CN113811512A - 产生副产品氨并将氨用作二次燃料的固体氧化物燃料电池装置 - Google Patents

产生副产品氨并将氨用作二次燃料的固体氧化物燃料电池装置 Download PDF

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CN113811512A
CN113811512A CN201980093410.6A CN201980093410A CN113811512A CN 113811512 A CN113811512 A CN 113811512A CN 201980093410 A CN201980093410 A CN 201980093410A CN 113811512 A CN113811512 A CN 113811512A
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ammonia
fuel cell
cathode
fuel
solid oxide
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瓦伦蒂娜·戈德斯坦
阿列克西·科森科
亚历山大·索博列夫
迈克尔·齐尼格拉德
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Samaria Ariel University
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Abstract

一种高温固体氧化物燃料电池装置，其以氢或碳氢化合物燃料为燃料并产生电力和作为副产品的氨，包括：(a)用湿空气供应的阴极区；(b)用燃料供应的阳极区；和(c)设置在阴极区和阳极区之间的氧传导电解质。阴极具有富含氨的尾气流。燃料电池还包括被配置以从尾气流中分离在阴极上产生的氨的气体分离器和用于利用分离的氨的器件，所述器件选自：被配置以产生待与供应到阳极的燃料混合的氢气的氨重整器、用于储存氨的收集罐、和以分离的氨为燃料的辅助固体氧化物燃料电池、及其任意组合。

