CN101155753B - 再利用收集的co2制备氢气的燃烧装置 - Google Patents

再利用收集的co2制备氢气的燃烧装置 Download PDF

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CN101155753B
CN101155753B CN2006800109703A CN200680010970A CN101155753B CN 101155753 B CN101155753 B CN 101155753B CN 2006800109703 A CN2006800109703 A CN 2006800109703A CN 200680010970 A CN200680010970 A CN 200680010970A CN 101155753 B CN101155753 B CN 101155753B
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J·-X·莫兰
C·比尔
S·叙拉尼蒂
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Abstract

本发明涉及一种制造包含CO2和水蒸汽的气体的燃烧装置，其由循环流化床反应室(1，2)、分离器(10，20)和包括置于致密流化床(12，12a，22)的部分的换热器设备组成。本发明装置的特征是置于床的换热器设备部分包括气体混合物所流经的催化剂管(120，120a，220)。上述的气体混合物包括天然气和/或石脑油或炼油气体或两种或多种所述气体。气体进行重整并转变为包含氢气的合成气体。由于催化剂管置于由燃烧灰形成的致密流化床中，催化剂可以均匀加热并促进天然气混合物的重整反应。

Description

再利用收集的CO2制备氢气的燃烧装置
本发明涉及使用矿物燃料的发电厂。这些发电厂产生大量需要加以控制的温室气体，特别是CO2。
这种压力使得有必要以经济的方式和最小的影响解决通过使用诸如非矿物碳的可再生生物能源捕获发电厂燃料气体中包含的CO2这样的新的问题。
此外，石油资源即将耗尽并且需要寻找作为CO2重要排放源的汽车运输用石油资源的替代品，这种日益迫切的形势使得需要寻找可选择的方式以生产替代燃料，特别是从非矿物(生物)燃料。
另一方面，在夜间几乎不使用电力生产资源，这成为发展多联产类型生产设施的动因。
为了减少污染，已知的方法为将包含含碳物质的可燃性固体转换为由回收CO2稀释的氧气，而不是转换为空气，从而产生不包含氮气的气体。另一种已知的方法为通过在热化学循环中燃烧来转换可燃性固体从而产生无氮气体。然而这些方法只能发电并且当产能下降时不能充分利用。
为了产生富含氢气的气体，特别是为了在燃料电池中使用以及为了生产运输用燃料，已知的方法为重整催化剂管束中的天然气，该管束部分浸入致密的流化床中。然而，该系统使用燃料加热流化床和水蒸气以产生富含氢气的合成气体。
本发明的目的是提供一种能量转换装置以同时发电并产生富含氢气的合成气体，另一方面可以使引入的水蒸气量最小并且无需额外的燃料。
本发明的燃烧装置产生包含CO2和水蒸气的气体并且包括循环流化床反应室，分离器，部分置于致密流化床的热量回收系统，其中置于热量回收系统的床的部分由气体混合物所流经的催化剂管组成。引入的气体由天然气和/或石脑油或炼油气体或两种或多种这些气体组成，该气体称为“待重整气体”。气体经重整转变为包含氢气的合成气体。催化剂管置于由燃烧残留物组成的致密流化床中，使得催化剂以均匀的方式重新加热并且激发气体混合物的重整反应。
从燃烧气体中回收的CO2用于与待重整气体混合并引入到催化剂管中。事实上，含碳固体燃料的燃烧产生CO2，其用于根据下述方程式重整气体混合物：
CH4+2CO2→3CO+H2+H2O
CH4+3CO2→4CO+2H2O
最后一个反应包括与CH4相比最大量的CO2，这使得所消耗的CH4的量最小化并获得最佳的CO/H2混合物。因而，通过与CO2和水蒸汽反应的结合实现了对气体混合物的重整。
源自催化剂管中回收的固体含碳燃料燃烧的气体中的水蒸汽也被使用。根据下述方程式实现对气体混合物的重整：
CH4+2H2O→CO2+4H2
CH4+H2O→CO+3H2
合成气体经过催化剂管中后进入氢气制造设备，这个过程包括进一步增加氢气含量的气水反应阶段。该阶段由下述反应表征：
CO+H2O→CO2+H2
该气水反应尤其重要，因为其通过使用由燃烧产生的水蒸汽允许(在必要情况下补加所需CO的转换率以得到合成气体中特定C/H比)在CO2和氢气随后分离前使所产生的CO完全转换为CO2和H2。
根据初始方案，燃烧是空气中的燃烧，也就是说固体燃料在空气中燃烧，因而气体主要包括被氮气稀释的CO2。
根据第二方案，燃烧是氧气中的燃烧，燃料在由装置产生或不由其产生的氧气中燃烧。在这种情况下，气体只包括痕量的氮气，混合物由约75％的CO2和约25％的H2O组成。
根据第三方案，燃烧是热化学循环中的燃烧，也就是说由于金属氧化物接连在氧化反应器中氧化并在燃烧室中还原而发生燃烧。燃烧所产生的气体包括55％的CO2和45％的H2O。
热化学循环燃烧使用金属氧化物转换氧气。
热化学燃烧循环中所使用的金属氧化物用作氢气生产设备中的催化剂。因此不需要向装置中引入任何额外的催化剂。
该金属氧化物为铁的氧化物。该催化剂在700/950℃发生作用。
为了与气体混合物反应，催化剂管部分由氧化镍制成。该催化剂必须在750/950℃发生反应，其在温度为约750-950℃的流化床中重新加热。
气体在压力下流经催化剂管。这使得反应器体积减小从而使管体积减小，并补偿电压损失。
