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CN102405274B - 从废气中分离二氧化碳的方法和设备 - Google Patents

从废气中分离二氧化碳的方法和设备 Download PDF

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CN102405274B
CN102405274B CN201080017230.9A CN201080017230A CN102405274B CN 102405274 B CN102405274 B CN 102405274B CN 201080017230 A CN201080017230 A CN 201080017230A CN 102405274 B CN102405274 B CN 102405274B
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加里·爱德华·梅修斯
詹姆斯·M·小麦克莱兰
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Abstract

本发明提供了从废气中分离二氧化碳并重新使用该废气作为没有排放顾虑的再循环气体的方法和设备。将气体源分为工艺气体和废气。将工艺气体和烃混合，并且进料到重整器中，用于形成还原气体；将至少部分废气进料到二氧化碳洗涤器中，形成与还原气体混合的贫二氧化碳气体。任选地，气体源和还原气体与用于将铁的氧化物转化为金属铁的直接还原方法相关联。

Description

从废气中分离二氧化碳的方法和设备
相关申请的交叉引用
本非临时本专利申请/专利要求于2009年4月20日提交的，命名为“从炉顶媒气燃料中分离二氧化碳的方法和设备(Method and Apparatus forSequestering Carbon Dioxide From a Top Gas Fuel)”的美国临时专利申请61/170,999的优先权的权益，该美国临时专利申请的全部内容通过引用结合在此。
发明领域
包括其它工艺在内，本发明总体上涉及了由铁的氧化物直接还原为金属铁的方法和设备。更具体地，本发明涉及了与这种工艺相关的从废气中分离二氧化碳的方法和设备。
发明背景
在许多工业过程中，对于从二级燃料源，例如炉顶气(top gas)燃料源中用直接还原方法除去二氧化碳有效且高效率的方法存在需要。换句话说，在许多工业过程中，对于从其它的废燃料源中除去二氧化碳，以使其可以被用作没有排放问题的一级燃料源有效且高效率的方法存在需要。在一些情况下，政府政策已经要求了这样的二氧化碳移除，并且对于二氧化碳排放控制的需要在未来只会增加。直接还原包括铁的氧化物矿石还原为金属化的铁粒料、团块或压块，其中铁的氧化物由含有氢气和/或者一氧化碳的气体还原，产生二氧化碳副产物。
发明概述
在本发明的一个典型实施方案中，从炉顶气燃料中分离二氧化碳的方法，包括：将炉顶气分为工艺气体和炉顶气燃料：将工艺气体与烃混合，并且将得到的重整器进料气体进料到二氧化碳和蒸汽重整器中，以重整重整器进料气体并形成还原气体；将炉顶气燃料进料到二氧化碳洗涤器中，以从炉顶气燃料中除去至少一些二氧化碳，并且在加入烃之后形成重整器燃料气体，将该重整器燃料气体进料到二氧化碳和蒸汽重整器中。该方法也包括压缩工艺气体和炉顶气燃料。该方法进一步包括从炉顶气产生蒸汽。该方法还进一步还包括洗涤炉顶气以除去灰尘。任选地，炉顶气从还原炉中获得。任选地，该方法还进一步包括将还原气体与氧、烃混合以形成促动气(促动gas)，并将该促动气进料到还原炉中。该二氧化碳洗涤器也产生贫二氧化碳气体。该方法还进一步包括将贫二氧化碳气体与还原气体混合。任选地，该方法还进一步包括在与还原气体混合或者被用作燃料之前，预热贫二氧化碳气体。二氧化碳和蒸汽重整器也产生烟道气。该方法还进一步包括从烟道气产生蒸汽。任选地，该方法还进一步包括使用烟道气预热其它气体。任选地，炉顶气和促动气与用于将铁的氧化物转化为金属铁的直接还原方法是相关联的。
