CN101754927B - 用于将烃燃料转化为富氢气体的重整反应器及方法 - Google Patents
用于将烃燃料转化为富氢气体的重整反应器及方法 Download PDFInfo
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Abstract
本发明涉及一种用于通过自热反应过程将烃燃料转化为富氢气体的重整反应器,该重整反应器优选具有圆柱形形状的双壁壳体,该壳体带有内壁和外壁以及两个侧面,其中内壁和两个侧面形成反应室。另外,内壁充有第一电荷,该第一电荷防止通过燃料入口喷射到反应室内的烃燃料分子撞击反应室的热的内侧表面且随后燃烧为炭黑。
Description
技术领域
本发明涉及一种根据权利要求1的用于通过自热反应将烃燃料转化为富氢气体的重整反应器,该富氢气体用于燃料电池和/或排放处理应用,并且涉及一种用于使用重整反应器将烃燃料转化为富氢气体的方法。
背景技术
在现有技术中已熟知,通过将例如汽油或柴油燃料的烃燃料重整来产生用在运输装置的燃料电池中的富氢气体。通常,氢气在大规模工业设备中产生且然后储存在运输装置的板上。近来开发的小规模车载氢源,即所谓的重整反应器,提供了按需要产生氢的可能性,而无需储存氢。
通常存在三种已知的将气态或液态烃燃料转化为氢的方法:催化蒸汽重整,部分氧化重整和自热重整。
在催化蒸汽重整过程中,将蒸汽和烃燃料的混合物在高温下(在700℃至1000℃之间)暴露于合适的催化剂、例如镍,反应是高度吸热性反应,且要求外部热源和蒸汽源。
在部分氧化重整过程中,将氢燃料和含氧气体例如环境空气的混合物一起导入反应室且使之受到高温,优选存在有催化剂。通常,所使用的催化剂是贵金属或镍,且温度在700℃至1700℃之间。反应是高度放热性反应,且一旦开始则生成足够的热以使反应自维持。为促进氧化反应,需要将供给燃料预热且减小反应器内的温度变化。
例如,专利申请US 6,770,106描述了用于将含有烃或甲烷的供给气体进行重整的部分氧化重整器,其中通过以用于预热的供给气体的通道覆盖反应器且因此通过供给气体通道热隔离来实现减小温度变化。反应热通过热交换器回收,用于预热供给气体的目的。
自热重整过程是蒸汽重整和部分氧化重整的组合。来自部分氧化重整反应的废热用于加热吸热的蒸汽重整反应。
所有重整过程的自然副产物是一氧化碳和二氧化碳。但因为烃燃料不设计为用于生成氢的供给原料,所以也存在其他的副产物,例如硫、石蜡、苯、甲基酰胺(methyl amid)和更大分子量的芳香族化合物。这些副产物可能对于燃料电池是有害的,且因此应该通过随后的步骤在重整反应器外去除。
另外的缺点是,烃燃料、特别是柴油趋向于通过与反应器的内侧表面接触而燃烧为炭黑。炭黑微粒又对于燃料电池非常有害,且必须在将经重整的氢应用到燃料电池前去除。
发明内容
因此,本发明的目的是降低燃料分子由于与反应器的内侧表面接触而燃烧为炭黑的风险。
该目的通过一种根据权利要求1的重整反应器以及一种根据权利要求17的方法来实现。
根据本发明,内壁和由此的反应空间的内表面充有第一电荷。这考虑到使得由燃料入口喷射到反应室内的燃料分子带电。使反应器壳体的内壁带有一定的电荷,使得由于静电排斥而在统计学上防止燃料分子的50%与反应室的内表面接触。这明显降低了燃料分子燃烧为炭黑的风险。
根据另一个有利实施例,燃料入口也带电。优选地,燃料入口带有与内壁相等的电荷。这导致所有燃料分子具有与内壁相同的电荷且因此与内壁电排斥。因此,燃料分子几乎不可能与内壁接触而燃烧为炭黑。
另一个优选实施例提供有用于在反应室内自热反应的催化剂,以加速将烃燃料转化成富氢气体。优选地,催化剂也能够带电。这在另一个实施例中实现,其中催化剂的电荷与内壁和/或燃料入口的电荷相反。这使燃料/氧化剂混合物向催化剂加速,且因此加速转化反应。催化剂能够是陶瓷单块或金属格栅。
本发明的另一个优选实施例利用了如下事实,即由于燃料微粒与反应器内壁接触而燃烧形成炭黑仅在一定的壁温度之上才发生。如果将壁温度保持为低,例如通过将壁冷却或通过将反应空间的温度保持在一定水平以下,则防止燃料微粒燃烧为炭黑。