Description

产生副产品氨并将氨用作二次燃料的固体氧化物燃料电池 装置
技术领域
本申请涉及燃料电池，更具体地，涉及用于产生电力和可供进一步使用的副产品氨的高温固体氧化物燃料电池。
背景技术
燃料电池是将燃料和氧化剂的化学能转化为电能的电化学设备。氢气或含氢物质用作燃料电池中的燃料。将氨直接供应到燃料电池的阳极的燃料电池是本领域已知的(例如参见US7157166)。另一种技术方案涉及以氨燃料分解成氢气和氮气时产生的氢气为燃料的燃料电池(US3532547)。
US8034499公开了一种能量转换系统，其包含用于为SOFC堆提供燃料以产生电力和富氢尾气的氨。在SOFC堆中，氨被裂解为氢气和氮气。氨储存在金属卤化物络合物中，并通过来自SOFC的废热以气态氨的形式释放出来。热交换器横跨SOFC阴极设置，使得进入的空气被阴极排出的空气调和。在两级能量转换系统中，将来自SOFC的富氢尾气作为燃料供应给二次能量转换设备，该设备可以是例如内燃机或燃气涡轮发动机，其可以使例如用于产生额外电力的发电机或动力车辆运转，或使第二燃料电池堆运转。
通过提供能够利用由上述燃料电池产生的副产品氨的设备和方法来进一步提高用氢或碳氢化合物燃料供应的高温固体氧化物燃料电池的效率是长期存在的需求。
发明内容
简言之，能量转换系统包括固体氧化物燃料电池堆，固体氧化物燃料电池堆用于产生电力和作为副产品的氨气，氨气为第二能量转换设备(例如其他燃料电池)提供燃料或用于不同用途。
上述固体氧化物燃料电池包括：(a)用氢或碳氢化合物燃料供应的阳极区；(b)用湿空气供应的阴极区；(c)设置在阴极区和阳极区之间的氧传导电解质。
本申请的核心目的是提供具有富含氨的尾气流的阴极区。该燃料电池还包括：气体分离器，该气体分离器被配置以从尾气流中分离在阴极上产生的氨；和用于利用分离的氨的器件，该器件选自：氨重整器，该氨重整器配置以产生待与供应到阳极的所述燃料混合的氢气；收集罐，该收集罐用于储存氨；和辅助固体氧化物燃料电池，该辅助固体氧化物燃料电池以分离的氨为燃料；及其任意组合。
本申请的另一个目的是公开包括传热器件的燃料电池，该传热器件被配置以将由燃料电池产生的热量传递到氨气分离器。本申请的另一个目的是公开气体分离器，该气体分离器可选地包括：
氨吸收器、氨蒸发器和分馏器；所述蒸发器由传递到所述蒸发器的由阴极和阳极之间的电化学反应产生的热量加热；
压缩机和膜装置，该压缩机被配置以将所述尾气泵送通过所述膜装置，使得将氨与其他排出的气体分离；
压缩机，该压缩机被配置以对所述尾气加压，使氨液化，同时将所述尾气的其他成分排放到大气中。
本申请的另一个目的是公开一种通过以氢或碳氢化合物燃料为燃料的高温固体氧化物燃料电池装置产生作为副产品的氨的方法。前述方法包括步骤：(a)提供高温固体氧化物燃料电池装置，该高温固体氧化物燃料电池装置包括：(i)用湿空气供应的阴极区；(ii)用所述燃料供应的阳极区；(iii)设置在阴极区和阳极区之间的氧传导电解质；该阴极具有富含氨的尾气流；该燃料电池还包括：气体分离器，该气体分离器配置以从所述尾气流中分离在阴极上产生的氨；和用于利用分离的氨的器件，该器件选自：氨重整器，该氨重整器被配置以产生待与供应到阳极的燃料混合的氢气；收集罐，该收集罐用于储存氨；和辅助固体氧化物燃料电池，该辅助固体氧化物燃料电池以分离的氨为燃料；及其任意组合；(b)向阳极区供应燃料；(c)向阴极区供应湿空气；(d)运行燃料电池；(e)在阴极区产生作为副产品的氨；(f)从尾气流中分离氨；和(g)通过选自以下方式中的至少一种方式利用分离的氨：将氨重整为氢气、将氨储存在收集罐中、以及为辅助燃料电池提供燃料。
附图说明
为了理解本申请并了解如何在实践中实施本申请，现在参考附图并且仅通过非限制性实施例的方式来描述多个实施方式，其中：
图1为设置有氨重整器的高温固体氧化物燃料电池装置的示意图；
图2为设置有氨收集罐的高温固体氧化物燃料电池装置的示意图；
图3为根据本申请的设置有以氨为燃料的二次能量转换设备的高温固体氧化物燃料电池装置的示意图；
图4为基于分馏器的分离器的详细示意图；
图5为基于膜的分离器的详细示意图；以及
图6为基于膨胀的分离器的详细示意图。
具体实施方式
提供以下描述以使本领域技术人员能够利用所述申请，并阐明发明人构思的本申请的最佳实施方式。然而，既然本申请的一般原理已被具体定义为提供以氢或碳氢化合物燃料为燃料并产生电力和副产品氨的高温固体氧化物燃料电池装置，各种修改对于本领域技术人员来说仍然是显而易见的。
现参照图1至图3，其展示了高温固体氧化物燃料电池装置100a至100c的可选实施方式，高温固体氧化物燃料电池装置100a至100c以氢或碳氢化合物燃料为燃料，氢或碳氢化合物燃料供应给阳极燃料电池，湿空气供应给阴极，并且在燃料电池的阴极上产生作为副产品的氨。
参照图1至图3，氢或任何碳氢化合物燃料被供应到燃料电池110的阳极区111。同时，由加湿器130产生的湿空气通过通道131供应到阴极区115。113是氧传导电解质。装置包括将氨与其他气体分离的系统-150。标记140表示由燃料电池110提供给负载(未示出)的电能。
