CN102695670A - 具有集成的碳捕集的重整/水裂解和用于发电的电化学系统的集成 - Google Patents

具有集成的碳捕集的重整/水裂解和用于发电的电化学系统的集成 Download PDF

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CN102695670A
CN102695670A CN2010800481302A CN201080048130A CN102695670A CN 102695670 A CN102695670 A CN 102695670A CN 2010800481302 A CN2010800481302 A CN 2010800481302A CN 201080048130 A CN201080048130 A CN 201080048130A CN 102695670 A CN102695670 A CN 102695670A
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fuel
rich
gas
reaction zone
fuel cell
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CN102695670B (zh
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L-S·樊
F·李
L·曾
D·斯瑞达
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Ohio State Innovation Foundation
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Abstract

提供基本零CO2排放的高效发电方法和系统。形成了在产生气态燃料(H2、CO等)的单元与燃料电池阳极侧之间的闭合回路。在某些实施方案中，对于气态燃料产生也利用来自燃料电池阴极侧的热和含氧排出气体。该用于转化燃料的系统可包括配置用于实施氧化-还原反应的反应器。所得发电效率由于在燃料电池阳极回路中用于气态燃料生产的最小化蒸汽消耗以及战略性质量和能量集成方案而改进。

Description

具有集成的碳捕集的重整/水裂解和用于发电的电化学系统的集成
本发明通常涉及在原位CO2捕集下发电的系统和方法。在某些实施方案中，利用使用一种或多种化学中间体的氧化还原(redox)系统以在CO2捕集下转化碳质燃料。这后面是与电化学转化装置的战略性集成以产生电力。在其他实施方案中，水裂解系统与电化系统集成。通过工艺集成，工艺辅助动力消耗和/或水利用和用于产生蒸汽的能量被最小化。
包括原油、天然气和煤炭的化石燃料代表着全世界现今能量供应的大多数。然而，化石燃料的使用需要将它们转变成载体，诸如热、电力、液体燃料或通过化学转化过程转变为化学品。在日益增加的能量需要和对于来自化石燃料应用的碳排放的伴随担忧之下，广泛的工作已经调整向发展可持续的碳中性的、有效且经济的能量系统。从使用化石燃料到使用核和诸如太阳能和生物质的可再生资源的转换因此代表着这类工作的自然进展。
现有发电技术具有一个或多个以下局限性/缺点：1)高成本(例如，光伏、气化、超超临界粉煤燃烧)；2)低效率(例如，亚临界粉煤燃烧)；3)环境问题(例如，化石燃料发电站)；和4)安全问题(例如，核动力)。
关于常规热电站的常见问题之一在于在冷却和重新加热蒸汽期间的大量能量损失。因此需要使蒸汽产生的需求最小化的系统和方法。
