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CN1269974C - 联合的直接还原铁方法和装置 - Google Patents

联合的直接还原铁方法和装置 Download PDF

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CN1269974C
CN1269974C CNB991185676A CN99118567A CN1269974C CN 1269974 C CN1269974 C CN 1269974C CN B991185676 A CNB991185676 A CN B991185676A CN 99118567 A CN99118567 A CN 99118567A CN 1269974 C CN1269974 C CN 1269974C
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gas
synthetic gas
separation plant
equipment
air
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CN1247901A (zh
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R·F·德尔内维奇
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Praxair Technology Inc
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Abstract

一种与一台汽轮机动力发生器联合，并且优选与一台低温空气分离装置联合的直接还原铁的制备系统，其中，由直接还原反应产生的尾气带动汽轮机，优选由空气分离装置制得的O2被用于产生直接还原反应的合成气，由空气分离装置制得的N2被用于阻抑NOx的产生，并且增大汽轮机中产生的动力。

Description

联合的直接还原铁方法和装置
本发明涉及通过直接还原铁矿石来制备铁，并且提供了一种将直接还原铁矿石与产生动力有效地联合在一起的改进方法。优选这种联合也包括一种空气分离装置，如一台低温空气分离装置。
通过将铁矿石直接与一种还原剂接触，将铁矿石或铁氧化物直接还原成金属铁。直接还原铁矿石制备金属铁需消耗大量的动力，但是这种直接还原装置的最适宜的地理位置经常是在操作这种装置的动力增量不容易利用和不能有效利用的地区。
相应地，本发明的一个目的在于提供一种通过直接还原铁矿石来制备铁的方法，该法能在任一地理位置有效地操作，而与该位置动力的外在可用性无关。
通过本发明可达到上述目的以及其它目的，本领域的技术人员可通过阅读公开内容来明白这些目的，本发明的一个方面是：
一种制备铁的方法，包括：
(A)产生合成气，并且将该合成气通入一个反应容器；
(B)将铁矿石装入该反应容器，使之与合成气在反应容器内进行反应来制备铁，反应器尾气包含CO、H2、CO2和水蒸气；
(C)从该反应容器中回收铁；
(D)从反应器尾气中除去至少一部分水蒸气，制备更干燥的尾气；和
(E)在一台燃气轮机中燃烧这种更干燥的尾气来产生动力。
本发明的另一个方面是：
制备铁的装置，包括：
(A)一台合成气发生器和将烃类流体通入该合成气发生器的设备；
(B)一个直接还原反应容器，将铁矿石装入该直接还原反应容器的设备，和将合成气从合成气发生器通入该直接还原反应容器的设备；
(C)从该直接还原反应容器中回收铁的设备；
(D)一台干燥器和将气体从直接还原反应容器通入该干燥器的设备；和
(E)一台燃气轮机和将气体从干燥器通入该燃气轮机的设备。
如此处所使用的，术语“合成气”指的是一种包含CO和H2的混合物。