在本发明的另一个典型实施方案中，从炉顶气燃料中分离二氧化碳的设备，包括：一个或者多个用于将炉顶气分为工艺气体和炉顶气燃料的导管；一个或者多个用于将工艺气体与烃混合，并且将得到的重整器进料气体进料到二氧化碳和蒸汽重整器中，以重整重整器进料气体并且形成还原气体的导管；以及一个或者多个用于将炉顶气燃料进料到二氧化碳洗涤器中的导管，以从炉顶气燃料中除去至少一些二氧化碳，并且在加入烃之后形成重整器燃料气体，将该重整器燃料气体进料到二氧化碳和蒸汽重整器中。设备还包括一个或多个用于压缩工艺气体和炉顶气燃料的气体压缩机。设备进一步包括用于从炉顶气产生蒸汽的低压蒸汽锅炉。该设备还进一步包括用于洗涤炉顶气以除去灰尘的湿式洗涤器。任选地，炉顶气从还原炉中获得。任选地，该设备还进一步包括一个或者多个用于将还原气体与氧和烃混合以形成促动气并将该促动气进料到还原炉中的导管。二氧化碳洗涤器也产生贫二氧化碳气体。设备还进一步包括一个或者多个用于混合贫二氧化碳气体和还原气体的导管。任选地，该设备还进一步包括用于在将其与还原气体混合或者将其用作燃料之前预热贫二氧化碳气体的预热器。二氧化碳和蒸汽重整器也产生烟道气。该设备还进一步包括从烟道气生成蒸汽的低压蒸汽锅炉。任选地，该设备进一步包括一个或者多个用于利用烟道气预热其它气体的导管。任选地，炉顶气和促动气与用于将铁的氧化物转化为金属铁的直接还原方法是相关联的。
在本发明的进一步典型实施方案中，从废气中分离二氧化碳并重新使用其作为没有排放顾虑的再循环气体的方法，包括：将气体源分为工艺气体和废气：将工艺气体和烃混合，将得到的进料气体进料到重整器中，用于重整该进料气并形成还原气体；将至少部分废气进料到二氧化碳洗涤器中用于从废气中除去至少一些二氧化碳，并形成与还原气体混合的贫二氧化碳气体。任选地，该方法也包括将至少部分废气进料到二氧化碳洗涤器中，以从废气中除去至少一些二氧化碳，并在加入进料到重整器中的烃之后形成燃料气体。
本发明的二氧化碳分离方法提供了一种有效回路，通过该回路可以重新俘获在初级过程中没有使用并且作为废气排出的一氧化碳和氢气，同时将不希望的排放最小化。
附图简述
在此通过引用多个附图示例和描述本发明，适当地，附图中的相同的附图标记被用于指示相同的方法步骤/设备部件，其中：
图1是本发明的用于从炉顶气燃料中分离二氧化碳的方法/设备的过程/原理图；和
图2是本发明的直接还原过程的方法/原理图。
发明详述
参看图1，在本发明的一个典型实施方案中，从炉顶气燃料10中分离二氧化碳的设备固有地包括垂直的竖式还原炉(vertical shaft-typereduction furnace)12等。在该实例中，还原炉12包括进料斗(没有被显示出来)，将铁的氧化物粒料、团块或压块在设定的速度下加入该进料斗中。铁的氧化物粒料、团块或压块从进料斗通过进料管道(没有被显示出来)，利用重力下降到还原炉12中，该进料管道起气体密封管道的作用。在还原炉12的底部是排放管道(没有被显示出来)，其进一步起气体密封管道的作用。排放进料器(discharge feeder)(没有被显示出来)，例如电振动进料器等，被安置在排放管道下方，并且接收金属铁粒料、团块或压块，从而建立了用于炉料(burden)重力下降通过还原炉12的系统。