致密的床优选置于燃烧室外。这由于床的较大尺寸改善了设备在生产合成气体时的适应性。
作为一个方案，致密的床沿着反应室的壁放置。以这种方式，催化剂管沿着室底部周长放置。因此可以具有可用的附加管重整表面。在这种情况下，通过减少沿着燃烧室壁收集的固体实现向包含重整管的流化床喂料，使得当部分装填时增加总体的装置性能，在最小装填时降低装置性能。由于不再只依赖于外部供给的固体，这种配置尤其有利，固体的量根据燃烧室的装载量变化很大，特别是在较低装载量时。
至少部分催化剂管置于固体中。由于固体确保对催化剂管进行更好的热润湿，因而使用微粒重新加热催化剂会产生更好的效果。使用固体而不是气体进行热交换允许使用较小的重整表面，从而需要较少的催化剂管和更紧密的床。对喂入致密床的固体流量的调整允许调整管的温度从而调整重整的动力学。
部分催化剂管置于固体之上。这使得增加了所用管的表面积。
根据一个方案，部分管置于反应室的底部。由于底部的硬度减少了长度可以为很长的管上的机械应力，将重整管置于室底部是可能的。
催化剂管由通过中间板支撑的长度很长的的管制成。在致密的床中可使用临时的板支撑长的重整管。
根据一个方案，中间板被冷却。以这种方式可以保证管的耐久性。
根据一个方案，催化剂管由带有中间室的短管组成。在这种情况下，管可以串联摆放或平行摆放。
通过阅读下述单独作为例子并涉及附图的描述可以更容易理解本发明，其中：
-图1是本发明热化学循环中的第一方案装置的全视图，
-图2是本发明在氧气中燃烧的第二方案装置的全视图，
-图3是本发明在空气中燃烧的第三方案装置的全视图，
-图3a是图3中第三方案装置的一种方案的全视图，
-图4第一方案中的床的顶视图，
-图5是第二方案中的床的顶视图，
-图6是第三方案中的床的顶视图，
-图7是第一方案催化剂管中床的横截面视图，
-图8是第二方案催化剂管中床的横截面视图，
-图9是第三方案催化剂管中床的横截面视图，
图1中所示的装置是热化学循环燃烧装置。其包括燃烧室1和氧化室2。
燃烧室1具有用以分离固体的旋风分离器10，其一端与后通道11相连，另一端与外部床12相连。料仓13中的燃料送入室1。过滤袋14，风扇15，灰尘与氧化物回收装置16和CO2处理站17。
氧化室2具有两个旋风分离器20，其一端与后通道21相连，另一端与外部床22相连。室2通过料仓23喂料。过滤袋24，排气风扇25和烟囱26置于后通道21之后。
平行地，回收CO2和水蒸汽中的气体混合物、特别是回收CO2所含的气体混合物引入床22中的催化剂管220，在其中发生气体重整。气体混合物由CO、H2、CO2和H2O组成。所存在的气体随后送入气水反应器221和氢气净化装置222。通过溶剂、膜或低温技术的方式进行净化222。离开反应器221的气体由H2、CO2和H2O组成。
金属氧化物从氧化室2中开始循环流动，在氧化室中其被氧化从而与旋风分离器20中的气体分离，初始部分进入燃烧室1中进行还原，第二部分返回室2，第三部分进入对温度进行控制的外部流化床22并返回室2，第四部分作为气水反应催化剂进入反应器221。
图2所示的装置是在循环流化床中进行氧气燃烧的装置。其包括燃烧室1，一个或多个与后通道11相连的分离器10和一个或多个流化床12。从后通道11散发出的气体在进入CO2压缩机组(未示出)之前转入过滤袋14；通风装置15，然后进入冷凝器19。
床12通过外部空气流态化，外部空气随后在分离的后通道3、过滤袋4、通风装置5和烟囱6中冷却。
床12包含催化剂管120，由燃烧产生并通过后通道11排出的回收气体和CO2/H2O混合物流经其中。一些残留氧气(小于5％)保留在回收的CO2/H2O中并有助于所产生合成气体的部分氧化，通过从固体温度到合成气体温度的独立增加促进反应。合成气体转入气水反应装置121，然后进入氢气净化器122。依靠管道121a向反应装置121供应外部的催化剂，依靠管道121b向反应装置供应蒸气。
如图3所示，可以使用标准空气燃烧装置通过用胺清洗捕获CO2。用胺清洗是将CO2从燃烧释放出的例如主要是氮气的其它气体中分离出的标准技术。该装置包括与一个或多个分离器10相连的燃烧室1。每个燃烧器10与外部流化床12相连并返回室1。床12通过空气进行流态化。
分离器释放出的气体进入后通道11，在其中气体被冷却，残余热量用于再加热空气加热器100中进入室1的气体。正如在前述方案的情况下，气体然后进入过滤袋14、通风装置15，随后进入冷凝器19和胺清洗器190中。CO2/H2O从随后经由烟囱6返回大气的气体中提取出来。
催化剂管120置于床12中，气体混合物在其中循环。提取的CO2/H2O与气体混合物被送入管120中从而对后者进行重整。所得的气体进入气水反应器121，催化剂121a和水蒸汽121b被引入其中。在净化器122中进行气体净化以增加氢气含量。
在图3a所示的方案中，床12a沿着室1的壁1a放置。与床12相反，通过减少沿着室1的壁1a收集的颗粒向该床12a供应固体。其通过空气进行流态化。
位于床12中的催化剂管120和位于床12a中的催化剂管120a中的气体混合物到达每个床12和12a中。一旦重整发生，气体向气水反应装置121移动。
图4显示了位于床12并通过中间板123支撑的长催化剂管120。
图5显示了带有与中间室124平行的短催化剂管120的床12。图5中气体混合物到达底部并从顶部排出。
图6显示了带有与中间室124相串联的短催化剂管120的床12。图6中气体混合物到达顶部和底部并从中部排出
图7显示了置于固体9中的催化剂管120。
图8显示了置于固体9顶部的催化剂管120。
图9显示了置于固体9中的催化剂管120和置于固体9顶部的催化剂管120。