如此处所使用的，术语“铁矿石”指的是铁的一种或多种氧化物，如Fe2O3和FeO。
如此处所使用的，术语“干燥器”指的是能从一种气体混合物中除去水分的设备。这种设备能利用一种材料，如一种吸附剂，来除去气体混合物中的水蒸气，或利用热交换途径，如一种冷却器和后续的相分离器，来除去气体混合物中被冷凝的水。
如此处所使用的，术语“燃气轮机”指的是一种使一台空气压缩机、燃烧器和气体膨胀机相联合的装置，该装置通过燃烧一种适当的燃料使压力升高，产生轴动力。通常这种空气压缩机和气体膨胀机组件被安装在也能驱动其它消耗动力的流体组件的轴上或一台发电机上。
如此处所使用的，术语“进料空气”指的是一种主要包含O2和N2的混合物，例如环境空气。
如此处所使用的，术语“空气分离装置”指的是能分离进料空气，并且能制备至少O2和N2之一的装置。
如此处所使用的，术语“低温空气分离装置”指的是一种包含至少一个塔的空气分离装置，其中至少这种塔的部分操作是在150K或低于150K的温度条件下进行的。
如此处所使用的，术语“塔”指的是一种蒸馏塔或分馏塔或区，即一种接触塔或区，其中，液体和蒸汽相逆流接触，以进行流体混合物的分离，就象例如通过使蒸汽相和液体相在一系列安装在塔内垂直放置的碟或板上和/或填充元件，例如规则或不规则填充元件内接触。
如此处所使用的，术语“变压吸附空气分离装置”指的是一种包含吸附和再生或解吸的主要步骤，对进料空气进行分离的空气分离装置，在吸附中，进料空气的一种组分被优先吸附到吸附剂上，在再生或解吸中通过减小压力来从吸附剂中除去这种被优先吸附的组分。
图1是本发明中合成气发生器是一种重整装置的一个优选实施方案的流程示意图。
图2是本发明中使用两种不同的合成气发生器的另一个优选实施方案的流程示意图。
图3是本发明中循环使用大量尾气的另一个优选实施方案的流程示意图。
图4是本发明中使用空气分离装置同时制备O2和N2的一个优选实施方案的流程示意图。
图5是本发明中使用一种固体或重质燃料来产生合成气的另一个优选实施方案的流程示意图。
本发明采用一种直接还原铁矿石所生成的副产物来产生动力，并且优选也将此副产物再循环到直接还原过程本身中去。这种动力的产生为动力不容易被利用的直接还原装置的定位提供了方便，并且由于再循环减小了直接还原过程的动力需求，增强了这种便利性。最优选该系统也与一种空气分离装置，例如一种低温空气分离装置联合，进一步提高总体布局的优势。
一方面，本发明包括一种制备铁的方法，其包括：
(A)产生合成气，并且将该合成气通入一个反应容器；
(B)将铁矿石装入该反应容器，使该铁矿石与合成气在该反应容器内进行反应来制备铁，并产生包含CO、H2、CO2和水蒸气的反应器尾气；
(C)从该反应容器中回收铁；
(D)从该反应器尾气中除去水蒸气，制备干燥的尾气；和
(E)在一台燃气轮机中燃烧这种干燥的尾气来产生动力；并且将进料空气通入一台空气分离装置，在这台空气分离装置中分离进料空气来制备O2，并使从空气分离装置中制得的O2与烃类流体发生反应，产生步骤(A)的合成气，
其特征在于
在空气分离装置中制备N2，并且在燃烧上述干燥的尾气之前，将在空气分离装置中制得的N2和干燥的尾气混合。
优选地，在该方法中一部分干燥的尾气被再循环到反应容器中。
优选地，在该方法中合成气是通过重整反应、部分氧化反应和自热反应中的至少一种反应来产生的。
优选地，在该方法中合成气是通过一种重整反应和一种部分氧化反应来产生的，并且将这种重整反应和部分氧化反应分别制得的合成气通入反应容器。
另一方面，本发明包括一种制备铁的装置，其包括：
(A)一台合成气发生器；
(B)一个直接还原反应容器，将铁矿石装入该直接还原反应容器的设备，和将合成气从合成气发生器通入该直接还原反应容器的设备；
(C)从该直接还原反应容器中回收铁的设备；
(D)一台干燥器和将气体从直接还原反应容器通入该干燥器的设备；和
