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CN101035611A - 再生重整装置的方法 - Google Patents

再生重整装置的方法 Download PDF

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Publication number
CN101035611A
CN101035611A CNA2005800341823A CN200580034182A CN101035611A CN 101035611 A CN101035611 A CN 101035611A CN A2005800341823 A CNA2005800341823 A CN A2005800341823A CN 200580034182 A CN200580034182 A CN 200580034182A CN 101035611 A CN101035611 A CN 101035611A
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fuel
reformer
charging rate
zone
time interval
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CN100551515C (zh
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马尔科·米尔内尔
斯特凡·克丁
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Enerday GmbH
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Webasto Thermosysteme GmbH
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Abstract

本发明涉及再生重整装置的方法，向该重整装置连续输送燃料(12，14)和氧化剂(16，18，20)，为了再生，和连续操作时的进料速度相比燃料(12，14)的进料速度降低。根据本发明，在随后的多个时间间隔，燃料(12，14)的进料速度和连续操作的进料速度相比降低。燃料(12，14)的进料速度在随后的时间间隔之间比在随后的时间间隔期间要高。本发明还涉及相应的重整装置。

Description

再生重整装置的方法
技术领域
本发明涉及再生重整装置的方法，向该重整装置连续输送燃料和氧化剂，为了再生，和连续操作时的进料速度相比燃料的进料速度降低。
本发明进一步涉及包括实现重整装置再生的控制器的重整装置，该控制器用于连续地向重整装置输送燃料和氧化剂，而且，为了再生，同连续操作时的进料速度相比降低燃料进料速度。
背景技术
普通的重整装置和方法有多种不同应用，它们特别用于将富含氢气的气体混合物输送到燃料电池内，基于电化学反应可以从中产生电能。这种燃料电池用于例如摩托车辆的辅助供电设备(APU)。
可以根据各种原理进行将燃料和氧化剂转化成重整产品的重整工艺。例如，已知催化重整，其中，燃料在放热反应中被氧化。催化重整的弊端在于产生大量的热量，热量可以毁坏系统元件，尤其是催化剂。
从碳氢化合物产生重整产品的另一个可能是蒸气重整，其中，在吸热反应中，利用蒸气，碳氢化合物被转化成氢气。
这两种原理的结合，即，基于放热反应和由吸热反应产生氢气(其中，用于蒸气重整的能量来自碳氢化合物的燃烧)的重整称为自热重整。然而，因为需要提供输送水的装置，所以会存在其他的缺点。氧化区和重整区之间的高温度梯度为系统的整体热平衡造成进一步的问题。
通常，空气和燃料在重整装置中转化为富含氢气的气体混合物的反应可以如下表示：
Figure A20058003418200061
由于该吸热反应中碳氢化合物的不完全转化(式中未示出)，如残余碳氢混合物或者烟灰的副产品会物化，其至少部分沉积在重整装置上，造成重整装置内的催化剂失去活性，甚至可以到达催化剂完全为烟灰覆盖的地步。这加剧了重整装置内压力下降，导致其被毁坏或者需要再生。
