CN102482724A - 同时生产铁和含有co和h2的粗合成气的方法 - Google Patents

同时生产铁和含有co和h2的粗合成气的方法 Download PDF

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CN102482724A
CN102482724A CN2010800233552A CN201080023355A CN102482724A CN 102482724 A CN102482724 A CN 102482724A CN 2010800233552 A CN2010800233552 A CN 2010800233552A CN 201080023355 A CN201080023355 A CN 201080023355A CN 102482724 A CN102482724 A CN 102482724A
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J·曼策尔
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Abstract

本发明涉及一种通过使用装有铁矿石和含碳的还原剂的高炉同时生产铁和含有CO和H2的粗合成气的方法，其中，向高炉输送的含碳的还原剂的量大于铁生产所需要的燃料量。向高炉输送工业纯氧用于高炉工艺和用于生产粗合成气。此外，为了控制作为高炉煤气离开高炉的粗合成气的CO/H2-比例和/或调适氧气喷射的喷入温度，向高炉额外输送CO2和/或水蒸汽。

Description

同时生产铁和含有CO和H2的粗合成气的方法
本发明涉及一种同时生产铁和含有CO和H2的粗合成气的方法。
合成气是气体混合物，其用于合成反应并且主要由CO和H2组成。对于某些CO/H2-组合，基于其来源或其应用形成特别的名称，如，水煤气，裂解气，甲醇-合成气或羰基合成气。合成气可以用作生产液态动力燃料的原料混合物，例如，可以采用合成气在费-托法中生产柴油动力燃料。可以按照MTG-工艺(甲醇制汽油技术)生产汽油动力燃料，其中合成气首先转化成甲醇，而后在进一步的工艺步骤中甲醇再转化成汽油。
原则上所有含碳的材料都可以用于生产合成气。属于此的不仅有化石燃料煤，石油和天然气还有其它原料，例如，塑料，泥炭，木材或其它生物质，如，城市或农业废物。如果使用固体材料，则首先必须耗费地将其粉碎，然后可以通过部分氧化或水蒸汽裂解生产粗合成气，然后在进一步的步骤中对粗合成气进行处理。所有这些措施都造成高的投资成本，这对由合成气生产液态燃料是个阻碍。
在US4013454中介绍了一种同时生产铁和甲醇或氨的方法。向高炉中加入铁矿石，含碳的还原剂和由氧和CO2形成的可燃气体。在高炉工艺中产生含大约80％的CO和20％的CO2的高炉煤气。高炉煤气通过化学反应以及吸附过程被处理成可以用于甲醇工艺或氨工艺的合成气。将基本上由CO和CO2组成的高炉煤气转化成适合甲醇工艺或氨工艺的合成气要求多个附加工艺阶段并因而需要额外的投资。
本发明的任务是，不仅降低生产合成气的投资成本和操作成本并且改善CO2平衡。
本发明的主题以及此项任务的解决方案是一种通过使用装有铁矿石和含碳还原剂的高炉同时生产铁和含有CO和H2的粗合成气的方法，其中，
-向高炉输送的含碳的还原剂的量大于铁生产所需要的燃料量。
-向高炉输送用于高炉工艺和用于生产粗合成气的工业纯氧和
-向高炉额外输送CO2和/或水蒸汽，以便控制作为高炉煤气离开高炉的粗合成气的CO/H2-比例和/或调适氧气喷射的喷入温度。
通常，从上方分层地向高炉装入铁矿石和焦炭，装料向下滑入高炉的总是较热的区域，在高炉的靠下的部分喷入氧气。部分含碳的还原剂由此燃烧生成上升至铁矿石堆中的CO2和CO。铁矿石被上升的气体和热的含碳还原剂还原为金属铁。按照本发明，与纯铁生产相比，还向高炉输送额外量的含碳还原剂。为了使粗合成气的产量最大化，该额外的量可以以焦炭，煤，石油，塑料，天然气，再循环气，焦炉气或废气形式输送。氧气量与燃料量相匹配并且同样是大于纯铁生产所需要的量。根据本发明，高炉工艺应如此实施，使得高炉煤气已经含有CO和H2并且它们的量比例与期望的合成气组成相当或至少是接近。此外，优选如此实施高炉工艺，使得作为高炉煤气排出的粗合成气的CO2份额低。为了控制CO/H2-份额，向高炉额外输送CO2和/或水蒸汽。CO2可与焦炭反应生成CO：C+CO2→2CO。此外，可以使用CO2以与H2反应生成CO和水：CO2+H2→CO+H2O。如果同样加入水蒸汽作为附加成分来控制离开高炉的高炉煤气的CO/H2-含量，那么水蒸汽可在高温下在高炉中与焦炭反应生成CO和H2：C+H2O→CO+H2。此外，也可以使用水蒸汽使CO转化成CO2和H2：CO+H2O→CO2+H2。
用本发明的方法可以明显成本有利地生产技术条件适合的合成气，因为将利用现有的铁生产设备。在按照本发明同时生产合成气和铁时，运行成本也较低，因为输送的绝大部分燃料是铁生产所需的。与传统的方法相比CO2-平衡明显更有利。从所输送的燃料中同时生产两种产品。因为高炉煤气被用作合成气，除了铁还可以生产出额外的有价值的物质(wertstoff)。高炉煤气不仅供热性预热可燃气体，而且本身还可以作为物质使用并且形成用于其它产品例如，柴油，汽油或甲醇的原材料。与传统的高炉工艺相比，仅对燃料有少量的额外需求。这比用于分开操作的方法的燃料总量明显低很多。作为对额外的燃料需求的补偿，获得另一种有价值的物质，例如，柴油动力燃料，对于柴油动力燃料在传统的通过煤气化来生产时，还必须再次汽化接近相同量的煤。
通过用工业纯氧操作高炉工艺可以在高炉内达到高的反应温度。这使得可以实现放弃对氧气预热。通过使用工业纯氧来生产粗合成气提供更高产率的合成气，因为与传统的利用空气预热的运行方式相比，在这里不需要消耗高炉煤气来进行预热。即使必须预热氧气，为此所需的高炉煤气的量也比在传统的高炉工艺中低，因为待预热的氧气流比额外含有氮气的空气流小得多。此外，在使用纯氧时，所生产的粗合成气不含氮气。这显著简化了进一步的处理，因为不需要进行耗费的氮分离。通过使用纯氧最终也使高炉工艺的CO2-平衡得以改善，因为不会为了空气预热而损失高炉煤气。在传统的高炉工艺中有大约三分之一的高炉煤气需要被用于空气预热，并且在这时转化成CO2。在按照本发明的供氧工艺中，这些量的高炉煤气可额外地用作合成气并且可以用于生产有价值的物质。
按照本发明的方法的另一个实施方案设计为，向高炉输送使粗合成气中的硫含量最小化的物质。为此优选碳酸钙和铁矿石一起输送。
按照本发明的方法的另一个优选的实施方案设计为，部分粗合成气返回到高炉中。粗合成气含有CO，而CO继而又作为铁矿石的还原剂。
作为高炉煤气离开高炉的粗合成气被除尘并且然后可以作为有价值的物质使用。如果作为高炉煤气产生的粗合成气还不具有技术条件适合的CO/H2-比例，则应从外部来源向高炉混入CO和/或H2，或借助CO-转化通过添加水蒸汽使粗合成气转化成H2和CO2。这样向高炉输送的CO2也可以从离开高炉的粗合成气生产。适宜的是，向高炉输送的CO2由经受CO转化的粗合成气生产。
按照本发明的方法的有利实施方案设计为，至少一部分粗合成气借助CO-转化通过添加水蒸汽转化成H2和CO2并且在后接的变压吸附设备(变压吸附法PSA设备)中获得H2，其中，为了调适温度，来自变压吸附设备的富含CO2的废气流重新返回到高炉。尤其是可以利用来自变压吸附设备的富含CO2的废气流来冷却氧气喷射。
在一个特别有利的方法变型里，在焦炉中生产混入高炉煤气的含H2的粗煤气。在此已经证明有利的是，首先净化炼焦厂煤气并在吸附设备中将H2与残余气体分离。然后H2气流可以有针对性地被配料给从高炉排出的高炉煤气。这种协调地由高炉工艺和焦炉工艺生产合成气，经证明特别有利，因为，在高炉中生产富含CO的粗煤气，并在焦炉中生产富含H2的粗煤气。在合成气生产时这两种工艺相互补充。此外，大多的炼焦厂都位于高炉附近，因为高炉工艺需要焦炭。
也可以使用煤的气化设备，天然气-部分氧化设备(POX)，自热式重整器或蒸汽重整器作为外部氢源。也可以通过有针对性的运行方式把第二个高炉调节到H2生产。
本发明的另一个优点在于，例如，如果多个高炉位于一个位置或在一个位置附近，可以把多个高炉的合成气汇聚在一起，并且以较大的规模，就是说，以精炼厂的规模并因此以总体上成本有利的方式进行进一步的合成与产品处理。或许也可以在现有的精炼厂进行处理。其它生产合成气的设备，例如，煤的气化设备，再生性原料的气化设备，和类似的设备也可以低成本地集成在一个综合建筑内。
按照本发明的方法生产的粗合成气可以用在不同的生产方法中，例如，可以用于费-托法的情况中以生产动力燃料。同样，该合成气也可以用于甲醇合成的情况中。甲醇可以按照MTG-方法(甲醇制汽油技术)转化成汽油。也可以考虑使合成气转化成合成天然气(SNG)。所生产的合成气也同样可以用于羰基合成或氨生产。