在还原炉12的大约中点处是促动和风嘴系统(没有被显示出来)，通过该促动和风嘴系统热在大约700℃至大约1050℃的温度引入还原气体。热还原气体向上流动通过还原炉12的还原区域，与粒料、团块或压块的流动相反，并通过位于还原炉12顶部的排气管道(没有被显示出来)离开还原炉12。进料管道在排气管道的下方延伸，该几何设置创造了废气分离压力通风系统(disengaging plenum)，其允许废气从原料管道分离并自由流向排气管道。热还原气体，在从促动和风嘴系统流向排气管道的过程中，起到加热铁的氧化物粒料、团块或压块，并将它们还原为金属铁粒料、团块或压块(也就是通过直接还原)的作用。热还原气体含有将铁的氧化物粒料、团块或压块还原并产生含有二氧化碳和水蒸气的废气或者炉顶气的氢气、氮气、一氧化碳、二氧化碳、甲烷和水蒸气。
参考图2，在此利用的直接还原方法通过调节贫二氧化碳气体、天然气和氧气向刚刚前面所述还原气体的加入，控制了还原条件、温度和促动气进入到还原炉12时刻的化学过程。这些直接还原方法一般描述在以下专利中：美国专利3,748,120，题目为“将铁的氧化物还原为金属铁的方法(Method of Reducing Iron Oxide to Metallic Iron)”，美国专利3,749,386，题目为“在气体还原过程中还原铁的氧化物的方法(Method for Reducing IronOxides in a Gaseous Reduction Process)”，美国专利3,764,123，题目为“用于将铁的氧化物还原为金属铁的设备(Apparatus for Reducing Iron Oxide toMetallic Iron)”，美国专利3,816,101，题目为“在气体还原过程中还原铁的氧化物的方法(Method for Reducing Iron Oxides in a Gaseous ReductionProcess)”，美国专利4,046,557，题目为“用于制备金属铁粒子的方法(Method for Producing Metallic Iron Particles)”，美国专利5,437,708，题目为“在竖式炉中制备铁的碳化物(Iron Carbide Production in Shaft Furnace)”，以上专利的全部内容通过引用结合在此。
还原炉的炉料充当大型绝热反应器并且促进促动气注入区域内的平衡反应。当促动气进入还原炉12并通过炉料时，气体反应至其平衡组成和温度，该过程是在还原炉12上部的炉料热电偶上观察到的。
渗碳反应被下列还原气体流因素影响：
1.初始还原气体氢气：一氧化碳比例；
2.初始还原气体甲烷含量；
3.初始还原气体温度；
4.还原气体中天然气的加入；
5.还原气体中氧气的加入；
6.还原气体中贫二氧化碳气体的加入；
7.最终促动气还原剂：氧化剂比例；和
8.最终促动气气压
在一般操作条件下，初始还原气体品质被紧密地控制，并成为直接还原方法的主要稳定性因素。当还原气体流向还原炉12时，基于最终促动气的甲烷含量分析加入天然气。这提供了一种对于初始还原气体中甲烷含量任何变化的稳定化调节，并影响了最终促动气的渗碳潜能。氧气被加入到还原气体中以提高最终促动气的温度，并改善铁矿石还原过程的动力学。
任选地，所使用的操作条件包括预热加入的天然气，还原气体甲烷含量等于或者少于大约12％，氧气加入流/吨等于或者少于大约30Nm3/t。
在直接还原设备的使用过程中，气体离开还原气体源40，并且第一传感器进行气体分析并测量气体温度。天然气然后在天然气入口与该气体混合。氧气然后在氧气入口与上述气体和天然气混合物相混合，从而形成促动气。第二传感器在促动气进入还原炉12之前进行气体分析并测量促动气温度。