根据在先技术，具体通过燃烧掉沉积在重整装置内的烟灰来实现该再生。这会产生高温，对催化剂或者衬底材料造成永久性(即不可逆转)的损坏。除此之外，开始燃烧烟灰后，大的温度梯度阻碍对重整装置的控制。因为存在过多的氧气，在燃烧过程中，氧气会出现在重整装置的出口，因此，不可能将以这种方式再生的重整装置用于SO燃料电池(SOFC)系统。
发明内容
本发明基于如下目的：实现重整装置的再生，这样可以消除上述问题，特别是避免高温、大的温度梯度和在重整装置的输出出现不希望的氧气。
该目的由独立权利要求的特征实现。
从本发明的有益实施例推演出从属权利要求。
本发明基于通用方法，其中，在若干个连续的时间间隔中，燃料的进料速度和连续操作时的进料速度相比是降低的，燃料的进料速度在连续的时间间隔之间比连续的时间间隔期间要高。在正常操作中，重整装置在650℃或以上接收连续的燃料和空气进料。重整装置工作于热平衡状态，因此，在静态操作中不需要考虑温度升高。然而，如所述的沉积导致催化剂某种程度上失去活性。当重整装置长期进行操作时关闭燃料进料口时，烟灰以远高于1000℃的温度燃烧，这会导致催化剂甚至整个重整装置被毁坏。这是因为燃烧烟灰时的反应为
C+O2→CO2
该反应逐步放热。在催化剂完全燃烧掉以后，重整装置端部输出氧气，这会导致SO燃料电池的阳极被毁坏。根据本发明的方法，建议降低脉冲式燃料进料，每个脉冲只持续很短的时间。向烟灰沉积输送氧气或者空气，这样可以开始氧化过程，也会导致催化剂温度升高。但是，在温度高到重整装置受到损坏之前，再次增加燃料进料。因此，在降低进料速度的时间间隔结束时，重整装置的一部分得到再生，即，基本上不存在烟灰或沉积。在再生间隔之后，可以继续重整过程。因为这会逐步吸热，重整装置冷却到常温。重复该过程，直到整个重整装置被再生。因此，重整分区进行。降低脉冲式燃料进料使得没有氧气进入燃料电池的阳极，因为氧气在反应中消耗了。
本发明其他的有益特征在于，在至少一个连续时间间隔中，燃料进料速度为零。由于在连续时间间隔中完全关闭燃料进料口，因而沉积的燃烧更充分。在燃料进料口没有完全关闭时，重整装置中产生的水增加。根据下式，水可以从重整装置中去除烟灰和其他沉积：
C+H2O→CO+H2
此外，测量重整装置排出物质中的氧气含量，并且在氧气含量超过门限值时重整装置转换为连续操作也是有用的。因此，重整装置输出处的氧气含量作为重整装置完全再生的指示。跟踪氧气含量还可以保证不会有过量的氧气和SO燃料电池的阳极接触。
这种情况下，使用含氧传感器(Lambda Sensor)测量氧气含量。
同样，氧气含量可以用燃料电池测量。为了免于安装含氧传感器，燃料电池的电输出值可以直接用于检测氧气含量的增加。
根据本发明的方法对于具有双燃料进料口的重整装置尤其适用，在再生时，燃料进料口之中的一个的进料速度基本上对应于连续操作的进料速度。因此，使用双燃料进料口的重整装置，改变燃料进料速度的可能性更大。这特别适用于部分不变地操作重整装置，而重整装置的其他部分通过改变功能进行再生。
因此，根据本发明的有益特征在于重整装置包括氧化区域和重整区域，重整区域可以供以热，而氧化区域使用第一燃料进料口供以燃料和氧化剂的混合物，在至少部分氧化燃料后，该混合物可以至少部分输送到重整区域，重整区域使用第二燃料进料口供以额外的燃料，第二燃料进料在连续时间间隔以降低的进料速度工作。因此，额外的燃料进料和来自氧化区域的废气一起形成重整过程开始的混合物。通过混合燃料和废气，可以得到小的λ值(例如λ＝0.4)，通过供以热量，可以实现吸热重整反应。关于根据本发明的再生，需要指出的是，重整装置在氧化区域的操作可以继续不变地进行，同时只有第二燃料进料口被关闭或降低。
尤其有益的是，氧化区域的放热氧化的热可以输送到重整区域。因此，氧化区域所得到的热量在重整反应中被转化，这样，由整个过程产生的净热量不会引起管理重整装置温度的问题。
重整区域包括氧化剂进料口是有用的，通过该氧化剂进料口，可以输送额外的氧化剂，由此得到另外一个影响重整的参数，并且可以对其进行优化。