通常存在为反应器提供外部冷却装置的可能性,但这增加了反应器的尺寸且增加了由燃料电池供给能量的系统的另外的能量消耗。因此,优选的实施例使用相对冷的氧化剂用于冷却反应器的内壁。这意味着同时能够省却内壁的热隔离,以此进一步减小反应器的尺寸。
将内壁冷却的另一个优点是能够恒定保持反应室内的温度,且能够控制氧化剂的温度。
如在本发明的另一个优选实施例中示出,设置在壳体内壁内的氧化剂出口形成为多个孔。这便于将氧化剂均匀分布在反应室内。优选地,孔的尺寸、形状和/或位置能够根据所使用的氧化剂、所使用的烃燃料和/或其温度而改变。最优选地,氧化剂出口设置在燃料入口附近。
从属权利要求中限定了其他优选的实施例和优点。
附图说明
下文将借助附图论述本发明的优选实施例。描述考虑为本发明的原理的范例,且不意图于限制权利要求的范围。
图1示出本发明的优选实施例的示意图。
具体实施方式
图1示出根据本发明的优选实施例的重整反应器。
重整反应器1具有壳体2,壳体2具有内壁4、外壁6以及侧壁8a、8b。内壁4和侧壁8a、8b限定了反应室,在反应室内将烃燃料和氧化剂放在一起且能够进行自热反应。
内壁4与外壁6之间限定了空间12。空间12又形成用于氧化剂入口16与氧化剂出口18之间的氧化剂14的通道。氧化剂出口18形成为多个孔,所述孔的尺寸、形状和位置取决于使用的氧化剂14、使用的烃燃料20及其温度而变化。多个孔能够具有均匀的尺寸和形状,但也能够使孔在尺寸和形状上相互之间变化。
进一步地,重整反应器1具有烃燃料入口22,该烃燃料入口22位于壳体2的侧壁8a的一个上。优选地,燃料入口22形成为燃料喷射器,该燃料喷射器将燃料喷雾供应在反应室10内。重整气体出口24设置在壳体2的相对的侧壁8b内。重整气体26是富氢气体,该富氢气体能够用于运行燃料电池,且是自热反应的产物。
另外,重整反应器1包括催化剂,该催化剂用于催化反应室10内的自热反应。催化剂28加速自热反应,但也能够使用无催化剂的根据本发明的重整反应器。催化剂28优选是金属格栅或陶瓷单块(monolith)。但能够将任何其他合适的基质用于催化剂28的设计。
如图1中示出,提供两个电荷源30和34。电荷源30连接到内壁4和燃料入口22,因此为反应室10的壁和烃燃料20的分子提供第一电荷32。在图1中,带电的壁通过典型的正电荷来示意性地指示。电荷源34与催化剂28连接,且为催化剂28提供与第一电荷32相反的第二电荷36。在图1中,相反的电荷36通过典型的负电荷指示。
下文中通过利用作为氧化剂的空气/蒸汽混合物而将作为烃燃料的柴油示范性转化到氢来描述重整反应器的运行。用于转化的反应是自热反应。
根据本发明,空气和蒸汽混合,然后空气/蒸汽混合物14通过氧化剂入口16注入到空间12内,该空间12用作空气/蒸汽通道,用于将空气/蒸汽混合物14从反应器的氧化剂入口16输送到氧化剂出口18。
在向下到壳体2的内壁4内的多个出口孔18的路径中,空气/蒸汽混合物14用于冷却反应室10的内壁4。通过冷却反应室10的内壁4,降低了反应器的反应室10内的柴油燃料分子在撞击反应室壁时燃烧为炭黑的风险。
然后,迫使空气/蒸汽混合物14经过孔18进入到反应器的反应室10内,从而在反应室10内形成均匀的空气/蒸汽烟雾。在将空气/蒸汽混合物引入到反应室10内之后,柴油燃料20通过燃料喷射器22喷射到空气/蒸汽烟雾内。在反应室10内侧出现空气/蒸汽烟雾和柴油燃料喷雾的湍流混合物,其中燃料喷雾20通过与空气/蒸汽烟雾的接触而蒸发。下面解释蒸发。
因为反应室10的内壁4带电荷、例如带正电荷,并且柴油燃料喷雾的柴油燃料分子也带有正电荷,所以柴油分子由于静电排斥而与反应室10的壁排斥开。因此,柴油分子不能与反应室10的加热的壁接触且随后燃烧为炭黑。
