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CN102186955B - 将含碳燃料转化为无碳能量载体 - Google Patents

将含碳燃料转化为无碳能量载体 Download PDF

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Publication number
CN102186955B
CN102186955B CN200980141285.8A CN200980141285A CN102186955B CN 102186955 B CN102186955 B CN 102186955B CN 200980141285 A CN200980141285 A CN 200980141285A CN 102186955 B CN102186955 B CN 102186955B
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reactor
metal oxide
reducer
gas
fuel
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CN102186955A (zh
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范良士
李凡星
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Ohio University
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Ohio University
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Abstract

提供了用于将燃料进行转化的系统，该系统包括第一反应器，该第一反应器包括许多陶瓷复合颗粒，所述陶瓷复合颗粒包含位于载体上的至少一种金属氧化物，其中所述第一反应器经配置以用燃料将至少一种金属氧化物还原从而产生还原的金属或还原的金属氧化物；第二反应器，该第二反应器经配置以将来自所述第一反应器的还原的金属或还原的金属氧化物的至少一部分氧化从而产生金属氧化物中间体；空气源；和第三反应器，该第三反应器与所述空气源连通并且经配置以通过将金属氧化物中间体氧化使来自从所述第一反应器排放的固体的剩余部分和从所述第二反应器排放的固体的至少一种金属氧化物再生。

Description

将含碳燃料转化为无碳能量载体
技术领域
本发明总体上涉及将含碳燃料进行转化的系统和方法。通常利用存在一种或多种化学中间体的还原-氧化(氧化还原)反应将含碳燃料进行转化。
背景技术
为了满足不断提高的对清洁和负担得起的能量载体的要求并且确保现代经济的可持续增长，高度需要将含碳燃料例如煤、原油、天然气、生物质、焦油砂和油母岩转化成无碳能量载体的有效且环境友好的技术。能量载体是可用于产生机械功或热或者操作化学或物理过程的物质或现象。
特别地当CO2法规为强制性时，现有的含碳燃料转化技术或者为资金密集型(气化或超-超临界粉煤燃烧)，具有低的效率(亚临界粉煤燃烧)，或者其二者兼有。
含碳燃料和空气/蒸汽/CO2之间借助于金属氧化物介质的化学反应可以表现为一种将燃料进行转化的有效方法。已提出许多使用金属氧化物的技术将含碳燃料进行转化。例如，Watkins的美国专利No.3,027,238描述了生产氢气的方法，该方法包括在还原区中还原金属氧化物，并且在氧化区中用蒸汽氧化经还原的金属以产生氢气。Thomas等的美国公开申请No.2005/0175533和Fan等的PCT申请No.WO2007/082089均描述了通过如下产生氢气的方法：在碳基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经还原的金属或金属氧化物，并且氧化所述经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。以含有金属或金属氧化物的陶瓷材料多孔复合物的形式提供金属或金属氧化物。
一种众所周知的方法为蒸汽-铁方法，其中将煤衍生的发生炉煤气与氧化铁颗粒(随后用蒸汽再生)反应以产生氢气。然而，在该系统中使用流化床，这使铁(Fe)在FeO和Fe3O4之间循环，没有将所述气体完全转化，并且没有能够产生纯的气体流。Ishida等的美国专利No.5,447,024描述了使用氧化镍颗粒通过化学循环方法将天然气转化为待用于涡轮机的热的方法。然而，该技术具有有限的适用性，这是因为其仅能够高花费地将天然气转化为热/电。因此，限制了该方法的原料和产物。