本发明尤其有益的特征在于，额外的燃料输送至注入混合区域，从此处，额外的燃料流进重整区域。因此，该注入混合区域设置在重整区域的上游，这样重整区域为重整反应准备了混合好的输出气体。
因此，额外的燃料至少部分被氧化区域的气体混合物的热能蒸发，因此，使得氧化的反应热也可以有益地用于燃料蒸发过程，这是有益的。
此外，氧化区域产生的气体混合物部分绕过注入混合区域输送到重整区域，因此，使得产生了另一个影响重整过程的可能，这样，重整装置产生的重整产品进一步得到改善，这是有益的。
本发明基于通用重整设备，其中控制器适于在若干连续时间间隔降低燃料进料速度(同连续操作的进料速度比)，燃料进料速度在连续时间间隔直接比连续时间间隔期间要高，由此在重整装置中应用了根据本发明的方法的有益和特殊特征。
本发明基于下述发现：可以防止高温、大的温度梯度、不希望的压力增加和不希望的氧气出现在重整装置的输出，因为燃料进料是脉冲式的，具体而言是对燃料进料口进行脉冲式关闭。
附图说明
以下通过参考附图根据优选实施例详细说明本发明，其中：
图1是辅助解释根据本发明的方法的流程图；以及
图2是根据本发明的重整装置的示意图。
具体实施方式
现在参考图1，其中示出辅助解释根据本发明的方法的流程图。在步骤S01的重整装置再生开始之后，在步骤S02关闭燃料进料。随后，在步骤S03感测重整装置中的温度，在步骤S04确定感测到的温度是否比预定门限值TS1高。如果否，在燃料进料关闭时，在步骤S03再次感测重整装置中温度。如果在步骤S04确定温度超过预定门限值TS1，在步骤S05打开燃料进料。随后在步骤S06再次感测重整装置中的温度。在步骤S07确定感测到的温度是否比预定门限值TS2低。如果否，不关闭燃料进料，在步骤S06再次感测重整装置中的温度。如果在步骤S07确定温度低于预定门限值TS2，在步骤S02再次关闭燃料进料，这样，开始重整装置再生的下一个时间间隔。
与监控温度并行，在步骤S08监控重整装置中的氧气平衡点。这用于确定再生结束。因此，当发生氧气平衡并且关闭燃料进料时，然后，在步骤S09打开燃料进料，之后，在步骤S10结束再生。
现在参看图2，其中示出根据本发明的重整装置的示意图。本发明不限于所示的特殊配置。相反，根据本发明的再生可适于多种类型的重整装置，只要可以临时降低或者中断燃料进料。所示的重整装置10基于优选地没有蒸气进口的部分氧化可以分别通过各自的进料口供以燃料12和氧化剂16的原则。例如，可能的燃料12为柴油，氧化剂16通常为空气。燃烧开始后迅速引起的反应热可以在可选的冷却区域36部分去除。然后，混合物进入氧化区域24，氧化区域24可以由设置在重整区域26内的管道实现。在替代实施例中，氧化区域由重整区域26内的多个管道或者特殊的管道结构实现。在氧化区域中，燃料和氧化剂以λ＝1的放热反应转化。然后，所得的气体混合物32金融注入混合区域30，其中气体混合物32和燃料14混合，由此气体混合物32的热量可以支持燃料14的蒸发。此外，还可以对注入混合区域30输送氧化剂。然后，这样形成的混合物进入重整区域26，在这里，该混合物以例如λ＝0.4的吸热反应被转化。用于吸热反应的热28来自氧化区域24。为了优化重整过程，可以对重整区域26输送额外的氧化剂18。此外，还可以将在氧化区域24产生的部分气体混合物34绕过注入混合区域30直接输送到重整区域26。然后，重整产物22从重整区域26流过，可以用于进一步的应用。
重整装置具有控制器38，该控制器38除了别的功能以外，可以控制主燃料进料12和次燃料进料14。
为了在图2所示的示例性实施例中的重整区域26中进行再生，脉冲式地关闭燃料进料14，同时用于保持重整装置中的氧化剂的燃料进料12继续操作而不改变进料速度，这样就够了。然后，重整区域26中提供的催化剂被包括氧气的燃烧废气烧掉。
应该理解，本说明书、附图和权利要求所公开的本发明的特征单一地或者结合起来对本发明的实现都很重要。
附图参考标号
12燃料
14燃料
16氧化剂
18氧化剂
20氧化剂
22重整产品
24氧化区域
26重整区域
28热
30注入混合区域
34气体混合物
36冷却区域
38控制器