在碳质燃料和空气/蒸汽/CO2之间在反应介质辅助下的化学反应可代表使燃料转化过程中的能量损失最小化的有效方式。已经提出了许多技术来使用金属氧化物转化碳质燃料。例如，Watkins的美国专利3,027,238号描述了一种生产氢气的方法，其包括在还原区中还原金属氧化物和在氧化区中用蒸汽氧化还原了的金属以产生氢气。然而，该技术限于气态燃料转化。此外，该气态燃料仅通过金属氧化物部分转化。Thomas的美国专利7,767,191号、Fan的PCT申请WO 2007082089号和Fan的PCT申请WO 2010037011号描述了通过以下来生产氢气的方法：在基于碳的燃料和金属氧化物之间的还原反应中还原金属氧化物以提供具有较低氧化态的被还原的金属或金属氧化物，和氧化被还原的金属或金属氧化物以产生氢气和具有较高氧化态的金属氧化物。
氢气也可以经光电解、热解和热化学路径由水裂解产生。
为了产生电力，上述方法教导了氢气产物在燃气涡轮机、燃气发动机和/或燃料电池中的进一步转化。然而，大量蒸汽用于这些工艺中以便产生氢气。氢气在常规氢燃料发电装置中的简单转化将导致大量蒸汽/水的冷却和重新加热，产生发电系统的极大不可逆性。
在对电力的需要日益增加的情况下，这要求在效率较高和污染物较少的情况下产生电力的改进的方法、系统和在其中的系统组件。
本发明的实施方案通常涉及在基本零CO2排放的情况下的高效发电方法和系统。形成了在产生气态燃料(H2、CO等)的单元与燃料电池阳极侧之间的闭合回路。在某些实施方案中，对于气态燃料产生也利用来自燃料电池阴极侧的热和含氧排出气体。本文公开的系统的发电效率显著大于目前技术水平方法，这归因于气态燃料生产的最小化的蒸汽消耗、燃料电池阳极回路以及战略性质量和能量集成方案。
鉴于以下附图和详述将更全面地理解由本发明的实施方案提供的其它特征和优势。
当结合以下附图阅读时，可更好地理解本发明的说明性实施方案的以下详述，其中类似结构用类似参考数字表示且其中：
图1为根据一个实施方案在最小蒸汽消耗下产生电力的方法的一般示意图，其中燃料电池与重整或水裂解系统集成以使在该方法中的蒸汽产生需求最小化。
图2为用于在最小蒸汽需求下发电的燃料电池与基于氧化还原的重整/水裂解区块的集成的实施方案的一般示意图。
图3进一步说明基于铁氧化物的氧化还原的重整/水裂解区块和燃料电池系统的实施方案的集成。
图4为使用来源于诸如煤炭或生物质的固体燃料作为原料的合成气的基于铁氧化物的氧化还原方法的实施方案的示意图。
图5为使用固体燃料诸如煤炭、生物质和/或固体废物直接作为原料的基于铁氧化物的氧化还原方法的实施方案及其与燃料电池的集成的示意图。
图6为与燃料电池集成的基于钙的重整/水裂解区块的实施方案的示意图。
图7为用于发电的与燃料电池集成的膜强化的重整/水裂解区块的实施方案的示意图。
图8为使用太阳能或核热能的基于锌的水裂解区块的实施方案及其与使用太阳能或核能的燃料电池的集成的示意图。
图9为说明使用氧化还原反应和固体氧化物燃料电池(SOFC)的集成的煤变电系统的实施方案的更详细示意图。
图10说明以下实施方案，其中来自基于氧化还原的重整/水裂解区块的还原器的未转化的燃料通过辅助燃料电池转化，接着进行氧精加工步骤(polishing step)。在氧化器与燃料电池区块之间的工作流体保持闭合回路。
通常参看图1，本发明的实施方案涉及在最小蒸汽消耗和/或辅助发电及低至零的碳排放下使热和化学能源转化为电力的系统和方法。除非另作说明或上下文另外要求，否则所有百分数都以重量％报道。
在一个实施方案中，系统被分成两个区块或子系统，即重整/水裂解区块和燃料电池区块。所述重整/水裂解区块由蒸汽/CO2和诸如太阳能、核和碳质燃料的能源产生诸如氢气、合成气和/或轻质烃的气态燃料。所述燃料电池区块使来自重整/水裂解区块的气态燃料转化为电力，同时产生含有未转化的燃料和蒸汽和/或CO2的排出物流用于重整/水裂解区块。
燃料电池区块的蒸汽/CO2排出物，其可能含有未转化的燃料，被再循环到重整/水裂解区块以产生气态燃料。在某些情况下，需要排出物的较低程度重新加热和重新加压。在所有情况下，蒸汽冷凝和重新加热是最小的。