Claims (8)

1.使用装有铁矿石和含碳的还原剂的高炉同时生产铁和含有CO和H2的粗合成气的方法，其中，
向高炉输送的含碳的还原剂的量大于铁生产所需要的燃料量，
向高炉输送用于高炉工艺和用于生产粗合成气的工业纯氧和
向高炉额外输送CO2和/或水蒸汽，以便控制作为高炉煤气离开高炉的粗合成气的CO/H2-比例和/或调适氧气喷射的喷入温度。
2.根据权利要求1所述的方法，其特征在于，为了使作为高炉煤气而产生的粗合成气量最大化，除了铁生产所必需的燃料外还向高炉输送额外的含碳的还原剂，所述含碳的还原剂以焦炭、煤、石油、塑料、天然气、循环气、焦炉气或废气的形式。
3.根据权利要求1或2所述的方法，其特征在于，向高炉输送用于降低粗合成气中的硫含量的物质。
4.根据权利要求1～3中任一项所述的方法，其特征在于，部分高炉煤气返回到高炉中。
5.根据权利要求1～4中任一项所述的方法，其特征在于，将作为高炉煤气离开高炉的粗合成气除尘。
6.根据权利要求1～5中任一项所述的方法，其特征在于，从离开高炉的粗合成气获得向高炉输送的CO2。
7.根据权利要求1～6中任一项所述的方法，其特征在于，从经受CO2转化的粗合成气获得向高炉输送的CO2。
8.根据权利要求1～7中任一项所述的方法，其特征在于，至少部分粗合成气借助CO-转化通过添加水蒸汽转化成H2和CO2并且在后接的变压吸附设备中获得H2，其中，为了调适温度，来自变压吸附设备的富含CO2的废气流重新返回到高炉中。
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