(E)一台燃气轮机和将气体从干燥器通入该燃气轮机的设备；以及
(F)将烃类流体通入该合成气发生器的设备；
所述装置还包括一台空气分离装置，将进料空气通入该空气分离装置的设备，和将O2从空气分离装置通入合成气发生器的设备，
其特征在于
该装置还包括将N2从空气分离装置通入燃气轮机的设备。
优选地，该装置还包括将气体从干燥器通入直接还原反应容器的设备。
参照附图详细描述本发明。现在参照图1，烃类流体100通常优选主要包含甲烷的天然气，但是可以包含部分或全部其它轻质烃类，并且包含蒸发的石脑油。将这种烃与再循环的尾气105混合，形成进料气流110，通入合成气发生器500。在图1所阐述的实施方案中，合成气发生器500是一种重整装置。在重整装置500中，CO2与烃发生吸热反应，形成合成气。通过燃烧天然气(如图中部件115所示)来给重整装置500供热，促进这种吸热反应。将在合成气发生器500中产生的包含CO和H2的合成气120，与从直接还原反应器中再循环的CO和H2一起，通入直接还原反应容器510，优选如图1所示，除自然热传递之外未经任何冷却。
将铁矿石210加入直接还原反应容器510，在容器510内，该铁矿石与一般为760-982.2℃(1400°F～1800°F)温度范围内的热合成气接触，与该合成气发生反应。该合成气与铁矿石的反应使铁矿石还原成金属铁，并产生CO2和水蒸气。如物流220所示，从直接还原反应容器510中回收得到的铁。
将直接还原反应容器150中的尾气125通入干燥器520，该尾气包含由直接还原反应所产生的CO2和水蒸气，以及未反应的CO和H2。在干燥器520中，这种尾气被冷却，并且从反应器510排出的尾气中的至少一部分水蒸气被冷凝。如图所示，得到的冷凝水如物流200所示的，从干燥器520中除去，得到的更干燥的尾气作为气流130从干燥器520通入第一台压缩机530，其中该气流通常被压缩到30～300psia的绝对压力范围内。应该理解，虽然尾气125经过处理，除去一部分所包含的水蒸气，但是得到的更干燥的尾气130实际上仍然保留一部分水蒸气，并且在干燥器520的出口处可以是饱和的。
从第一台压缩机530得到的尾气135中的一部分105被再循环。在图1所阐述的本发明的实施方案中，105部分被再循环到重整装置500。另一部分140，通常包含约5～70％的更干燥的尾气，被通入第二台压缩机540，其中，该尾气通常被进一步压缩到150～500psia绝对压力范围内。然后，将进一步压缩过的更干燥的尾气145通入燃气轮机560，其中，该尾气燃烧产生动力。如果需要的话，可往燃气轮机560中加入另外的燃料150，如天然气，用于增大产生动力。如具有代表性的方式155所示，由燃气轮机560产生的动力可以是电力的或机械的。也就是说，汽轮机560可以被用来驱动发电机，或者被用来直接驱动机器，如压缩机。
图2阐述了本发明的另一个实施方案，其中，可以使用一台部分氧化装置或一台自热装置作为第二种合成气发生器，产生另外的合成气。图2所阐述的本发明实施方案的部件中，与图1所阐述的实施方案的部件相对应的，则序号相同，并且将不再详细描述。
现在参照图2，将进料空气10通入空气分离装置700。优选空气分离装置700是一种低温空气分离装置，但它也可以是一种变压吸附空气分离装置。在空气分离装置700中，进料空气被分离成产物O215，也可有产物N220。如果该空气分离装置是一种低温空气分离装置，也可以制备以产物流21为代表的其它产物，如Ar和/或液态O2。将在空气分离装置中制得的O2浓度至少为70mole％，优选至少为90mole％的O215，与烃类流体101一起通入合成气发生器501，烃类流体101与流体100特性相同，并且通常两者的来源是一样的。
