CN1123530C - 制备富含氢气气体的方法 - Google Patents

制备富含氢气气体的方法 Download PDF

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CN1123530C
CN1123530C CN99100429A CN99100429A CN1123530C CN 1123530 C CN1123530 C CN 1123530C CN 99100429 A CN99100429 A CN 99100429A CN 99100429 A CN99100429 A CN 99100429A CN 1123530 C CN1123530 C CN 1123530C
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H·F·A·托普瑟
I·戴布克杰尔
P·E·H·尼尔森
B·沃斯
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Abstract

一种用含有二甲醚和/或甲醇的原料在重整催化剂的存在下，通过蒸汽重整二甲醚产生富含氢气的气体来制备富含氢气气体的方法，其中吸热蒸汽重整反应所需的热量通过与蒸汽重整反应有关的加热过程中蒸汽重整原料工艺中所包含的部分氢气氧化来提供。

Description

制备富含氢气气体的方法
技术领域
本发明涉及在含氧气氛的存在下，用含有二甲醚(DME)和/或甲醇(MeOH)的原料绝热催化蒸汽重整制备富含氢气气体的方法。
背景技术
从EP-A-0761942和EP-A-0754649中知道在固体酸催化剂的存在下，可将DME重整成富含氢气和一氧化碳的气体。在DME的蒸汽重整过程中的反应过程是：
            (1)
           (2)
                  (3)
上述反应是吸热反应，并需要用于适当反应速率的热量。根据EP-A-0761942描述的方法，热是通过气体涡轮机的热废气供给的。从WO98/18572还已知在与放热的水煤气转移反应有关的热传导中用蒸汽催化水解DME。
发明内容
现已发现，当在与DME/MeOH的蒸汽重整过程中形成的部分氢气的部分氧化反应有关的热传导中进行反应时，DME可绝热地进行蒸汽重整。
基于上面的发现，本发明提供一种在生产富含氢气的重整催化剂的存在下，用含有二甲醚和/或甲醇的原料通过蒸汽转化二甲醚和/或甲醇制备富含氢气气体的方法，其中在与蒸汽重整反应有关的热传导下，通过蒸汽转化原料中的部分氢气的氧化来提供用于吸热蒸汽重整反应所需的热量。
上述蒸汽重整反应和氢气的部分氧化反应是在绝热排列的单个或多个催化区中进行的。当采用单个催化区时，优选采用一种对上述DME和MeOH蒸汽重整反应和氢气的氧化反应都具有活性的催化剂。可使用上述类型的催化剂是包括沸石材料、硅酸铝、氧化硅氧化铝、氧化铝和其混合物的固体酸，所述的固体酸与甲醇裂解催化剂例如Cu、或Cu-Zn-氧化铝以优选在1∶5和5∶1之间的重量比例结合，以按常规催化剂制备法进行涂覆二氧化硅和以一种或多种贵金属例如铂和/或钯掺杂的外壳。此类具有蒸汽重整和氧化活性的催化剂优选用于流化床反应器，其中在反应器的底部输入DME和/或甲醇的操作蒸汽、蒸汽和含氧气的气氛导入。
另外，本发明方法可在急冷型绝热重整炉或具有上述DME和/或甲醇重整催化剂的多个固定床催化剂层的绝热热交换重整炉和氧化催化剂的中间床中进行。
当使用急冷型重整炉时，在装有重整催化剂的第一床中输入DME和/或甲醇的预热工艺气体和蒸汽并将它们部分转变成含有氢气的气体。然后部分氢气与输入到部分重整气体(来自顶部催化剂床)中的含氧气氛发生氧化反应，并在置于顶部催化剂床和其后的重整催化剂固定床之间的氧化催化剂床中进行氧化。在氧化催化剂床中进行氧化反应放出的热量由此传给反应工艺气体其量足以保持在其后的重整催化剂中进行的吸热重整反应。
含氧气氛可分几步加入到工艺处理气体中，而每一步都按上述的方法进行。
用于本发明方法的含氧气氛可为任何含氧气气氛，其量足以氧化要求量的氢气，以提供以合适的反应速度进行吸热重整反应所需的热量。
含氧气氛可以是纯氧、富氧的空气、或缺氧空气。
在上述方法中使用空气或缺氧的空气的优点是在该方法中可产生有用的氨合成气体。