随着逐渐提高的对更清洁和更有效的能量载体例如电、氢气和燃料的要求，出现了对以较高效率和较低排放产生上述能量载体的改进系统和其中的系统部件的需要。
发明内容
本发明的实施方案提供了将固体、液体和气体燃料转化为有效能量载体的新型系统和方法。在一个实施方案中，提供了用于将固体、液体或气体燃料进行转化的系统并且该系统包括含有许多陶瓷复合颗粒的第一反应器。所述陶瓷复合颗粒包含位于载体上的至少一种金属氧化物，并且所述第一反应器经配置以用燃料将该至少一种金属氧化物还原从而产生还原的金属或还原的金属氧化物。该系统包括经配置的第二反应器以将所述还原的金属或还原的金属氧化物至少部分再氧化从而产生金属氧化物中间体。该系统还包括空气源和与该空气源连通的第三反应器并且该第三反应器经配置以通过氧化所述金属氧化物中间体使至少一种金属氧化物再生。在优选的形式中，燃料为固体燃料或气体燃料。任选地，将燃料转化增强气体(优选包括CO2、蒸汽和/或H2)送到其中使该气体与固体流逆向流动的第一反应器。
还提供了制备为例如丸粒形式的陶瓷复合颗粒的方法，该方法包括以下步骤：将金属氧化物与至少一种陶瓷材料混合以形成混合物，将该混合物成粒，和干燥该成粒混合物。将干燥、成粒的混合物加工成使得颗粒的特征长度大于约200μm的颗粒形式。所述颗粒在用于反应器系统之前在约500-约1500℃的温度下热处理并且可以任选地将它们还原和氧化。
考虑以下详细描述、附图和所附权利要求将更全面地理解由本文所述主题的实施方案提供的另外特点和优点。
附图说明
当结合下面的附图阅读时可以最佳地理解本文所述主题的说明性实施方案的以下详细描述，在所述附图中相似的结构用相似的附图标记表示并且其中：
图1是其中提供了由煤和/或生物质产生氢气和/或电的系统而不需要空气分离单元(ASU)的实施方案的示意性图解；
图2A是将煤和/或生物质转化为CO2和蒸汽，并同时将复合颗粒中的Fe2O3还原为Fe和FeO的还原器的示意性图解；图2B和2C描述了还原器中固体燃料注入口和反应器出口的替代设计；
图3是煤焦/生物质转化增强方案的示意性图解；
图4A和4B是还原器的第一级和第二级中气体固体流动型式的示意性图解；
图5是显示移动床还原器的实施方案中煤和氧载体的转化的图表；
图6是将含碳燃料转化为氢气、可封存(sequestrable)的CO2和热的系统的替代实施方案的示意性图解；
图7描述了含碳燃料转化系统的实施方案的热集成方案；
图8是将气体燃料例如合成气、甲烷和其它烃转化为氢气和/或电的系统的示意性图解；
图9是显示在移动床还原器中合成气和氧化铁的转化的图；
图10是显示在移动床还原器中甲烷和氧化铁的转化的图；
图11是显示由移动床氧化器产生的氢气的浓度的图；
图12是显示根据本发明实施方案制得的Fe2O3基金属氧化物复合颗粒的抗碎强度的图；
图13是显示在多个氧化还原循环后氧载体颗粒的磨耗率的图；
图14是显示氧载体颗粒的还原-氧化速率相对于氧化还原循环数目的图；
图15是显示氧载体颗粒在与煤反应4个还原-氧化循环，与合成气反应3个还原-氧化循环和与天然气反应1个还原-氧化循环后的反应性的图；
图16是描述还原器的一个实施方案的期望工作线的图。
图17是由生物质发电的实施方案的示意性图解；
图18是由天然气或其它富含甲烷的气体产生氢气/电的实施方案的示意性图解；
图19是使用非机械气体密封件和固体流动控制装置的氧化还原系统的设计的示意性图解；和
图20描述了非机械气体密封和固体流动控制的替代设计。
具体实施方式
总体上参考图1和8，本文所述主题的实施方案涉及通过金属氧化物陶瓷复合物的氧化还原反应将含碳燃料转化为无碳能量载体例如氢气、热和电的系统和方法。图1描述了当直接使用固体含碳燃料作为原料时系统配置方式的一个实施方案，而图8描述了当使用气体含碳燃料作为原料时系统配置方式的一个实施方案。
在图1所描述的实施方案中，系统10包括第一反应器12(在本文中也称作还原器)，其经配置以将来自燃料源14的固体含碳燃料氧化为CO2和蒸汽并同时将系统中充当氧载体的金属氧化物基陶瓷复合颗粒还原。固体燃料可以通过使其夹带入气体(例如含氧气体)流中来供给。如所示，将金属氧化物复合颗粒供给物储存在容器16中并且在需要使将其供给到还原器12。如图1中所示可以视需要通过管道(conduit)11加入额外的复合颗粒。通过金属氧化物氧载体颗粒至少部分地提供或除去还原器12中所需或产生的热。通过管线18将燃料的燃烧产物(CO2和蒸汽)从还原器12除去。如所示，通过使气态料流穿过给加有来自管线21的冷却剂例如水的换热器19使蒸汽冷凝。CO2料流在任选于分离器20中除去污染物例如汞后送去封存。典型地，由还原器12产生相对纯(即＞95％)的CO2料流。