为了保持重整/水裂解区块和燃料电池区块两者的操作压力，从主气态物流中分离出排出物和/或气态燃料的流股(bleed)并重新加压。同时，将重新加压的补充物流与主气态物流合并。因为CO2/蒸汽与CO/H2燃料一起在重整/水裂解区块和燃料电池区块之间循环，蒸汽/CO2充当工作流体用于发电。涡轮机(蒸汽涡轮机和燃气涡轮机两者)的使用在该方案中最少化，因为来自燃料电池的部分转化的气态燃料几乎完全再循环到燃料生产阶段。在重整/水裂解区块和燃料电池区块之间形成工作流体的闭合回路。通过使蒸汽冷凝和重新加热最少化且使燃料电池中的燃料转化率最大化，使该工艺的不可逆性被最小化。
在使用诸如固体氧化物燃料电池(SOFC)的高温燃料电池的情况下，耐硫水平比较高。因此，诸如氧化钙吸附剂床的简单热气清除单元可与工作流体回路集成。
重整/水裂解区块的操作压力可与燃料电池区块相当。两个区块都在1.01×105Pa至8.11×106Pa(1atm至80atm)之间的压力下操作。各单元的温度介于300℃至1300℃之间。来自系统的高温高压废物流可用于预热进料物流，产生动力并重新加压补充物流。
用于重整/水裂解区块的能源可为碳质燃料或来自诸如太阳能或核的其他来源的热能。所述碳质燃料可包括煤炭、甲烷、生物质、合成气、石油焦、超稠油、蜡和油页岩。
在使用碳质燃料的情况下，使用载氧体或CO2吸附剂将燃料重整/气化为氢气和/或CO。在使用来自太阳能或核的热能的情况下，使用热化学水裂解方案来将热能转化为氢气和氧气。
图2说明一般工艺构造，其中使用基于金属氧化物的载氧粒子用蒸汽/CO2间接重整或气化碳质燃料。在还原阶段中的反应为
MeOx+燃料＝MeOy+CO2+H2O。
在大多数情况下，选择金属氧化物、反应器设计和操作模式以使得至少80％的燃料转化为CO2和蒸汽。在一些情况下，氧精加工步骤用以将未转化的燃料(＜20％)完全燃烧成可封存的CO2和H2O。在优选的实施方案中，至少95％的燃料转化为CO2和蒸汽。来自还原步骤的排出气体物流因此为可封存的。
在图2的氧化阶段中的反应为
MeOy+(x-y)H2O/CO2＝MeOx+(x-y)H2/CO
从燃料电池阳极侧的排出物中直接取出的用于氧化阶段的进料(在某些情况下进行较低程度的重新压缩)含有燃料，诸如H2/CO。在燃料电池排出物/氧化进料中的燃料浓度通常为0-60％。在进料物流中的H2O/CO2被至少部分地转化为H2/CO，因此在该气态物流中的燃料浓度增加。在氧化阶段的产物物流中的H2/CO浓度通常为30％-99％且比在燃料电池阳极的排出物流中的H2/CO浓度高至少5％。来自氧化阶段的富燃料物流随后被直接引导回到燃料电池以便发电。
图3说明具体工艺构造，其中碳质燃料用作燃料且铁氧化物用作载氧体。在该实施方案中，使用三个反应器氧化还原系统以与在Thomas的美国专利7,767,191号、Fan的PCT申请WO 2007082089号和Fan的PCT申请WO 2010037011号中所公开的方式类似的方式转化燃料。第一反应器，还原器，被构造以将碳质燃料氧化成CO2和蒸汽，同时还原基于金属氧化物的载氧体。在该还原器中需要或产生的热由载氧体粒子提供或除去。第二反应器，氧化器，被构造以用蒸汽或CO2(部分)氧化被还原的载氧体的一部分。第三反应器，燃烧器，使用空气来燃烧氧化器中的被部分氧化的载氧体和来自还原器的被还原的载氧体的剩余部分。
氧化器的进料为来自燃料电池阳极侧的排出物且氧化器的产物直接用作燃料电池阳极的进料。氧化器在工作流体(CO/H2/CO2/H2O)物流中富集燃料含量。在优选的实施方案中，燃料电池阳极侧和氧化器的气态物流形成闭合回路，其中气态物流的加入和排放最低。为了保持工作流体的压力，在主回路或分流回路(split loop)内进行流体的重新加压。在某些实施方案中，高温吸附剂床，诸如使用基于氧化钙的吸附剂的高温吸附剂床，被集成到回路中以防止诸如H2S的污染物的积聚。在其他情况下，仅对排放物流进行硫处理，不处理主工作流体物流。
载氧体包括具有布置在载体上的至少一种金属氧化物的多个陶瓷复合粒子。陶瓷复合粒子描述在Thomas的美国专利7,767,191号、Fan的PCT申请WO 2007082089号和Fan的PCT申请WO 2010037011号中。
