反应转化率下降产生的损失的情况比同步产物的损失小。因此,由于需要额外的蒸汽而在局部产生的蒸汽量被提高。另外表明,这种设备的开工时间可大大缩短,因为微调加热器可用作起动加热器。
上面所述的目的可用下面合适类型的设备解决,即在至少一个合成步骤中设置一个微调加热器用于加热间接加载到甲醇反应器中的气体混合物。
本发明的其它优点、细节和特征从下面的说明书和借助附图说明。附图简易表示了一般情况下为多个的通常构造相同的甲醇合成设备步骤中的一个。
设置一个压缩机2用于压缩用1表示的进料气体,其中在另外的气体道路中设置一个气/气热交换器3用于预热进料气体。如此预热的气体经管线4输送到微调加热器5,它将进料气体1加热到所需温度。在输送管线6中设置一个温度测量调节装置7用于测温,其中用蒸汽控制阀8调节蒸汽输送9,使得在催化剂填充的甲醇反应器10中总能调节到最佳的进气温度。
在催化剂填充的甲醇反应器10中进料气体发生反应而生成热。反应热被用于由供给水11产生蒸汽。热的气体产物13在气/气热交换器3中释放出它的部分热能。反应器中产生的气态甲醇在甲醇冷凝器14中从合成气体中冷凝出来,在冷凝物分离器15中与合成气体分开并作为甲醇产物16排放出。剩下的合成气体17可在后面的步骤中进一步使用。
在本发明的设备中甲醇反应器10中反应的调节主要是通过图中未详细示出的冷却介质(水11或蒸汽12)的压力调节进行,冷却介质包围在催化剂填充的管子周围。如果催化剂活性下降,则需要提高反应器中的整个温度水平,这通过调高冷却介质的压力实施,从而冷却介质的蒸发温度上升。这样,催化剂中的温度升高,出口温度13也同样升高。
经过热交换器3,管线4中的温度也升高,但不是以达到最佳反应条件所需的程度。这通过微调加热器5达到。很明显,微调加热器5达到了阻止气/气热交换器3的面积需求的基本任务,一方面是增大温度差,另一方面是能够取消常用的安全额外费用,更确切地说特别是因为这样,因为热过渡在微调加热器中改进了7倍。在此,产生的面积附加费因而比热交换费要小得多,这是本发明的一个重要优点。
当然,本发明所述的实施例还可在许多方面改变,而不脱离基本构思。例如,可以将微调加热器必要时设计成两步方式或更多。

Claims (5)

1.由氢、一氧化碳和二氧化碳在压力下合成甲醇的工艺,包括至少一个含有至少一个催化剂填充的甲醇反应器的合成步骤,其中在多个步骤时设置至少一个使用压缩机的步骤和所有的合成步骤设置用于甲醇的自有产物出口和自有气/气热交换器用于将离开甲醇反应器的气体混合物的热量传递给预设用于甲醇反应器中的气体混合物,其特征在于,在至少一个合成步骤中特定用于催化剂填充的甲醇反应器中的气体混合物直接在加入所述甲醇反应器之前在一个另外的微调加热器中加热。
2.根据权利要求1的工艺,其特征在于,特定用于催化剂填充的甲醇反应器中的气体混合物的温度在用微调加热器对其加热后测量。
3.根据权利要求1或2的工艺,其特征在于,微调加热器的热输入能够调节。
4.根据前述权利要求之一的工艺,其特征在于,微调加热器以外来介质加热。
5.根据权利要求4的工艺,其特征在于,微调加热器用蒸汽加热。
CNB008125058A 1999-09-07 2000-08-31 甲醇合成工艺和设备 Expired - Fee Related CN1181023C (zh)

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DE19942736 1999-09-07
DE19942736.4 1999-09-07
DE19948585.2 1999-10-08
DE19948585A DE19948585A1 (de) 1999-09-07 1999-10-08 Verfahren und Anlage zur Methanolherstellung