再次参看图1，根据本发明，来自还原炉12排气管道的炉顶气通过另一管道(没有被显示出来)流向低压蒸汽锅炉14。这使得能够有效地产生在该工艺中用于别处的蒸汽，例如在此下面更详细描述的二氧化碳除去步骤。将锅炉给水进料到低压蒸气锅炉14中，如上面所述，产生的蒸汽通过该工艺再循环或者用于别处。
炉顶气然后被引导至湿式洗涤器20，设置该湿式洗涤器通过水输出冷却炉顶气并除去灰尘。湿式洗涤器20可以是本领域中普通技术人员已知的任何常规类型，例如带有填料塔的文丘里管(没有被显示出来)，其中炉顶气向下流通过文丘里管，然后向上通过逆流填料到达冷却水。
炉顶气通过阀(没有被显示出来)的影响下以两股流离开湿式洗涤器20。第一流代表工艺气体，第二流代表炉顶气燃料(也就是废料)。这些流的比例是由与第一流连接的二氧化碳和蒸汽重整器24中可获得的热量限定的，所述可获得的热量典型为恒定的，从而得到代表性的比例是1∶1(利用再循环的贫二氧化碳气体)、2∶1(没有利用再循环的贫二氧化碳气体)，等等。
来自湿式洗涤器20的工艺气体被进料到压缩机22中并被压缩到所需的压力，然后被进料到混合器中(没有被显示出来)，在那里将工艺气体与天然气混合。该重整器进料气体然后被进料到二氧化碳和蒸汽重整器24中。二氧化碳和蒸汽重整器24包括燃料点火的燃烧器(没有被显示出来)，通过燃烧及多个催化重整器管(没有被显示出来)产生包含氮气、二氧化碳和水的热烟道气，后者利用重整器进料气体和来自燃烧的热量形成还原气体，该还原气体在引入氧气、天然气以及贫二氧化碳气体得到促动气之后被进料回到还原炉12中。
来自湿式洗涤器20的炉顶气燃料在被引入到二氧化碳洗涤器28之前，还被进料到压缩机26中并被压缩到所需压力。二氧化碳洗涤器28具有低压蒸汽的输入和锅炉给水、硫和二氧化碳的输出，该低压蒸汽任选地从用于从炉顶气燃料10中分离二氧化碳的设备的低压蒸汽锅炉14，32的任一个中获得。锅炉给水可以被输入到用于从炉顶气燃料10中分离二氧化碳的设备的低压蒸汽锅炉14，32的任一个中。二氧化碳洗涤器28的另一个输出是贫二氧化碳气体，其当与天然气混合时，部分变成重整器燃料气体，该重整器燃料气体被进料到二氧化碳和蒸汽重整器24中。
二氧化碳洗涤器28可以包括任何类型的烷醇胺，例如MEA、MEDA，诸如此类，或者本领域中普通技术人员已知的任意类型的热钾洗涤系统。低压蒸汽被用于再生二氧化碳洗涤器28中使用的溶液，并作为锅炉给水离开。在二氧化碳洗涤方法中，硫和二氧化碳被从炉顶气燃料中分离。减去硫和二氧化碳的炉顶气燃料作为贫二氧化碳气体离开二氧化碳洗涤器28。再次，将部分贫二氧化碳气体与天然气混合形成重整器燃料气体，并通过燃料点火的燃烧器引入到二氧化碳和蒸汽重整器24中。将剩余的贫二氧化碳气体再循环并与还原气体混合，将其在引入氧气和天然气之后进料回到还原熔炉12中，从而形成促动气。任选地，后一部分的贫二氧化碳气体，或者全部的流，在与存在的还原气体混合或者使用其作为燃料之前被引入到预热器30中。
在本发明的一个典型的实施方案中，该贫二氧化碳气体/还原气体流最终表现为供给到还原熔炉12中的促动气的大约20％，而二氧化碳和蒸汽重整器还原气体流最终表现为供给到还原熔炉12中的促动气的大约80％，尽管在此也预期其它百分比。
烟道气排放管道(没有被显示出来)被设置在二氧化碳和蒸汽重整器24上，用于在燃烧之后除去包含氮气、二氧化碳和水的烟道气。烟道气流经一个或者几个热交换器，包括低压蒸汽锅炉32。再次，这使得能够有效地产生在该工艺中用于别处的蒸汽，例如在此上面被详细描述的二氧化碳除去步骤。锅炉给水任选地从二氧化碳洗涤器28，被进料到低压蒸汽锅炉32中，并且如上面所述，再生的蒸汽再循环通过该工艺或者用在别处。低压蒸汽锅炉32可以因此被连接到任选的预热器30。