回头参看在图3的第一反应器(即，还原器)中的还原反应，该还原器利用诸如合成气、甲烷和轻质烃、煤炭、焦油、油页岩、油砂、沥青砂、生物质、蜡和焦炭的各种碳质燃料来还原含铁氧化物的陶瓷复合材料，以产生被还原的金属和/或金属氧化物的混合物。可能的还原反应包括：
FeOx+燃料→FeOy+CO2+H2O
燃料+CO2→CO+H2
燃料+H2O→CO+H2
FeOx+CO/H2→FeOy+CO2/H2O。
具体地讲，在还原器中形成金属铁(Fe)。同时，自该还原器产生含有至少60％CO2(干基)的排出物流。在优选的方案中，CO2浓度超过95％且可直接封存。
还原器的优选设计包括具有一级或多级的移动床反应器、多级流化床反应器、阶梯式反应器、旋转窑炉或本领域的普通技术人员已知提供逆流气固接触模式的任何合适的反应器或容器。在固体和气体之间的逆流模式用以强化气体和固体的转化。逆流流动模式使固体和气体两者的反混都最少化。此外，其保持反应器的固体出口处于更具还原性的环境下，同时反应器的气体出口保持在更具氧化性的环境下。因此，气体转化和固体转化二者都被强化。
回头参看在图3中的第二反应器(即，氧化器)中的氧化反应，该氧化器使用富含CO2和/或蒸汽的来自燃料电池阳极的排出气体物流将来自还原器的含铁载氧粒子转化到较高氧化态。在该物流中存在的未转化燃料不会参与该反应。可能的反应包括：
Fe+CO2/H2O＝FeO+CO/H2
3FeO+CO2/H2O＝Fe3O4+CO/H2
在某些实施方案中，将仅一部分的来自还原器的被还原的载氧体引入氧化器中，其余部分绕过氧化器且直接送到燃烧器中。通过这样做，从氧化还原区块产生更多的热以补偿在还原器中需要的反应热。或者，将亚化学计量之量的燃料电池阳极排出气体送到氧化器中以使得在随后的燃烧器中产生更多热。
虽然未转化的燃料可能存在于燃料电池阳极排出物流中，在该气体物流中的燃料含量显著富集，引起在铁/铁氧化物和H2O/CO2之间的反应。
氧化器的优选设计也包括移动床反应器和提供逆流气固接触模式的其他反应器设计。优选逆流模式，以便获得蒸汽到氢气的高转化和CO2到CO的高转化。
回头参看在图3中的第三反应器(即，燃烧器)中的氧化反应，含氧气体诸如空气和/或来自燃料电池阴极侧的部分转化的空气至少部分地用以将在自氧化器产生的载氧体中的铁氧化为Fe2O3。在燃烧器中的反应包括：
4FeO+O2＝2Fe2O3
4Fe3O4+O2＝6Fe2O3。
燃烧器的优选反应器设计包括快速流化床反应器、夹带床反应器、输送床反应器或机械输送系统。燃烧器的功能包括：将载氧体氧化到较高氧化态；和使载氧体重复循环到还原器的入口用于另一氧化还原循环。
图4说明转化气态燃料的重整/水裂解区块的一个实施方案的示意流程图。在该实施方案中，使用气化系统以将诸如煤炭、生物质、石油焦和蜡的固体燃料转化为气态燃料。使用诸如含有氧化钙、氧化锌等高温吸附剂的高温吸附剂除去气态燃料中的硫。在气态燃料中需要的硫水平为＜500ppm。在优选的方案中，在气态燃料中的硫水平降低到＜20ppm。
燃料气体随后作为燃料引入在图4中的还原器中用于氧化还原循环。作为来自气化器的气态燃料的替代品，也可将来自重整器或热解器的燃料用于氧化还原系统中。诸如甲烷和轻质烃的气态燃料也可作为燃料直接引入氧化还原系统中。
在Fan的PCT申请WO 2010037011号和本发明的实施方案中描述的方法和系统之间的一个差异在于第二反应器(即氧化器)的气态进料除了H2O和CO2以外含有诸如H2和CO的燃料气体。在某些实施方案中，用于燃烧器的含氧气体包括来自阴极的排出气体的至少一部分。
所述燃烧器为高度放热的。在燃烧器中产生的热可用以补偿在还原器中需要的热。该热也可用以预热进料流且产生用于附加能量消耗的动力。从系统中排出的高压气态物流可用以驱动膨胀机用于气体压缩。
表1说明在所述方法的一个实施方案中主要物流的质量流量。表2说明所述系统的一个实施方案的能量平衡。在这种情况下，甲烷用作燃料。H2O/H2用作工作流体。利用SOFC系统的燃料电池区块将富燃料(H2)气体物流转化为与H2平衡的70％蒸汽。工艺的HHV效率，定义为在电力产品中的能量除以甲烷进料的较高热值，大于60％。在这种情况下，基本所有产生的CO2被压缩到1.52×107Pa(2200psi)且以备封存。