当来自空气/蒸汽混合物14的氧与柴油燃料20的具有更短的链的“较轻”的烃分子反应时(CxHy+O2->CO2+CO+H2O),通过反应室10内发生的均匀氧化加热了反应室10的壁。由该过程产生的过程热用于使柴油燃料喷雾的剩余的烃分子(具有较长的链)蒸发。在此过程后,因为剩余空气的部分可忽略,所以反应室10内存在烃和蒸汽的均匀气态混合物。
均匀的气态混合物然后被引入到催化剂28中,其中柴油燃料20的烃经受自热反应过程。为了加速而将均匀气态混合物引入到催化剂28内,催化剂28也能够带有第二电荷,该第二电荷与柴油分子的电荷相反。在所示实施例中,燃料分子带正电。因此,催化剂带负电,使得分子由于静电吸引而由催化剂吸引。这使均匀气态混合物加速在催化剂方向上移动。
在催化剂内发生的自热反应过程中,氢(H)、CO和CO2作为主要过程产物而产生。这些产物在随后的步骤中在重整器外被处理,其目的是将H与所有其他过程产物分离。
因为通过施加电荷且由于静电排斥而防止因柴油分子的燃烧而形成炭黑,所以减少了富氢气体的杂质。这便于使纯氢与其他过程产物分离。
附图标记列表
1 重整反应器
2 壳体
4 内壁
6 外壁
8a、8b 侧面
10 反应室
12 空间=氧化剂通道
14 氧化剂
16 氧化剂入口
18 氧化剂出口
20 烃燃料
22 烃燃料入口
24 富氢气体出口
26 富氢气体
28 催化剂
30 第一电荷源
32 第一电荷
34 第二电荷源
36 第二电荷
Claims (15)
1.一种用于通过自热反应将烃燃料(20)转化为富氢气体(26)的自热式重整反应器(1),所述富氢气体用于燃料电池和/或排放处理应用,所述重整反应器(1)具有壳体(2),所述壳体(2)带有内壁(4)和外壁(6)以及两个侧面(8a、8b),在所述内壁(4)与外壁(6)之间形成有一空间(12),其中所述内壁(4)和所述两个侧面(8a、8b)形成所述重整反应器(1)的反应室(10),其中,所述空间(12)被设计为设置在所述外壁(6)上的氧化剂入口(16)与设置在所述内壁(4)上的氧化剂出口(18)之间的氧化剂通道,用于向所述反应室(10)提供氧化剂,并且其中,在所述两个侧面中的一个侧面(8a)上设置有燃料喷射器(22),用于将燃料喷射到所述反应室(10)中,其特征在于,所述内壁(4)充有第一电荷(32)。
2.根据权利要求1所述的重整反应器(1),其中所述燃料喷射器(22)充有所述第一电荷(32)。
3.根据权利要求1所述的重整反应器(1),其中在所述反应室(10)内还设置有用于所述自热反应的催化剂(28)。
4.根据权利要求3所述的重整反应器(1),其中所述催化剂(28)充有第二电荷(36)。
5.根据权利要求3所述的重整反应器(1),其中所述催化剂(28)是陶瓷单块或金属格栅。
6.根据权利要求4所述的重整反应器(1),其中所述第一电荷(32)与所述第二电荷(36)相反。
7.根据权利要求1所述的重整反应器(1),其中所述氧化剂出口(18)位于所述燃料喷射器(22)附近。
8.根据权利要求7所述的重整反应器(1),其中所述氧化剂出口(18)设计为将氧化剂(14)引入到所述反应室(10)内的多个孔。
9.根据权利要求8所述的重整反应器(1),其中所述多个孔具有各种尺寸和/或形状。
10.根据权利要求9所述的重整反应器(1),其中所述多个孔位于若干不同的位置。
11.根据权利要求10所述的重整反应器(1),其中所述多个孔的尺寸和/或形状和/或位置取决于所使用的烃燃料和/或所使用的氧化剂。
12.根据权利要求8-11中的任一项所述的重整反应器(1),其中所述氧化剂(14)是空气或蒸汽或空气/蒸汽混合物。
13.根据权利要求12所述的重整反应器(1),其中所述空气/蒸汽混合物是预混合的。
14.根据权利要求1-11中的任一项所述的重整反应器(1),其中所述壳体(2)具有圆柱形形状。
15.一种用于使用根据权利要求1至14所述的重整反应器(1)通过自热反应将烃燃料转化为富氢气体的方法,所述富氢气体用于燃料电池和/或排放处理应用。
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