第二反应器22(在本文中也称作氧化器)经配置以用蒸汽和/或CO2将部分或全部还原的金属氧化物氧载体颗粒(部分地)氧化并且产生基本上纯的氢气料流。通过管线23将氢气从氧化器22移出。如所示，可以使用换热器25用热的氢气料流加热管线40中的进入蒸汽。可以通过分离器27除去氢气料流中的任何污染物例如硫化氢气体。氢气可以用于例如产生电力、液体燃料合成或其它用途。第三反应器24(在本文中也称作燃烧器)使用例如通过可选的压缩机28经由管线26供给的含氧气体如空气燃烧来自氧化器22的被部分氧化的金属氧化物氧载体颗粒和来自还原器12的剩余被还原的金属氧化物氧载体颗粒。在当还原器12需要另外的热的情形中，将由燃烧器24产生的热的至少一部分集成到该还原器。在一些情形中，可以使用空气分离单元(未示出)从空气中分离出氧气并将该氧气送入还原器以将燃料部分燃烧并且将另外的热提供到还原器12。然而，这样的空气分离单元的容量(capacity)比具有相同燃料加工能力的常规气化设备中所用的空气分离单元的容量小得多。因此，图1所描述的系统和方法的一个优点是其可降低将氧气从空气中分离出的空气分离单元的大小或消除对该空气分离单元的需要。这降低了建造和操作燃料转化系统的资金费用并且提高了该系统的总效率。在优选的实施方案中，完全避免了空气分离单元。虽然图1所述的系统描述了固体燃料转化，但还可使用该系统将气体燃料和液体燃料进行转化。燃烧器24中的工作压力可与还原器和氧化器中的压力相仿，或者可以不同。在前种情形中，可便利地使用基于非机械的固体和气体流量控制装置来连接反应器。在后种情形中，应该使用机械阀。然而，可在较低的压力下操作燃烧器，从而产生降低的燃烧器能量消耗。此外，可从由还原器排放出的固体提取热使得在明显低于还原器的温度下操作氧化器。通过这样，提高了蒸汽到氢气的转化。
如图1中所示，可任选地将来自燃烧器24的热废空气送到与涡轮机62和发生器64联接的膨胀机60中并用于产生电66。可以将来自该膨胀机的废气送到用于除去污染物例如硫氧化物和氮氧化物的分离设备。
可通过以下产生另外的热：i)将来自还原器12的还原的金属氧化物氧载体颗粒的较小部分引入氧化器14中，将剩余的还原的金属氧化物氧载体颗粒直接引入到燃烧器24；或者ii)将亚化学计量的量的蒸汽和/或CO2引入到氧化器22使得通过该蒸汽和/或CO2使还原的金属氧化物氧载体颗粒不完全地再生。
氧载体包含许多具有位于陶瓷载体上的至少一种金属氧化物的陶瓷复合颗粒。在Thomas的美国公开申请No.2005/0175533和Fan等的PCT申请No.WO 2007/082089中描述了用于本发明的系统和方法的合适陶瓷复合颗粒。除Thomas所描述的颗粒、颗粒配方和合成方法外，还在下述其它实施方案中，开发了改善陶瓷复合颗粒的性能和强度的方法。
所述其它实施方案包括以下步骤：将金属氧化物与至少一种粉末形式的陶瓷载体材料混合，接着是随着水或粘合材料例如淀粉、硅酸钠和/或硅酸钾的加入进行的可选成粒步骤。可以在成粒之前在混合步骤中加入促进剂物质。然后将成粒的粉末在约50℃-500℃的温度下于空气或氮气中干燥以使水分含量降低到低于10％。然后将成粒的粉末加工成特征长度大于约200μm的丸粒。将成粒的粉末转变为丸粒的方法可以包括但不限于挤出、造粒和加压方法例如制粒。用于生产丸粒的压力为约0.1-25MPa。
在制得含有金属氧化物的陶瓷复合颗粒之后，进行最终处理步骤。最终处理步骤包括在500℃-1500℃下烧结所述颗粒，接着用氢气还原所述颗粒中的金属氧化物，然后用空气氧化所述颗粒，持续至少一个还原-氧化循环从而使所述颗粒的性能稳定。应注意可按照该方法将反应器系统中磨耗产生的废粉末进行再加工和再活化。
金属氧化物组分优选包含选自Fe、Cu、Ni、Sn、Co、Mn、In和它们的组合的金属。载体材料包含选自SiC，Al、Zr、Ti、Y、Si、La、Sr、Ba的氧化物和它们的组合中的至少一种组分。这些载体包括天然矿石例如膨润土和海泡石。陶瓷复合物包含至少约10重量％的载体材料。在其它实施方案中，颗粒包含促进剂材料。该促进剂包含纯金属、金属氧化物、金属硫化物或它们的组合。这些金属基化合物包含Li、Na、K、Rb、Cs、Be、Mg、Ca、Sr、Ba、B、P、V、Cr、Mn、Co、Cu、Zn、Ga、Mo、Rh、Pt、Pd、Ag和Ru中的一种或多种元素。陶瓷复合物包含至多约20重量％的促进剂材料。在陶瓷复合物的示例性实施方案中，金属氧化物包含在为氧化铝(Al2O3)和锐钛矿(TiO2)的混合物的载体上负载的Fe2O3。
再次参考还原器12中发生的还原反应，该还原器利用固体含碳燃料例如煤、焦油、生物质、油母岩、油砂、焦油砂、蜡、焦炭等将陶瓷复合颗粒的最少一种金属氧化物还原以产生还原的金属和/或金属氧化物的混合物。优选将燃料以颗粒形式供给到还原器。可能的还原反应包括但不限于：