表1.使用甲烷作为燃料的用于发电的集成的重整-燃料电池的质量平衡
*所述CO2物流含有小于0.5％的杂质，诸如未转化的燃料
+来自氧化器的排出物含有70％的H2和30％的蒸汽
表2.使用甲烷作为燃料的用于发电的集成的重整-燃料电池的能量平衡
  甲烷(MWth)  附加动力(MWe)  动力生产(MWe)  净动力(M)We
  1000   80   700   620
在使用煤炭和煤炭气化器的情况下，工艺效率根据煤炭和煤炭气化器的类型而在38％和60％之间变化(HHV，具有CO2捕集)。当将生物质气化并用于氧化还原系统时，效率比其煤炭对应物低1-10％。因为在生物质中的所有CO2都被捕集，所以从生命周期分析观点来看，来自系统的净CO2排放为负。
参看在图5中说明的实施方案，诸如煤炭、生物质、蜡、重质残渣、石油焦和沥青砂的固体燃料在不需要气化器/热解器/重整器的情况下在氧化还原系统中直接转化。该实施方案描绘与如本文中例示的固体氧化物燃料电池(SOFC)集成的直接煤炭氧化还原系统。
由于在约800℃至1000℃之间的在SOFC系统中的高操作温度，释放大量热且需要将其回收以强化工艺效率。当前工艺设计通常组合了SOFC和燃气涡轮机-蒸汽涡轮机系统以便将燃料完全转化为电力。在SOFC中首先转化了约60％-90％的燃料，且剩余部分将在燃气涡轮机系统连同基础兰金循环(bottoming Rankine cycle)中完全转化。然而，该系统的成本高，因为所有三个组件(即，氢气生产系统、燃料电池和涡轮机系统)为资本密集型的。用于发电的常规IGCC-SOFC路径可达到至多55％的效率。
在Fan的PCT申请WO 2010037011号中描述的直接化学回路(DCL)方法将固体燃料转化为氢气。在该DCL系统内，基于铁氧化物的载氧体在三种反应器之中循环，所述三种反应器为还原器、氧化器和燃烧器。在该还原器中，煤炭和/或生物质由含Fe2O3的粒子气化为CO2和H2O，所述含Fe2O3的粒子被还原为Fe和FeO。被还原粒子的一部分与蒸汽在氧化器中反应以产生氢气，同时剩余的被还原的粒子连同来自氧化器的被部分氧化的粒子一起进料到燃烧器中。最后，含Fe2O3的粒子通过用诸如被压缩的空气的含氧气体燃烧而再生并再循环回去。在燃烧器中释放且由铁氧化物载送到还原器的热可完全补偿在系统中的任何热量亏损。通过该DCL系统，氢气和二氧化碳在不同反应器中产生，其通过消除对于产物分离的需要而节约大量能量。并且，其节约CO2去除和空气分离单元的设备投资成本。该DCL系统可从煤炭以70-85％的效率和从生物质以60-75％的效率产生氢气。
在该实施方案中，我们集成了DCL系统和SOFC系统以便自煤炭高效率发电。DCL-SOFC方法和系统具有在高压或低压下的多种构造。具体地讲，我们描述了以下实施方案，其中氧化器和阳极集成在如图5和图9中所示的氢气和蒸汽的闭合回路内。
考虑1000MW的热输入，且相应地在DCL-SOFC系统中加工131.8吨/小时的烟煤。首先将煤炭粉碎成恰当大小的粒子，且随后通过烟气由7.23％湿度干燥到5％湿度。在该DCL系统中，还原器和氧化器两者都采用移动床设计。将含有45.6重量％的Fe2O3和54.4重量％的Al2O3(作为惰性物质)的约3549.5吨/小时的载氧体进料到还原器的顶部，且将煤炭从还原器的中部注入。在移动床还原器中，固体向下流动，而气体向上上升。逆流设计可在900℃、1.01×105Pa(1atm)下将煤炭完全转化为CO2和H2O。将铁氧化物还原成Fe、FeO和痕量FeS的形式。将71.5％被还原的铁粒子用于在氧化器中的氢气产生，且其他28.5％在燃烧器中燃烧。氧化器在850℃下操作，将90.4％摩尔H2O和9.6％摩尔H2的气态混合物转化为35.9％H2O和64.1％H2和ppm水平的H2S的混合物。该气态混合物随后进料到耐硫SOFC的阳极以便发电。同时，Fe和FeO将被氧化成Fe3O4，其流向燃烧器中以便Fe2O3再生。