合成气发生器501可以是一台部分氧化装置或一台自热装置。在部分氧化装置中，O2与烃类流体反应，产生CO和H2。在自热装置中，尽管氧化反应程度比部分氧化装置中的反应程度小一些，但是从空气分离装置中出来的烃由O2部分氧化，生成CO和H2，另外，给该自热装置提供蒸汽，以通过蒸汽-烃重整的工艺，来产生另外的CO和H2。然后，将在合成气发生器501中产生的合成气通入直接还原反应容器510。优选如图2所阐述的一样，从发生器501中出来的合成气气流118被通入气流120中，形成联合气流121，再通入反应容器510。图2所阐述的系统的其余部分与图1所阐述的相似。如果需要，一部分更干燥的尾气130(如气流131所示)可以被取出来用于本过程的其它地方，例如作为一种燃料来源用于重整装置500中产生热。
图3阐述了本发明的一个优选实施方案，其中尾气被逆流和顺流再循环到合成气发生器。图3中的序号与其它图表中共同部件的序号相同，并且将不再详细讨论那些共同部件。
现在参照图3，压缩后的尾气135被分成140和36两部分。将36的第一部分160再循环到直接还原反应容器510的进料中，将第二部分137与燃料115一起通入燃烧加热器600。然后，将燃烧加热器600中加热后的尾气305通入气流100，再将得到的联合气流110通入部分氧化装置500，产生合成气。将部分氧化装置500中的热合成气118与尾气再循环气流160联合，形成气流320，进料到反应容器510。采用燃烧加热器可以最优化系统的总成本。通过预加热一部分再循环气体，可以减少部分氧化装置中维持吸热重整反应所需的氧气的量。
图4阐述了本发明的一个优选实施方案，其中，合成气发生器既可以是一台部分氧化装置，也可以是一台自热装置，空气分离装置是一种低温空气分离装置。图4中的序号与其它图表中共同部件的序号相同，并且将不再详细讨论那些共同部件。
现在参照图4，将烃类流体100与燃料115一起通入燃烧加热器600。再将经燃烧加热器600加热后的烃类流体111和由低温空气分离装置700制备的O215通入合成气发生器501，该发生器既可以是一台部分氧化装置，也可以是一台自热装置。如果合成气发生器501是一台自热装置，那么优选在燃烧加热器600的上游，将蒸汽加入烃类流体100。
将从第一台压缩机530中得到的更干燥的尾气105与从合成气发生器501中得到的合成气117联合，形成合成气气流120。在图4所阐述的本发明实施方案中，含烃燃料116被直接加入到热合成气120中，形成直接还原反应容器510的进料气流122。这吸取了热合成气气流中部分重整的优点，并且利用通过直接铁还原反应将烃还原成C和H2的能力。由于气流120和122的高温和再循环气流105中CO2的存在，气流未进入反应容器510之前，在气流122中将发生部分烃的重整。在反应容器510中，除发生裂解生成C和H2外，将发生烃的另外的重整。往反应容器510的合成气原料中添加烃类燃料116的一个优点是减少了必须在合成气发生器501中制备的合成气的量，这样，就减小了合成气发生器和空气分离装置的尺寸。另外，因为这种重整反应是吸热反应，所以可以减少气流105中的再循环量，同时仍然提供所需的直接还原反应容器510的入口温度。
在图3和图4所阐述的本发明实施方案中，将水190加入干燥器520，并且通过与热的尾气125的直接热交换而蒸发，然后得到的气流195通入汽轮机560，用于产生另外的动力。
在图4所阐述的本发明实施方案中，燃气轮机中也采用了由空气分离装置700制得的N2。虽然一些N225可以由装置700回收，但是至少有一些产物N2(通常N2浓度至少为95mole％)随气流26通入N2压缩机710，其中N2被压缩到通常为30～300psia的压力。然后，将得到的压缩后的N2气流30与更干燥的尾气气流140联合，形成气流136，然后，在第二台压缩机540中进一步压缩，接着作为气流146通入汽轮机560中产生动力。由空气分离装置制得的N2有两个用途。第一个用途是降低燃气轮机燃烧室中的火焰温度，从而降低燃烧室中所产生的氮氧化物(NOx)水平。添加N2的第二个用途是增大动力。这种附加量的N2能确保燃气轮机在其机械限度附近操作，从而确保该燃气轮机资产的最大利用。