2Fe2O3+C→4FeO+CO2
C+CO2→2CO
C+H2O→CO+H2
Fe2O3+CO/H2→2FeO+CO2/H2O
FeO+CO/H2→Fe+CO2/H2O
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，级段式(step)反应器，回转窑炉或本领域技术人员已知的任何其它合适的反应器或容器。在任何反应器设计中，使用金属氧化物氧载体固体颗粒和气体之间的逆流型式提高了气体和固体转化。逆流型式使金属氧化物复合物氧载体固体和气体二者的返混最小化。此外，逆流使还原器12的固体出口28维持处在更大还原性的环境中，并同时使还原器12的气体出口30维持处在更大氧化性的环境中。其结果是，基于热力学原理气体和固体转化均得到提高。
图16例示了使用合成气作为原料的还原器基于热力学分析的优选工作线。优选的工作线(实心直线)对应于气体合成气燃料完全转化(＞99％转化率)为CO2和蒸汽并同时将氧载体颗粒例如含有氧化铁的复合颗粒还原近50％。类似地，当使用固体燃料例如煤时的优选工作模式将使煤完全转化(＞99％转化率)为CO2和蒸汽并同时取决于煤的等级将氧化铁氧载体复合颗粒还原33-85％。一般而言，对还原器中的工作条件进行设置使得至少95％的含碳燃料转化为具有高CO2和蒸汽浓度的气体料流并同时将复合颗粒中的氧化铁还原33％-85％。优选的氧化铁还原率为约36-85％。优选地，还原的氧化铁应该具有约1∶25-3.55∶1的金属铁与氧化亚铁(Wuestite)摩尔比。
含碳燃料的转化率定义为：
X气体＝n消耗的O/n完全转化的O
n消耗的O是指在还原器中氧从氧载体转移到燃料的摩尔数；n完全转化 的O表示使燃料完全转化为CO2和蒸汽所需氧的摩尔数。
氧化铁(或上述任何类型的金属氧化物)的转化率定义为：
y = n ^ O / n ^ Fe - n O / n Fe n O / n Fe × 100 %
此处，nO/nFe对应于Fe2O3中氧原子和铁原子之间的摩尔比，而对应于还原的固体产物即FeOx中氧原子和铁原子之间的摩尔比(0＜x＜1.5)。例如，Fe2O3还原为Fe3O4对应于(3/2-4/3)/(3/2)×100％＝11.11％的固体转化率，FeO对应于33.33％的转化率，Fe对应于100％固体转化率。其它金属氧化物的转化率的定义遵循类似定义。类似定义适用于使用其它金属时。
图2描述了经配置用于固体含碳燃料转化的还原器12的具体实施方案。提供了两级移动床。上级(upper stage)32(第一级)将来自下级(lower stage)34(第二级)的气相和来自固体燃料的挥发物转化为CO2和蒸汽，而下级34将从管线14给加到还原器的固体燃料例如粉状(即颗粒)的煤、焦炭生物质或煤焦转化。通过管线70进入第一级的金属氧化物颗粒，例如含有Fe2O3的颗粒，作为还原的金属(例如Fe)和金属氧化物(例如FeO)的混合物通过管线28离开第二级。通过管线74将含氧气体和可选的燃烧增强气体例如CO2、H2O或H2给加到第二级的底部；热的燃烧气体、CO2和蒸汽通过管线18离开第一级的顶部。例如，当使用含有Fe2O3的颗粒作为氧载体时，Fe2O3转化率为20％-85％。还原器的两级设计允许固体-固体和固体-气体都良好混合。此外，可容易地实现固体移动。在某些实施方案中，还原器中部分粉状固体燃料被气相夹带。其结果是，部分固体燃料向上移动并且在第一级和第二级中均得到燃烧。因此，取决于燃料的物理和化学性能以及反应器中的操作条件，反应器第二级的高度可明显短于或长于反应器第一级的高度。因为反应器设计的灵活性，可以将固体燃料的注入点改动到还原器入口和还原器出口之间的任何位置。
在某些实施方案中，通过管线14注入到还原器第一级32和第二级34之间的粉状固体燃料，被还原器中的气相夹带并且对着金属氧化物氧载体颗粒固体逆向流动。在夹带步骤期间固体燃料转化为CO2和蒸汽。燃料在从还原器12第一级的顶部离开之前至少95％可被转化。部分灰分(ash)也可被夹带并且从该还原器第一级的顶部除去。如图2B和2C中所示，可以在多个位置将粉状固体燃料注入反应器中以使燃料在反应器中较好地分布。
在还原器12的第一级和第二级中发生的反应包括：
颗粒还原：CH4+4Fe2O3→CO2+2H2O+8FeO
煤低温炼焦(devolatilization)：煤→C+CH4
CO+FeO→Fe+CO2
C+CO2→2CO
焦炭气化和颗粒还原：
C+CO2→2CO
C+H2O→CO+H2
CO+FeO→Fe+CO2
H2+FeO→Fe+H2O
