CN1187259C - 使用催化结构件的蒸汽转化法生产合成气 - Google Patents

使用催化结构件的蒸汽转化法生产合成气 Download PDF

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CN1187259C
CN1187259C CNB998094307A CN99809430A CN1187259C CN 1187259 C CN1187259 C CN 1187259C CN B998094307 A CNB998094307 A CN B998094307A CN 99809430 A CN99809430 A CN 99809430A CN 1187259 C CN1187259 C CN 1187259C
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P·塞尔克里斯坦森
V·卢卡森汉森
J·R·罗斯特鲁普－尼尔森
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Abstract

本发明通过一种将烃进料进行催化蒸汽转化来制备富含氢气和一氧化碳气体的方法，包括以下步骤：(a)任选将烃进料的生产气体通过用热气流加热的含蒸汽转化催化剂的第一反应器；(b)从第一反应器出来的料流随后通过含蒸汽转化催化剂且用燃料燃烧加热的管式反应器，从而得到蒸汽转化产物气体的热气流和燃气热气流，且其中的转化催化剂放在形状与反应器壁基本相同且按能与反应器壁进行热传导关系布置的金属载体上。

Description

使用催化结构件的蒸汽转化法生产合成气
本发明涉及通过烃进料与催化结构件接触进行蒸汽转化来生产合成气的方法。
所谓的催化结构件是指催化剂层固定在另一种材料表面如金属表面上的催化体系。另一种材料起到为体系提供强度的承载结构作用，这样就能将本身机械强度不足的催化剂设计成一定的形状。
合成气是以烃为原料采用蒸汽转化法通过反应(1)-(3)来生产的：
蒸汽转化技术的先有技术是使用各种尺寸和形状的转化催化剂颗粒。催化剂颗粒放入固定床反应器(转化炉管)中。转化反应为吸热反应。在传统的转化器中，必须由管外的环境提供反应所需的热量，通常是以辐射和对流组合形式为向转化炉管外侧供热。热量通过热传导经管壁传递到炉管内侧，再通过对流传递给气相。最后，热量通过对流从气相传递到催化剂颗粒。在转化炉管的同轴位置处，催化剂的温度可能比炉管内壁温度低100℃以上。
现已发现，当蒸汽转化过程中使用催化结构件时，传热效率会更高。热量通过热传导从炉管内壁传递到催化剂。这是一种比借助气相对流传热更为有效的传热机理。所得到的结果是炉管内壁的温度与催化剂的温度几乎相同(温差小于5℃)。并且炉管厚度可以减少(参见下文)，这使得转化炉管内外侧的温差会更小。因而当用催化结构件炉管替换传统蒸汽转化炉管时，在所有其它条件相同的情况下，可以同时达到更高的催化剂温度和更低的炉温。炉管外壁的温度低较为理想，因为这样可延长炉管的寿命，催化剂的温度高较为有利，因为反应速度随温度升高而加快，且反应(3)的平衡会向方程右侧移动，使得进料可以得到更好的利用。
在管径相同的情况下，催化转化炉管的压降要大大低于传统炉管的压降。这样就能使用管径更小的反应炉管，而仍能维持合理的压降。管径更小会使炉管有更长的寿命、耐受更高的温度和减少炉管材料的耗用量。
最后一点，与传统的转化催化剂固定床型转化炉管相比，使用催化结构件转化炉管时所用的催化剂量减少。
图1示出合成气生产装置的前端部分。进料2在单元4中被预热、脱硫后，与工艺蒸汽6混合，进一步加热后进入绝热的预转化器8。从预转化器8出来的料流在排列于燃气管道12内的热交换器盘管10中进一步被加热后，送入管式转化器14，在其中进行甲烷转化为氢气、一氧化碳和二氧化碳的反应。从管式转化器出来的下游气体的处理取决于产品的用途。
催化结构件可用于图1所示的单元中的两个：
1.将预转化器流出气体在进入管式转化器14之前进行加热所用的预热盘管中；
2.管式转化器14中
金属表面涂覆催化涂层(薄层涂覆(wash-coating))是熟知的工艺方法(例如参见Cybulski，A.和Moulijn，J.A所著的结构催化剂和反应器.(Marcel Dekker，Inc.，纽约，1998)第3章中的描述)。例如采用喷涂、刷涂或浸涂的方法将含陶瓷前体的淤浆液施涂于表面。施涂后，通常要将淤浆液干燥并于350-1000℃范围的温度下焙烧。最后，用催化活性物质浸渍陶瓷层。或者催化活性物质与陶瓷前体同时施涂。
遗憾的是，比起固定床反应器，催化结构件反应器存在几个缺点：
若催化剂层因老化或中毒而失去活性时不能更换。
催化剂层只能施涂于某些材料，反应炉管必须由此类比传统炉管材料要昂贵的材料制造，。蒸汽转化反应要在加压条件下进行且管厚度大。因而材料费用会对成本产生很大影响。
并且，生产长催化结构件反应器有一定困难。反应炉管的长度可能达到10m或更长，转化催化剂层的厚度在如此长度上很难达到均匀一致，且施涂小尺寸管子时为得到均匀涂层所用的方法如对管子进行离心处理的方法更难应用于此尺寸的管子。另外，对这种尺寸的炉管进行热处理也很困难。
采用如下所述方法，分开制造催化结构件和反应器可克服这些缺点。
将金属载体切成适当尺寸，如上所述薄层涂覆片材。薄层涂覆后，将片材成型成适当形状。或者，在薄层涂覆之前先将片材成型为最终的形状。金属载体的形状与反应器壁基本相同并按能与反应器壁直接进行热传导的关系布置。
若催化层没有足够活性时可以更换。将催化剂粘结到金属表面所用的钢尽管较贵，但其只占所用全部金属的很小部分。催化结构件可分成较小的部分制造，以便于生产和运输。
因此本发明提供一种将烃进料进行催化蒸汽转化来制备富含氢气和一氧化碳气体的方法，包括以下步骤：
(a)任选将烃进料的生产气体通过用热气流加热的含蒸汽转化催化剂的第一反应器；
(b)从第一反应器出来的料流随后通过含蒸汽转化催化剂且用燃料燃烧加热的管式反应器，从而得到蒸汽转化产物气体的热气流和燃气热气流，
其中的转化催化剂放在形状与反应器壁基本相同且按能与反应器壁进行热传导关系布置的金属载体上。
在本发明的具体实施方案中，给步骤(b)反应器内提供的转化催化剂同时用形状与反应器壁基本相同且按能与反应器壁进行热传导关系布置的金属载体和转化催化剂颗粒来提供。
在本发明一个优选的实施方案中，蒸汽转化催化剂包括镍和/或贵金属。