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1310862C (zh) * 2005-04-30 2007-04-18 四川天一科技股份有限公司 甲醇合成塔

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060235090A1 (en) * 2002-12-21 2006-10-19 Haldor Topsoe A/S Process for synthesis of methanol
CN101243027B (zh) * 2005-08-18 2012-02-08 埃克森美孚化学专利公司 甲醇合成和反应系统
US20070282021A1 (en) * 2006-06-06 2007-12-06 Campbell Gregory A Producing ethanol and saleable organic compounds using an environmental carbon dioxide reduction process
US20090077892A1 (en) * 2007-07-27 2009-03-26 Shulenberger Arthur M Biomass energy conversion apparatus and method
WO2009052764A1 (fr) * 2007-10-19 2009-04-30 Ren Lou Appareillage de réaction composite et procédé chimique de production utilisant celui-ci
CN101519336B (zh) * 2008-02-29 2012-11-14 杭州林达化工技术工程有限公司 合成气制烃类的方法和设备
DE102008049622B4 (de) * 2008-09-30 2012-10-31 Lurgi Gmbh Verfahren und Anlage zur Herstellung von Methanol
CN102012125B (zh) * 2010-10-19 2012-04-25 四川天一科技股份有限公司 焦炉气制甲醇转化废水汽提塔废水热量回收的方法
CN103910604B (zh) * 2014-03-31 2015-10-28 神华集团有限责任公司 甲醇合成塔出口高温气体的处理工艺和甲醇合成系统
EP3401300B1 (de) 2017-05-12 2021-06-23 L'air Liquide, Société Anonyme Pour L'Étude Et L'exploitation Des Procédés Georges Claude Verfahren zur herstellung von methanol
EP3401299B1 (de) 2017-05-12 2021-11-03 L'air Liquide, Société Anonyme Pour L'Étude Et L'exploitation Des Procédés Georges Claude Reaktor zum durchführen exothermer gleichgewichtsreaktionen
CN107382665B (zh) * 2017-07-13 2023-06-30 南京国昌化工科技有限公司 一种甲醇合成的工艺和装置
CN110026134A (zh) * 2019-05-23 2019-07-19 河北金牛旭阳化工有限公司 一种串联合成塔以及使用其制备甲醇的方法
DE102020120879A1 (de) 2020-08-07 2022-02-10 Karlsruher Institut für Technologie, Körperschaft des öffentlichen Rechts Vorrichtung und Verfahren zur Herstellung von Methanol aus Kohlendioxid

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2904575A (en) 1957-11-21 1959-09-15 Exxon Research Engineering Co Production of methanol
DE2117060A1 (en) 1971-04-07 1972-10-26 Methanol synthesis with improved reboiler heating
GB1484366A (en) 1974-07-02 1977-09-01 Ici Ltd Methanol
DE3220995A1 (de) 1982-06-03 1983-12-08 Linde Ag, 6200 Wiesbaden Verfahren zur gewinnung von methanol
DE3518362A1 (de) 1985-05-22 1986-11-27 Linde Ag, 6200 Wiesbaden Verfahren zur herstellung von methanol
DE4004862A1 (de) 1990-02-16 1991-08-22 Uhde Gmbh Methanolsynthese mit frischgaszufuhr
DE4028750A1 (de) 1990-09-11 1992-03-12 Uhde Gmbh Verfahren und anlage zur nutzung der energie einer methanol-synthese
US5179129A (en) * 1991-03-01 1993-01-12 Air Products And Chemicals, Inc. Staged liquid phase methanol process
GB9604437D0 (en) 1996-03-01 1996-05-01 Ici Plc Exothermic catalytic chemical process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1310862C (zh) * 2005-04-30 2007-04-18 四川天一科技股份有限公司 甲醇合成塔

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WO2001017936A3 (de) 2002-02-28
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