涉及固体燃料转化的问题之一是提高固体燃料转化率。图3描述了通过将CO2加入到图2中还原器第二级的底部提高固体转化率的方案。CO2的添加引发了使碳气化并同时将金属氧化物还原“链式反应”。在该过程期间，将产生更多充当气化增强剂的CO2，从而产生进一步提高的反应速率。其它气化增强剂包括H2O和H2。应注意，虽然CO2和H2O的注入可以稍微影响金属氧化物转化率，但是它们仍被认为是可行的气化增强剂，这是因为它们在燃料转化系统中易于获得。获得这类增强剂的一种方法是使来自还原器第一级的含有CO2和蒸汽的废气的一部分再循环到还原器第二级固体出口(底部)。上述燃料转化增强技术还可适用于气态/液态含碳燃料例如甲烷和高级烃的转化，这是因为CO和H2与金属氧化物反应比与烃或固体燃料反应更快。
图4进一步描述了还原器第一级的固体出口(底部)以及还原器第二级的固体出口(底部)的优选设计。第一级具有受限流动出口例如内壁上具有多个叶片38的漏斗型出口36。这样的设计允许气体从第二级的顶部穿透到第一级。同时，金属氧化物基陶瓷复合颗粒将以受控制方式从出口36排放出。在第一级的底部和第二级的顶部之间形成固体颗粒的丘状物。固体燃料分散到第一级的环形区域40并且与金属氧化物基陶瓷复合颗粒充分混合。第二级的固体出口42也使用限流设计例如漏斗型。漏斗优选具有约15-75°的角度。这样的角度允许具有不同尺寸的固体以相近的速度向下移动，从而避免小固体以比较大固体快得多的速率离开还原器。此外，固体可充当气体分配器以确保固体和气体之间的良好混合。在某些实施方案中，可使用多个漏斗型固体出口，特别是对于第一级出口。图2、特别是图2B和2C描述了出口设计的一个实例，其中随3个固体燃料注入口14a、14b和14c一起使用三漏斗型出口36a、36b和36c。这种设计提供了反应器中更均匀的固体分布。还可使用漏斗型出口和固体燃料注入口的其它构造方式。
反应器之间气体流和固体流的有效调节是重要的。可使用机械阀例如旋转阀或球阀-盘式进料器系统控制固体和气体移动。还可使用非机械阀、环路密封(loop seal)和/或区域密封(zone seal)调节气体和固体流。图20中示意性地描述了若干合适的非机械气体密封和固体流动控制装置。可将这些装置安装在反应器或反应器各级之间以控制级间的物质流动。
图5还以图表的形式描述了在移动床还原器中获得的氧化铁基颗粒状氧载体和煤的转化率。下表1中列出了更详细的结果。
表1.使用煤、煤焦和挥发分的燃料反应器示范结果的汇总
  燃料类型   煤挥发分   褐煤煤焦   烟煤煤焦   无烟煤
  燃料转化率(％)   99.8   94.9-99.5   90.5   95.5
  废气中CO2浓度(％干基)   98.8   99.23   99.8   97.3
  气化增强剂   H2/CO2   CO2/H2O   CO2   CO2
一般而言，可随着约33％-85％金属氧化物转化率获得大于90％的固体燃料转化率。来自还原器的废气流在冷凝出蒸汽后具有大于95％的CO2。
现参照图17，其中相似的附图标记表示相似的要素，以示意性形式显示了由生物质发电的实施方案。配置方式与图1中所示配置方式类似。在该实施方案中，将所有还原的金属氧化物颗粒直接送到燃烧器24。其结果是，完全旁通氧化器(未示出)。图2中显示出该实施方案的还原器的优选配置方式。由该系统产生的热气体流可用于锅炉/热量回收蒸汽发生器(HRSG)或者用于具有用于发电的膨胀机/气体涡轮机的联合循环系统。类似地，图1所示实施方案中的燃烧器热气体还可用于锅炉/HRSG，尽管图1中出于说明性目的显示的是膨胀机。可用于图1中所示过程的金属包括Fe、Ni、Cu和Mn。当使用Fe2O3时，就发电目的而言优选的固体还原率为11％-75％。表2显示了由生物质气化获得的实验结果：
表2.使用Fe2O3基陶瓷复合物和气化增强剂(CO2和H2O)由粉状木质生物质获得的实验结果
在一些情形中，固体燃料可以含有杂质例如灰分、硫和汞。固体燃料中的灰分将随金属氧化物基陶瓷复合物一起离开还原器。部分硫还将以金属-硫化合物的形式例如在高温时的FeS(Fe0.877S)离开还原器。其余的硫以H2S/SO2的形式离开还原器。硫可随CO2一起被封存而无需处理。所有汞还将随废气流一起离开还原器。可使用已知技术除去汞或将其封存。
再次参考图1，离开还原器12的固体的一部分将进入第二反应器22(氧化器)。氧化器的优选设计包括移动床反应器、多级流化床反应器、级段式反应器、回转窑炉或本领域技术人员已知的任何其它合适的反应器或容器。在任何反应器设计中，使用氧载体固体颗粒和气体之间的逆流型式来提高气体和固体转化。逆流型式使氧载体固体和气体二者的返混最小化。此外，逆流使反应器22的固体出口保持处在更大氧化性的环境中，并同时使反应器22的气体出口保持处在更大还原性的环境中。其结果是，气体和固体转化均得到提高。