在装置100a(图1)中，由分离器150分离的氨被供应到重整器120，重整器120用于裂解氨并产生氢气，氢气与被供应到阳极区111的燃料混合。氮气被排放到大气中。
图2示出了实施方式100b，其中分离的氨通过管道151被收集并储存在罐170中。
在图3中，实施方式100c(图3)设置有辅助燃料电池180，该辅助燃料电池180通过管道175以收集并储存在罐170中的氨为燃料。
由辅助燃料电池180产生的电能用140a表示。来自阳极区111的尾气流包括水蒸气和二氧化碳(в случае метана)。来自阴极区115的尾气流包括在阴极区115内产生的氨。阴极尾气流经通道119供应到氨分离器150。可选地，如下文所公开的，基于通过传热器件117对吸收在水中的氨的蒸发和分馏，在燃料电池110内产生的热量被传递到氨分离器150。
燃料电池10的运行可以通过以下等式示意性地描述：
使用甲烷作为燃料时：
阴极N2+3H2O+6e-→2NH3+3O2- (1)
O2+4e-→2O2- (2)
阳极CH4+5O2-→CO2+2H2O+1/2O2+10e- (3)
总反应СH4+N2+H2O+1/2О2→2NH3+CO2+O2 (4)
对于氢燃料电池：
阴极N2+3H2O+6e-→2NH3+3O2- (1a)
O2+4e-→2O2- (2a)
阳极5H2+5O2-→5H2O+10e- (5)
总反应N2+O2+5H2→2NH3+2H2O (6)
现参照图4、图5和图6，其分别呈现了氨分离器的可选实施方式150a、150b和150c。图4中的实施方式150a包括氨吸收器200、氨蒸发器210和分馏器220。尾气通过通道119供应到氨吸收器中，在氨吸收器中氨被吸收在水中，然后被供应到氨蒸发器210中，氨蒸发器210通过传热器件117由燃料电池110(未示出)产生的热量加热。在氨蒸发器210内产生的蒸气被提供到分馏器220，在分馏器220中氨和水蒸气馏分被分离。
参照示出了实施方式150b的图5，尾气经由通道119被收集在罐230中，罐230被配置用于储存排出的尾气。前述尾气被压缩机240泵送并通过膜装置250，使得氨155与其他排出气体160分离。
在图6中，示出了实施方式150c。从阴极区(未示出)排出的尾气通过通道119供应到罐230。罐230被配置用于积聚上述尾气。压缩机240用于对尾气加压，使得氨液化并积聚在罐260中，同时将尾气的其他成分排放到大气中。氨在通过膨胀阀270时被冷却。因此，低温气态氨可用于冷却在热交换装置280中循环的工作体。此外，气态氨经由管道155提供给消耗者。
根据本申请，公开了一种以氢或碳氢化合物燃料为燃料并产生副产品氨的高温固体氧化物燃料电池装置。上述燃料电池包括：(a)用湿空气供应的阴极区；(b)；用所述燃料供应的阳极区(c)设置在所述阴极区和阳极区之间的氧传导电解质。
本申请的一个核心目的是提供具有富含氨的尾气流的阴极；所述燃料电池还包括：气体分离器，该气体分离器被配置以从尾气流中分离在所述阴极上产生的氨；和用于利用分离的氨的器件，该器件选自：氨重整器，该氨重整器被配置以产生待与供应到所述阳极的所述燃料混合的氢气；收集罐，该收集罐用于储存所述氨；和辅助固体氧化物燃料电池，该辅助固体氧化物燃料电池以所述分离的氨为燃料；及其任意组合。
根据本申请的另一个实施方式，气体分离器包括氨吸收器、氨蒸发器和分馏器；所述蒸发器由传递到所述蒸发器的由阴极和阳极之间的电化学反应产生的热量加热。
根据本申请的另一个实施方式，气体分离器包括压缩机和膜装置。该压缩机被配置以将所述尾气泵送通过所述膜装置，从而将氨与其他排出气体分离。
根据本申请的另一个实施方式，气体分离器包括压缩机，该压缩机被配置以对尾气加压，使氨液化，同时将尾气的其他成分排放到大气中。
根据本申请的另一个实施方式，公开了一种通过以氢或碳氢化合物燃料为燃料的高温固体氧化物燃料电池装置产生副产品氨的方法。前述方法包括步骤：(a)提供高温固体氧化物燃料电池装置，该高温固体氧化物燃料电池装置包括：(i)用湿空气供应的阴极区；(ii)用所述燃料供应的阳极区；(iii)设置在所述阴极区和阳极区之间的氧传导电解质；所述阴极具有富含氨的尾气流；所述燃料电池还包括：气体分离器，该气体分离器被配置以从所述尾气流中分离在阴极上产生的氨；和用于利用分离的氨的器件，该器件选自：氨重整器，该氨重整器被配置以产生待与供应到所述阳极的所述燃料混合的氢气；收集罐，该收集罐用于储存所述氨；和辅助固体氧化物燃料电池，该辅助固体氧化物燃料电池以所述分离的氨为燃料；及其任意组合；(b)向所述阳极区供应所述燃料；(c)向所述阴极区供应湿空气；(d)运行所述燃料电池；(e)在所述阴极区产生作为副产品的所述氨；(f)从所述尾气流中分离所述氨；和(g)通过选自以下中的至少一种方式利用分离的氨：将氨重整为氢气、将氨储存在所述收集罐中以及为辅助燃料电池提供燃料。
根据本申请的另一个实施方式，从所述尾气流中分离所述氨的步骤包括：通过传热器件加热所述尾气流，所述传热器件被配置以将由所述燃料电池产生的热量传递到所述氨气分离器。
本申请的上述实施方式旨在仅作为示例。在不脱离本发明的范围的情况下，本领域技术人员可以对特定实施方式进行改变、修改和变化，本发明的范围仅由所附权利要求限定。