尽管参考优选的实施方案和其具体的实施例，对本发明进行了示例和描述，但是执行相似功能和/或实现类似结果的其它实施方案和实施例，对于本领域中那些普通的技术人员来说将是非常明显地。从而所有在本发明的精神和范围内的这类等价的实施方案和实施例都是被预期的，并且意为由下述权利要求所涵盖。在此方面，本发明上面的详细描述被认为是非限制性的并且完全涵盖最大可能范围。

Claims (14)

1.一种用于从炉顶气燃料中分离二氧化碳的方法，所述方法包括：给定分为工艺气体和炉顶气燃料的炉顶气：
将所述工艺气体与烃混合，并且将得到的重整器进料气体进料到二氧化碳和蒸汽重整器中，以重整所述重整器进料气体并形成还原气体；和
将至少部分的所述炉顶气燃料进料到二氧化碳洗涤器中，以从所述炉顶气燃料中除去至少一些二氧化碳并形成与所述还原气体选择性混合的贫二氧化碳气体；
其中所述工艺气体和所述炉顶气燃料的比例是由与工艺气体连接的所述二氧化碳和蒸汽重整器中可获得的热量限定的；并且
其中当所述贫二氧化碳气体被用于与所述还原气体混合时，所述工艺气体和所述炉顶气燃料的比例为1∶1，而当所述贫二氧化碳气体没有被用于与所述还原气体混合时，所述工艺气体和所述炉顶气燃料的比例为2∶1。
2.权利要求1所述的方法，所述方法还包括将至少部分的所述炉顶气燃料进料到所述二氧化碳洗涤器中，以从所述炉顶气燃料中除去至少一些二氧化碳，并且在加入烃之后形成重整器燃料气体，将所述重整器燃料气体进料到所述二氧化碳和蒸汽重整器中。
3.权利要求2所述的方法，所述方法还包括压缩所述工艺气体和所述炉顶气燃料。
4.权利要求1所述的方法，所述方法还包括从所述炉顶气产生蒸汽。
5.权利要求4所述的方法，所述方法还包括洗涤所述炉顶气以除去灰尘。
6.权利要求1所述的方法，其中所述炉顶气从还原炉中获得。
7.权利要求1所述的方法，所述方法还包括将所述还原气体与氧气和烃混合以形成促动气，并将所述促动气进料到还原炉中。
8.权利要求1所述的方法，所述方法还包括在将所述贫二氧化碳气体与所述还原气体混合和使用其作为燃料的一种操作之前，预热所述贫二氧化碳气体。
9.权利要求1所述的方法，其中所述二氧化碳和蒸汽重整器还产生烟道气。
10.权利要求9所述的方法，所述方法还包括从所述烟道气产生蒸汽。
11.权利要求10所述的方法，所述方法还包括利用所述烟道气预热其它气体。
12.权利要求1所述的方法，其中所述炉顶气和所述还原气体与用于将铁的氧化物转化为金属铁的直接还原方法是相关联的。
13.一种用于从废气中分离二氧化碳并重新使用其作为没有排放顾虑的再循环气体的方法，所述方法包括：
给定分为工艺气体和废气的气体源：
将所述工艺气体与烃混合，并且将得到的进料气体进料到重整器中，用于重整所述进料气体并形成还原气体；和
将至少部分的所述废气进料到二氧化碳洗涤器中用于从所述废气中除去至少一些二氧化碳，并形成与所述还原气体选择性混合的贫二氧化碳气体；
其中所述工艺气体和所述废气的比例是由与工艺气体连接的所述重整器中可获得的热量限定的；并且
其中当所述贫二氧化碳气体被用于与所述还原气体混合时，所述工艺气体和所述废气的比例为1∶1，而当所述贫二氧化碳气体没有被用于与所述还原气体混合时，所述工艺气体和所述废气的比例为2∶1。
14.权利要求13所述的方法，所述方法还包括将至少部分的所述废气进料到所述二氧化碳洗涤器中，以从所述废气中除去至少一些二氧化碳，并且在加入烃之后形成燃料气体，将所述燃料气体进料到所述重整器中。
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