Claims (5)

1.一种将含烃进料进行催化蒸汽转化来制备富含氢气和一氧化碳气体的方法，包括以下步骤：
(a)将烃进料的生产气体通过用燃料燃烧加热的含蒸汽转化催化剂的管式反应器；
其中的蒸汽转化催化剂粘结在成型成形状与反应器壁相同且按能与反应器壁进行直接热传导关系布置的金属载体片材上。
2.按权利要求1的方法，进一步包括以下步骤：
步骤(a)之前，将烃进料通过用热气流加热的含蒸汽转化催化剂的第一反应器，形成部分转化的烃进料；
其中的第一反应器的蒸汽转化催化剂粘结在成型成形状与反应器壁相同且按能与反应器壁进行直接热传导关系布置的金属载体片材上。
3.按权利要求1或2的方法，其中的步骤(a)管式反应器内的蒸汽转化催化剂是与转化催化剂颗粒组合使用。
4.按权利要求1或2的方法，其中蒸汽转化催化剂包括镍和/或贵金属。
5.按权利要求3的方法，其中蒸汽转化催化剂包括镍和/或贵金属。
CNB998094307A 1998-07-16 1999-07-01 使用催化结构件的蒸汽转化法生产合成气 Expired - Fee Related CN1187259C (zh)

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