Claims (22)

1.制造包含CO2和水蒸汽的气体的燃烧装置，包括循环流化床反应室(1，2)，分离器(10，20)，部分置于致密流化床的热量回收设备，其中置于热量回收设备的床的部分包括气体混合物所流经的催化剂管(120，120a，220)，所述气体混合物由天然气和/或石脑油或炼油气体或两种或多于两种这些气体组成，该气体称为“待重整气体”，该气体经重整转变为包含氢气的合成气体。
2.权利要求1所述的燃烧装置，其中从燃烧气体中回收的CO2与待重整气体混合并引入到催化剂管(120，120a，220)中。
3.权利要求1所述的燃烧装置，其中水蒸汽在催化剂管(120，120a，220)中回收。
4.权利要求1所述的燃烧装置，其中在催化剂管(120，120a，220)之后，重整的气体混合物进入包括气水反应阶段(121)的氢气转化设备(121，122)。
5.权利要求1-4任一项所述的燃烧装置，其中燃烧是空气中的燃烧。
6.权利要求1-4任一项所述的燃烧装置，其中燃烧是氧气中的燃烧。
7.权利要求1-4任一项所述的燃烧装置，其中燃烧是热化学循环中的燃烧。
8.权利要求7所述的燃烧装置，其中热化学循环中的燃烧使用金属氧化物。
9.权利要求8所述的燃烧装置，其中金属氧化物用作氢气生产设备(121)中的催化剂。
10.权利要求9所述的燃烧装置，其中金属氧化物是铁的氧化物。
11.权利要求1-4任一项所述的燃烧装置，其中催化剂管(120，120a，220)部分由氧化镍制成。
12.权利要求1-4任一项所述的燃烧装置，其中气体在压力下流经催化剂管(120，120a，220)。
13.权利要求1-4任一项所述的燃烧装置，其中所述的床(12)置于燃烧室外部。
14.权利要求1-4任一项所述的燃烧装置，其中所述的床(12a)沿着反应室(1)的壁(1a)放置。
15.权利要求1-4任一项所述的燃烧装置，其中至少一部分催化剂管(120，120a，220)置于固体中。
16.权利要求1-4任一项所述的燃烧装置，其中部分催化剂管(120，120a，220)置于固体之上。
17.权利要求1-4任一项所述的燃烧装置，其中部分催化剂管(120，120a，220)置于反应室(1)的底部。
18.权利要求1-4任一项所述的燃烧装置，其中催化剂管(120，120a，220)由通过中间板(123)支撑的长管形成。
19.权利要求18所述的燃烧装置，其中中间板(123)被冷却。
20.权利要求1-4任一项所述的燃烧装置，其中催化剂管(120，120a，220)由带有中间室(124)的短管组成。
21.权利要求1-4任一项所述的燃烧装置，其中所述催化剂管是设置以激发气体混合物的重整反应，使该气体经重整转变为包含氢气的合成气体。
22.权利要求1-4任一项所述的燃烧装置，其中所述催化剂管置于由燃烧残留物组成的致密流化床中，使得催化剂以均匀的方式重新加热并且激发气体混合物的重整反应，使该气体经重整转变为包含氢气的合成气体。
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