Claims (13)

1、使用燃料(12，14)和氧化剂(16，18，20)在连续操作中再生重整装置的方法，为了再生，所述燃料(12，14)的进料速度和连续操作时的进料速度相比降低，其特征在于，
-在若干连续的时间间隔，所述燃料(12，14)的进料速度和连续操作时的进料速度相比降低，以及
-所述燃料(12，14)的进料速度在所述连续的时间间隔之间比在所述连续的时间间隔期间要高。
2、根据权利要求1的方法，其特征在于，在至少一个所述连续时间间隔期间，所述燃料(12，14)的进料速度为零。
3、根据权利要求1或2的方法，其特征在于，
-测量离开所述重整装置的物质中的氧气含量，以及
-在所述氧气含量超过门限值时所述重整装置变为连续操作。
4、根据前述任何一项权利要求的方法，其特征在于，使用含氧传感器测量所述氧气含量。
5、根据前述任何一项权利要求的方法，其特征在于，使用燃料电池测量所述氧气含量。
6、根据前述任何一项权利要求的方法，其特征在于，对于具有双燃料进料口的重整装置，在再生时，所述燃料进料口之中的一个的进料速度基本上对应于连续操作时的所述进料速度。
7、根据权利要求6的方法，其特征在于，
-所述重整装置包括氧化区域(24)和重整区域(26)，
-对所述重整区域(26)供以热(28)，
-对所述氧化区域使用第一燃料进料口供以燃料(12)和氧化剂(16，18，20)的混合物，在至少部分氧化燃料(12)后，所述混合物至少部分输送到所述重整区域(26)，
-所述重整区域(26)使用第二燃料进料口供以额外的燃料(14)，
-所述第二燃料进料口在所述连续时间间隔中以降低的进料速度工作。
8、根据权利要求7的方法，其特征在于，所述氧化区域(24)的放热氧化的热量可以输送到所述重整区域(26)。
9、根据权利要求7或8的方法，其特征在于，所述重整区域(26)包括氧化剂进料口，通过所述氧化剂进料口，可以输送额外的氧化剂(16，18，20)。
10、根据权利要求7至9中的任意一项的方法，其特征在于，
-输送额外的燃料(14)至注入混合区域(30)，
-所述额外的燃料(14)可用从所述注入混合区域(30)流进所述重整区域(26)。
11、根据权利要求7至10中的任意一项的方法，其特征在于，所述额外的燃料(14)至少部分被所述氧化区域(24)排出的所述气体混合物(34)的热能蒸发。
12、根据权利要求10或11的方法，其特征在于，所述氧化区域(24)产生的所述气体混合物(34)部分绕过所述注入混合区域(30)输送到所述重整区域(26)。
13、重整装置，其包括实现所述重整装置再生的控制器(38)，所述控制器(38)适用于以连续操作对所述重整装置输送燃料(12，14)和氧化剂(16，18，20)，为了再生，所述燃料(12，14)的进料速度和所述连续操作时的进料速度相比降低，其特征在于，
-所述控制器(38)适于在若干连续时间间隔期间，同所述连续操作的进料速度相比，降低所述燃料(12，14)进料速度，以及
-所述燃料(12，14)的进料速度在所述连续的时间间隔之间比在所述连续的时间间隔期间要高。
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