图5阐述了本发明的另一个实施方案，其中用来产生合成气的燃料是固体和/或重质液体。图5中的序号与其它图表中的共同部件的序号相同，并且将不再对这些共同部件进行详细讨纶。
现在参照图5，将固体和/或重质液体燃料205，如煤、石油焦炭或渣油，与O215和锅炉进料水191一起通入部分氧化装置501。从装置501中取出合成气气流212，如果需要，将其通入脱硫装置505，该脱硫装置可以是一种传统的吸收装置、一种以胺为基础的系统或一种高温装置。矿渣作为物流101从装置501中除去，蒸汽作为物流196从装置501通入汽轮机560。脱硫后的合成气气流213被分成气流214和217，气流214被通入汽轮机560，气流217与再循环蒸汽105合并形成气流222。在燃烧加热器506中用燃料216来加热该气流，得到的气流224通入直接还原反应容器510进行上述工艺操作。
现在通过采用本发明，可以比传统系统更有效地通过直接还原铁矿石来制备铁。该直接还原反应的副产物可以被用来产生动力，也可以被用来减少进行直接还原反应所必须产生的合成气的量。产生的动力本身可用于操作空气分离装置，该空气分离装置的产物又可以被用来产生合成气，也可以用于NOx还原反应和增大产生的动力。
虽然已参照某些优选实施方案，详细描述了本发明，但是本领域的技术人员应认识到，在权利要求书的精神和范围内，本发明还有其它实施方案。

Claims (6)

1.一种制备铁的方法，包括：
(A)产生合成气，并且将该合成气通入一个反应容器；
(B)将铁矿石装入该反应容器，使该铁矿石与合成气在该反应容器内进行反应来制备铁，并产生包含CO、H2、CO2和水蒸气的反应器尾气；
(C)从该反应容器中回收铁；
(D)从该反应器尾气中除去水蒸气，制备干燥的尾气；和
(E)在一台燃气轮机中燃烧这种干燥的尾气来产生动力；并且将进料空气通入一台空气分离装置，在这台空气分离装置中分离进料空气来制备O2，并使从空气分离装置中制得的O2与烃类流体发生反应，产生步骤(A)的合成气，其特征在于
在空气分离装置中制备N2，并且在燃烧上述干燥的尾气之前，将在空气分离装置中制得的N2和干燥的尾气混合。
2.如权利要求1的制备铁的方法，其中一部分干燥的尾气被再循环到反应容器中。
3.如权利要求1的制备铁的方法，其中合成气是通过重整反应、部分氧化反应和自热反应中的至少一种反应来产生的。
4.如权利要求1的制备铁的方法，其中合成气是通过一种重整反应和一种部分氧化反应来产生的，并且将这种重整反应和部分氧化反应分别制得的合成气通入反应容器。
5.制备铁的装置，包括：
(A)一台合成气发生器；
(B)一个直接还原反应容器，将铁矿石装入该直接还原反应容器的设备，和将合成气从合成气发生器通入该直接还原反应容器的设备；
(C)从该直接还原反应客器中回收铁的设备；
(D)一台干燥器和将气体从直接还原反应容器通入该干燥器的设备；和
(E)一台燃气轮机和将气体从干燥器通入该燃气轮机的设备；
以及
(F)将烃类流体通入该合成气发生器的设备；
所述装置还包括一台空气分离装置，将进料空气通入该空气分离装置的设备，和将O2从空气分离装置通入合成气发生器的设备，其特征在于
该装置还包括将N2从空气分离装置通入燃气轮机的设备。
6.权利要求5的装置，其特征在于
该装置还包括将气体从干燥器通入直接还原反应容器的设备。
CNB991185676A 1998-09-10 1999-09-09 联合的直接还原铁方法和装置 Expired - Fee Related CN1269974C (zh)

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