Claims (4)

1.一种高温固体氧化物燃料电池装置，其以氢或碳氢化合物燃料为燃料并产生电力和作为副产品的氨，所述燃料电池包括：
a.用湿空气供应的阴极区；
b.用所述燃料供应的阳极区；
c.设置在所述阴极区和所述阳极区之间的氧传导电解质区；
其中所述阴极具有富含氨的尾气流；所述燃料电池还包括被配置以从尾气流中分离在所述阴极上产生的氨的气体分离器和用于利用分离的氨的器件，所述器件选自：被配置以产生待与供应到所述阳极的所述燃料混合的氢气的氨重整器，用于储存所述氨的收集罐，和以所述分离的氨为燃料的辅助固体氧化物燃料电池，及其任意组合。
2.根据权利要求1所述的燃料电池装置，其中，所述气体分离器包括压缩机和膜装置；所述压缩机被配置以将所述尾气泵送通过所述膜装置，使得氨与其他排出的气体分离。
3.根据权利要求1所述的燃料电池装置，其中，所述气体分离器包括压缩机，所述压缩机被配置以对所述尾气加压，使得氨液化，同时将所述尾气的其他成分排放到大气中。
4.一种通过以氢或碳氢化合物燃料为燃料的高温固体氧化物燃料电池装置产生作为副产品的氨的方法；所述方法包括步骤：
a.提供向阳极加燃料氢或碳氢化合物燃料以及用湿空气供应阴极区的高温固体氧化物燃料电池装置，所述燃料电池包括：
i.用湿空气供应的阴极区；
ii.用所述燃料供应的阳极区；
iii.设置在所述阴极区和所述阳极区之间的氧传导电解质；
所述阴极具有富含氨的尾气流；所述燃料电池还包括被配置以从尾气流中分离在所述阴极上产生的氨的气体分离器和用于利用分离的氨的器件，所述器件选自：被配置以产生待与供应到所述阳极的所述燃料混合的氢气的氨重整器，用于储存所述氨的收集罐，和以所述分离的氨为燃料的辅助固体氧化物燃料电池，及其任意组合。
b.向所述阳极区供应所述燃料；
c.向所述阴极区供应湿空气；
d.运行所述燃料电池；
e.在所述阴极区产生作为副产品的所述氨；
f.从所述尾气流中分离所述氨；
g.通过选自以下方式中的至少一种方式来利用分离的氨：将氨重整为氢气、将氨储存在所述收集罐中以及为辅助燃料电池提供燃料。
CN201980093410.6A 2019-01-02 2019-09-18 产生副产品氨并将氨用作二次燃料的固体氧化物燃料电池装置 Pending CN113811512A (zh)

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