还原器12、氧化器22和燃烧器24之间的连接可以是机械式，即旋转阀或闭锁料斗组件。在另一种设计中，使用非机械阀和气体密封件例如用于循环流化床或流化催化裂化器的那些将还原器12、氧化器22和燃烧器24直接连接。反应器中的压力差以及少量的曝气气体防止产物气体从氧化器22泄漏到还原器12中或反之亦然。图19中描述了这样的非机械反应器设计。仅使用三个连接部(图19中“A”、“B”和“C”)中的一个来控制反应器系统中的全部固体循环速率。优选地，使用氧化器22和燃烧器24之间的连接部(图19中连接部“C”)来调节固体流动。用于反应器各级之间的这种连接的合适非机械阀包括L形阀、J形阀、环路密封或N形阀。此处使用的曝气气体可以是蒸汽和/或废空气。对于燃烧器24和还原器12之间的连接部(图19中连接部“A”)，能够以CO2和/或废空气作为曝气气体使用区域密封或环路密封。对于还原器12和氧化器22之间的连接部(图19中连接部“B”)，能够以H2和/或蒸汽作为曝气气体使用区域密封或环路密封。图20A(N形阀)、20B(L形阀)、20C(环路密封)和20D(竖管和区域密封)中显示了非机械气体密封件和固体阀的优选设计。为还原器12和氧化器22均安装相对平滑的漏斗型反应器出口以确保反应器(具有大的内径)和非机械装置(具有小得多的内径)之间的平滑连接。这减少了曝气气体的使用。还可以在燃烧器24和还原器12之间安装颗粒分离装置(未示出)。使用该装置从燃烧器废气中分离出细料。优选的分离装置具有多于两级。第一级从细粉末和废气中分离出较大的微粒(例如20-200+μm)。第二级从废气中分离出较小的细料。可以将这些细料再加工为较大的颗粒/丸粒。
来自氧化器22的气态原料可以是蒸汽、CO2或它们的组合并且通过管线40进入。当使用蒸汽时，氧化器的蒸汽转化率可以为约50-99％，这取决于氧化器温度和还原器中的固体转化率。当使用Fe2O3基陶瓷复合颗粒时，优选至少5％(按摩尔计)的铁相以获得最佳的蒸汽转化率。当使用CO2时，气体转化率(40-95％)也取决于温度和固体转化率。当使用CO2和蒸汽的混合物时，可将氧化器产物流冷凝并且部分再循环以降低最终产物流中CO2浓度和改善气体转化率。
还原器12中形成的金属-硫化合物将在氧化器22中进行被部分再生，从而产生H2S。因此，氧化器的产物流经常污染有高达750ppm的H2S。可通过吸附剂技术、溶剂技术或其它常规酸去除技术除去H2S。金属氧化物陶瓷复合物中的灰分将在氧化器中不反应并且将随同部分再生的金属氧化物陶瓷复合物一起被排放出。当使用Fe2O3基陶瓷复合物时，来自氧化器的固体产物中的铁相主要为Fe3O4，具有一些剩余的金属-硫化合物。在某些实施方案中，引入亚化学计量的量的蒸汽/CO2以使还原的氧化铁再生为低于Fe3O4的氧化态，例如Fe/FeO混合物、FeO或FeO/Fe3O4混合物。通过这样，可由随后的燃烧器产生的热将增加，代价是降低氧化器中的氢气/CO产量。
再次参考图1，将来自氧化器的部分再生的金属氧化物陶瓷复合颗粒随同来自还原器12的还原的陶瓷复合颗粒的一部分一起引入到第三反应器24(燃烧器)。燃烧器24的优选设计包括快速流化床反应器、载流床(entrained bed)反应器、传送床反应器或机械输送系统。任选地，为了给金属氧化物陶瓷复合物再生提供足够的时间，可以对第三反应器24采用两级设计。对于这样的设计，以鼓泡或湍流流化状态操作第三反应器的位于底部的级I以提供足够的固体和气体停留时间。当使用这样的设计时，级I的直径通常大于级II。
使用燃烧器24以将金属氧化物基陶瓷复合物基本上完全氧化回到其较高氧化态。在该燃烧器中可以使用空气或其它含氧气体。来自燃烧器的气态产物是温度比入口气体温度高得多的贫氧气体。该气体产物还可以含有SO2和NOx。当使用Fe2O3基陶瓷复合物时，固体产物中的铁相主要为Fe2O3。灰分也将随同由磨耗产生的细陶瓷复合物粉末一起出来。部分灰分可以从还原器的气体出口离开。
燃烧器24中产生明显量的热。在一种配置中，气体产物和固体产物都将热从燃烧器带走。通过管线42将固体产物直接注入回到还原器12。其结果是，使用固体产物中携带的显热来补偿还原器12中所需的热。此外，还可通过换热将废气中所含的显热传递到还原器。
可使用机械方法例如旋风分离器分离灰分和废陶瓷复合物。对于15秒的机械分离，证明灰分分离效率为至少75.8％，这对应于当使用烟煤作为固体燃料时陶瓷复合物中小于1％的灰分含量。