鼓风器驱动1992吨/小时的空气以进料DCL-SOFC系统。该空气在HRSG段中预热到900℃，且随后行进到SOFC装置的阴极。在于900℃下操作的SOFC中消耗30％的氧气和85％的氢气。废空气用于燃烧器中以使Fe2O3在1280℃下再生。随后将废氢气/蒸汽混合物冷却到约240℃用于随后的脱硫单元。在氢气/蒸汽混合物再循环回到氧化器中之前，仅将少量蒸汽补充到该氢气/蒸汽混合物中。
在DCL-SOFC工艺期间，通过简单冷凝接着压缩到1.37×107Pa(＞135atm)来获得纯度＞99％的CO2以便温室气体控制。压缩步骤消耗约35.8MW的功。诸如Cl、S和Hg的其他污染物可与CO2共封存或通过传统技术除去。可由布置在还原器之前的旋风分离器从载氧体中除去灰分。
表3汇总主工艺物流的流量。由于DCL和SOFC的集成，可由DCL-SOFC系统产生535MW的电力，且可通过回收低位热由蒸汽涡轮机系统产生96MW的电力。总工艺可在CO2压缩的情况下产生640MW的电力，这等于64％的煤炭到动力的效率(HHV)。可进一步优化所说明的实施例以获得大于70％的效率。
DCL-SOFC系统可以高效率将煤炭和生物质的广泛组合转化为电力。可能的设计也包括工作流体(氢气和蒸汽的混合物)的低压和低温操作。也可在SOFC之前用热气清除单元除去在氢气/蒸汽混合物中的H2S。应注意到，当用诸如生物质的低硫燃料(约小于0.2重量％)进料系统时，不需要脱硫单元。
表3.DCL-SOFC工艺的工艺流程图
Figure BDA0000156899470000111
Figure BDA0000156899470000121
Figure BDA0000156899470000131
表4.煤变电工艺构造和工艺效率
Figure BDA0000156899470000132
虽然在该实施方案中例示的DCL-SOFC系统和方法对于工作流体组成、重整/水裂解区块的类型和燃料电池区块具有特殊性，但上述参数的选择具有极大自由度。例如，CO和CO2可代替H2/H2O作为工作流体使用。在Fan的PCT申请WO 2010037011号中描述的各种构造可用于重整/水裂解区块。诸如熔融碳酸盐燃料电池(MCFC)的其他燃料电池也可以与DCL系统集成。在这种情况下，将由DCL还原器产生的CO2的一部分注入MCFC的阴极侧以促进转化。另外，DCL系统可被构造以使得来自还原器的排出物不完全转化。在这种情况下，未转化的燃料在获得浓缩的CO2物流之前被送到另一燃料电池和/或氧精加工步骤(参见图10)。当所有被还原的载氧体粒子都用于氢气生产时，即，直接燃烧的分流比为0，且假设在来自燃烧器的烟气中的高位热可用于加热还原器，发电效率可在CO2压缩的情况下达到70％。表4显示数种构造和相应发电效率。
图6说明以下实施方案，其中钙吸附剂强化重整过程且用作重整/水裂解区块。在这种情况下，燃料在CaO/Ca(OH)2吸附剂和蒸汽/来自燃料电池阳极的富蒸汽排出气体存在下重整/转变成H2：
CaO+CxHy+H2O→CaCO3+H2。
废吸附剂随后在高温下使用来自系统的废热在煅烧炉中再生：
CaCO3＝CaO+CO2。
任选增加水合步骤以使吸附剂再活化。随后压缩并封存来自煅烧炉的浓缩的CO2。在这种情况下，可使一部分工作流体分流以避免工作流体积聚。
图7说明使用膜强化的重整器/水煤气变换反应器作为重整/水裂解区块的选择。在该实施方案中，燃料在重整器中重整/转变，且从膜中同时除去CO2。重整器的保留侧富集具有重整燃料的工作流体，而渗透侧产生浓缩的CO2。
图8说明显示氧化锌水裂解循环和燃料电池的集成的实施方案。在该实施方案中，使用来自太阳能或核能源的热能促进基于氧化锌的水裂解循环。使用从水裂解中获得的氢气来富集包含H2O和H2的工作流体。