上述方法的另一个优点是从工艺过程中的流出气体中回收的二氧化碳通过已知的尿素生产系统用来生产尿素。
本发明的上述特点和优点通过参考附图结合下面的本发明具体实施方案的详细描述将更显而易见。
附图说明
图1表示根据本发明的具体实施方案，在绝热DME重整炉中从DME原料蒸汽进行重整生产氨合成气体方法的简单流程图；和
图2表示根据本发明另一实施方案在绝热热交换DME重整炉中进行的类似方法。
具体实施方式
在图1所示的重整炉中，DME的进料气和蒸气被导入DME重整催化剂的第一床6中。任选地通过在热交换器7中重整进料气5提供的热量使该进料气预热到约270℃。
经过床6，将进料气部分地重整成含氢工艺气体。在混合器中使工艺气体与空气2的第一股汽流和氧化催化剂床9中氧化的工艺气体中的部分氢混合。由此，使氧化反应过程中放出的热传给反应的工艺气体，该工艺气体在DME重整催化剂床10中被进一步重整。
随后，另外的热量通过在分别经管路3和4供有空气的氧化催化剂床11和13中的部分氢气的氧化被提供到反应工艺气体中。然后使工艺气体也在催化剂床12和14中进一步重整成最终产物气体5。
在图2所示的热交换DME重整器中DME和含有进料汽流1的汽流用通过工艺气体中部分氢的氧化提供的热量重整含氢工艺气体的上述方法类似。如图1所示，与上述方法相反，将进料气体在图2的热交换重整炉中，在一个步骤中，通过催化剂床4与氧化催化剂床5中获得的部分氢和氧化反应间接热交换进行重整。与图1所示的上述方法类似，可通过在热交换器6中的热交换，用产物气体3的热量预热进料气体。
用于上述方法中实际的气体成分和工艺参数概括于下表中，其中，位置数字与图中的参考数字相对应。
                                 表1
图1
位置     1     2     3     4     5
压力(ato)     34     33     33     33     31.5
温度(℃)     350     166     166     166     458
流速(kmol/h)     7707     894     669     808     13979
成分O2H2H2ON2COCO2ArMeOHDME 85.7114.29 20.850.5677.630.030.94 20.850.5677.630.030.94 20.850.5677.630.030.94 39.5831.3413.160.5215.210.160.03
图2
  位置     1     2     3
  压力[ato]     39     39     37.5
  温度[℃]     269     173     350
  流速[kmol/h]     11047     2488     17615
  成分O2H2H2ON2COCO2ArMeOHDME 89.5810.42 20.860.4977.690.030.94 32.7843.0510.970.4912.560.130.01
尽管对本发明特定的实施方案进行了描述，但对于本领域中的熟练技术人员来说所作的各种改变和改进都是显而易见的。因此，优选地是本发明不受本文中公开的具体方案的限制而受所附的权利要求的限制。

Claims (2)

1.一种用含有二甲醚和/或甲醇的原料制备富含氢气气体的方法，该方法包括以下步骤：在重整催化剂的存在下，通过蒸汽重整上述原料而提供富含氢气的工艺气体，所述催化剂在二甲醚和甲醇的蒸汽重整中具有组合活性，其中催化剂由固体酸和涂有二氧化硅和一种或多种贵金属掺杂外壳的甲醇重整催化剂的混合物组成；
在氢气氧化催化剂的存在下，氧化富含氢气的工艺气体中的部分氢气；和
将在氢气的氧化中放出的热传递给蒸汽重整原料，其量足以维持原料的吸热蒸汽重整反应。
2.根据权利要求1的方法，其中原料在被引入蒸汽重整步骤之前被预热到270℃～350℃。
CN99100429A 1998-01-21 1999-01-21 制备富含氢气气体的方法 Expired - Fee Related CN1123530C (zh)

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US6059995A (en) 2000-05-09
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