现参照图6，图6例示了燃料转化系统的替代配置。在该配置中，其中相似的附图标记表示相似的要素，第一反应器12集成了还原器和燃烧器的功能(例如图1中所示的配置)。第一反应器12具有壳程13和管程15。通过管线14将固体或气体含碳燃料引入到壳程13中，另外在该壳程中将由容器16供给的陶瓷复合颗粒进行转化(即还原)。通过管道19将来自壳程的还原固体的一部分直接再循环回到管程并用空气使其燃烧。燃烧中释放的热补偿壳程中所需的热。此外，来自第三反应器24(燃烧器)的热固体也将部分补偿还原器12中所需的热。通过端口40将蒸汽和CO2供给到氧化器22，而通过管线23移出氢气料流。将具有再生金属氧化物的陶瓷复合颗粒从燃烧器24送回到容器16。可以捕集来自这些颗粒的热并将其用于产生蒸汽或电(管线35所示)。通过管线37除去灰分和废颗粒。
现参照图7，其中相似的附图标记表示相似的要素，图7描述了该方法的一般化热集成方案。在这样的方案中，燃烧器24中产生的热用于：1)补偿还原器12中的热需要，和2)产生电用于寄生式(parasitic)能量消耗。热集成的目的是使系统中产生的过量热最小化，从而使燃料到产物的能量转化最大化。如所示，在还原器12中还原金属氧化物颗粒，同时通过管线94和96将还原的颗粒送到氧化器22和燃烧器24。将氧化的颗粒98从氧化器22送到燃烧器24，并同时将再生的颗粒92再循环回到还原器12。使用箭头H所示反应产生的热将任何所需的热供给到还原器12和用于生产蒸汽或电力(在100处)。
现参照图8，其中相似的附图标记表示相似的要素。图8描述了将气体/液体含碳燃料进行转化的一般化系统。液体含碳燃料可以包括汽油、油类(oil)、石油、柴油、喷气燃料、乙醇等；气态含碳燃料包括合成气、甲烷、一氧化碳、氢气、气态烃气体(C1-C6)、烃蒸气等。
在图8所描述的实施方案中，将气态燃料例如合成气燃料或甲烷进行转化，并且可将该系统分成两个反应器：氢气发生反应器80和燃烧器86。可将该氢气发生反应器进一步分成两级：还原器级82和氧化器级84。氢气发生反应器中的每级还可认为是单独的反应器。
氢气发生反应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、级段式反应器、回转窑炉或本领域技术人员已知的任何合适的反应器或容器。在任何反应器设计中，使用固体和气体之间的逆流型式来提高气体和固体转化。逆流型式使固体和气体二者的返混最小化。此外，其提高了气体和固体的热力学转化。固体的停留时间通常为约15分钟-约4小时。还原器停留时间典型地为约7.5分钟-约2小时，氧化器停留时间也通常为约7.5分钟-约2小时。
在还原器82中，在位于或接近还原器底部处引入气体燃料，并然后使其相对于陶瓷复合颗粒逆流移动。当使用合成气作为燃料，可能的反应包括：
Fe2O3+CO/H2→2FeO+CO2/H2O
FeO+CO/H2→Fe+CO2/H2O
当使用天然气或其它富含甲烷的气体作为燃料时，可能的反应包括：
4Fe2O3+CH4→8FeO+CO2+2H2O
4FeO+CH4→4Fe+CO2+2H2O
CH4+H2O→CO+3H2
CH4+CO2→2CO+2H2
Fe2O3+CO/H2→2FeO+CO2/H2O
FeO+CO/H2→Fe+CO2/H2O
还可将燃料转化增强剂例如CO2、蒸汽和/或氢气引入到还原器级82中以基于类似于图3中所示机制提高甲烷转化。用于甲烷和其它气态/液体含碳燃料转化的热集成方案类似于固体燃料转化方案中所说明的那种。图18描述了甲烷转化的实施方案。
图16中所示的固体工作线是合成气转化的期望工作线。甲烷和其它燃料转化的工作线显示出与图16类似的性质。虽然在各种工作温度、燃料组成和压力下工作线的斜率会改变，但是金属氧化物复合颗粒和气体燃料之间的化学计量比通常维持在约3∶1-1.18∶1。其结果是，金属氧化物转化率通常为33％-85％并同时大于95％的气体燃料被转化为CO2和H2O。例如，当使用甲烷时，金属氧化物转化率通常为35％-70％。当使用Fe2O3基陶瓷复合颗粒时，来自还原器的产物为铁和氧化亚铁的混合物。
可将气态燃料预处理以使其含有小于750ppm的H2S、COS和一些单质汞。还原器配置和陶瓷复合颗粒将允许H2S、COS和汞离开还原器而不与陶瓷复合物反应。其结果是，这些污染物质可随同CO2一起被封存。
图9描述了当使用合成气作为气态燃料时移动床还原器级中合成气和氧化铁的转化率。图10描述了当使用甲烷作为气态燃料时移动床还原器级中甲烷和Fe2O3的转化率。在这两种情形中均使用Fe2O3基陶瓷复合物。如所可看出的，对于～50％Fe2O3转化率，可获得大于99.8％的燃料转化率。
然后将还原的陶瓷复合物的一部分引入到氧化器84。在氧化器中，蒸汽和/或CO2在位于或接近底部处引入并且相对于固体以逆流方式流动。氧化器配置以及气体和固体转化率与先前所讨论的固体燃料转化系统中还原器的类似。