本领域技术人员将显而易见的是，可在不偏离本发明的范围的情况下进行各种变化，且所述变化不被视为受说明书和附图中描述的特殊实施方案限制，而是仅受随附权利要求书的范围限制。

Claims (21)

1.一种将碳质燃料或热能转化为电力的系统，其包括：
重整/水裂解区块，用于将富蒸汽和/或CO2的气体物流和碳质燃料和/或热能转化为富燃料(H2和/或CO)的气体物流和排出气体物流；
燃料电池区块，分别用于由阳极和阴极将所述富燃料的气体物流和含氧气体物流转化为贫燃料的气体物流和废含氧气体物流；和
在所述重整/水裂解区块和所述燃料电池区块之间的闭合回路。
3.权利要求1的系统，其中所述燃料电池区块包括固体氧化物燃料电池或熔融碳酸盐燃料电池。
4.权利要求1的系统，其中所述碳质燃料包括合成气、一氧化碳、富甲烷气体、轻质烃、液体碳质燃料、煤炭、生物质、沥青砂、油页岩、石油焦、重质液体烃、蜡以及它们的混合物。
5.权利要求1的系统，其中排放小于10％的所述富燃料或富蒸汽/CO2的气体物流。
6.权利要求1的系统，其中所述热能包括太阳能或核能。
7.权利要求1的系统，其中所述富燃料物流通过水裂解、电解、吸附剂或膜强化的重整和/或水煤气变换反应或蒸汽-铁反应产生。
8.权利要求1的系统，其中使用金属氧化物粒子的氧化还原性质来辅助所述碳质燃料转化。
9.权利要求1的系统，其中使用氧化钙吸附剂来强化所述碳质燃料转化。
10.一种由碳质燃料和蒸汽生产电力和单独的富CO2物流的方法，其包括：
通过在第一反应区中使含Fe2O3的粒子与碳质燃料反应将所述粒子还原到包括金属铁的较低氧化态；
在第二反应区中用来自燃料电池阳极的富蒸汽或CO2的气体氧化含金属铁的粒子的至少一部分，同时产生富燃料(H2和/或CO)的气体物流；
使来自所述第二反应区的富燃料的气体物流回到所述燃料电池的阳极；
在第三反应区中用含氧气体氧化来自所述第一反应区的剩余的含金属铁的粒子和从所述第二反应区中的氧化反应获得的含铁氧化物的粒子，以产生含Fe2O3的粒子；和
使所述含Fe2O3的粒子回到所述第一反应区。
11.权利要求10的方法，其中所述燃料电池包括固体氧化物燃料电池堆。
12.权利要求10的方法，其中所述碳质燃料包括合成气、一氧化碳、富甲烷气体、轻质烃、液体碳质燃料、煤炭、生物质、沥青砂、油页岩、石油焦、重质液体烃、蜡以及它们的混合物。
13.权利要求10的方法，其中所述剩余的CO2在冷凝出湿气之后被封存。
14.权利要求10方法，其中在所述第三反应区中使用的所述含氧气体的至少一部分为从所述燃料电池阴极的出口产生的含氧气体。
15.权利要求10的方法，其中将离开所述第三反应区的所述含氧气体的至少一部分引入所述燃料电池阴极的入口。
16.权利要求10的方法，其中排放小于10％的所述富燃料或富蒸汽/CO2的气体物流。
17.权利要求10的方法，其中所述金属氧化物粒子含有承载材料，所述承载材料包括选自由以下各物组成的集合中的至少一种的陶瓷材料：Al、Ti、Zr、Y、Si、La、CR、Mg、Mn、Cu、Ca的氧化物；Si和Ti的碳化物；海泡石；斑脱土和高岭土。
18.权利要求10的方法，其中将所述富燃料的物流的一部分或所述富CO2的气体的蒸汽引入所述第一反应区的底部以强化所述铁氧化物粒子和所述碳质燃料二者的转化。
19.权利要求10的方法，其中所述碳质燃料为固体粒子形式，所述固体粒子被所述第一反应区中的气体悬浮，直至它们在被淘选向所述第一反应区的顶部之前转化至少50％。
20.权利要求10的方法，其中将从所述闭合回路排放的所述富燃料或富蒸汽/CO2的物流重新加压并引导回到所述闭合回路中。
21.权利要求10的方法，其中从所述第三反应区释放的热用以预热去往所述燃料电池阴极或所述第三反应区的进料气体物流。
22.权利要求10的方法，其中所述燃料电池包括熔融碳酸盐燃料电池且所述燃料电池阴极需要的CO2的至少一部分由通过所述第一反应区产生的富CO2的气体物流提供。
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