图11显示了在移动床氧化器工作期间氢气产物浓度。获得的平均氢气纯度＞99％。
图8中所示的燃烧器类似于燃料转化系统中的燃烧器。优选的热集成方案利用来自燃烧器的热来提供还原器中的热需要。在优选的配置中，使用旋风分离器或其它机械分离技术将废陶瓷复合物与其它颗粒分离。
图12显示了陶瓷复合物的抗碎强度。在通过还原-氧化循环进行处理后，陶瓷复合颗粒显示出约20MPa的平均抗压强度。
图13显示了陶瓷复合颗粒的磨耗率。陶瓷复合颗粒的平均磨耗＜0.6％/还原-氧化循环。
图14显示了陶瓷复合颗粒的再循环能力。当使用合成气作为燃料时，陶瓷复合颗粒可维持大于100次还原-氧化循环而不丧失它们的反应性。
图15显示了陶瓷复合颗粒的再循环能力。陶瓷复合颗粒可以与各种等级的煤、合成气和烃反应持续多个循环而不丧失它们的反应性。
当还原器和氧化器为移动床而燃烧器为载流床时，陶瓷复合颗粒的优选尺寸为约200μm-约40mm。这样的颗粒尺寸允许在燃烧器中流化而不使其在还原器和氧化器中流化。
用于将固体燃料和烃转化为无碳能量载体的系统和方法所述的实施方案就氢气生产而言可按约65-80％的典型能量转化效率达到高达约90％的HHV能量转化效率。用于将合成气燃料进行转化的系统和方法所述的实施方案就氢气生产而言可按约55-70％的典型能量转化效率达到高达约85％的HHV能量转化效率。表3显示了用于电(power)和H2联产的生物质设备(plant)的性能。
表3用于电和H2联产的生物质设备的性能
  生物质原料(lb/hr)   78800
  HHV输入(MWth)   100
  氢气(lb/hr)   3805(69.05％)
  净电(MWe)   4.55(4.55％)
  效率(％HHV)   73.6
在一种配置方式中，可将还原器与流化催化裂化单元进行集成。还原器将气态烃在加氢裂化器中进行转化并同时还原陶瓷复合物。然后将还原的陶瓷复合物引入到氧化器以产生氢气。然后可将产生的氢气用于加氢裂化。
在一些情形中，可将用于例如烃重整或水煤气变换的反应的催化剂与陶瓷复合物混合以提高燃料转化率。该催化剂的重量含量通常为约0.01％-约30％。
对本领域技术人员而言将明显的是，可以做出各种改变而不背离本发明的范围，并不认为本发明的范围受到说明书和附图中所述的具体实施方案的限制，而是其仅受附属权利要求的范围限制。

Claims (8)

1.用于将燃料进行转化的系统，该系统包括：
第一反应器，该第一反应器包括具有第一级和第二级的移动床，许多陶瓷复合颗粒组成所述移动床，所述陶瓷复合颗粒包含位于载体上的至少一种金属氧化物；用于将燃料和含CO2以及O2的气体提供到所述第二级的入口；其中所述第一级包括与所述第二级连通的限流出口，其中所述第一反应器经配置以用所述燃料在所述颗粒上将至少一种金属氧化物还原从而产生还原的金属或还原的金属氧化物，并且从而将所述还原的金属氧化物颗粒的至少一部分提供至第二反应器并且将所述还原的金属氧化物颗粒的剩余部分提供至第三反应器；
所述第二反应器，该第二反应器与所述第一反应器连通且经配置以将来自所述第一反应器的还原的金属或还原的金属氧化物颗粒的至少一部分氧化从而产生金属氧化物中间体以及富含氢气和/或CO的气体料流；
空气源；和
所述第三反应器，该第三反应器与所述空气源连通并且经配置以通过将金属氧化物中间体和还原的金属和金属氧化物氧化，使来自从所述第一反应器排放的颗粒的一部分和从所述第二反应器排放的颗粒的一部分的至少一种金属氧化物再生；
其中使用来自第三反应器的固体产物中携带的显热来补偿第一反应器中所需的热。
2.如权利要求1所要求的系统，其中第一反应器具有漏斗型出口。
3.如权利要求1所要求的系统，其中第一反应器和第二反应器之间的连接以及第二反应器和第三反应器之间的连接的至少一个为非机械气体密封以及选自环路密封、L形阀、J形阀、N形阀和区域密封的固体流动控制装置。
4.如权利要求1所要求的系统，其中所述第一反应器在所述第一级和所述第二级之间具有环形开口，该环形开口允许气体从第一级的固体排放端口和环形开口的顶部移动离开。
5.如权利要求1所要求的系统，其中所述第二反应器是在固体和气体之间具有逆流流动的具有一级或多级的移动床反应器、多级移动床、回转窑炉或级段式反应器。
6.如权利要求1所要求的系统，其中所述第二反应器包括漏斗型出口。
7.如权利要求1所要求的系统，其中所述第三反应器是快速流化床反应器、载流床反应器或传送床反应器。
8.如权利要求1所要求的系统，其中所述第三反应器包含两级，第一级是鼓泡或湍流流化床反应器，第二级是载流床、快速流化床或传送床反应器。
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