CN102498058A - 利用深冷净化制取氨补充合成气 - Google Patents

利用深冷净化制取氨补充合成气 Download PDF

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CN102498058A
CN102498058A CN2010800393369A CN201080039336A CN102498058A CN 102498058 A CN102498058 A CN 102498058A CN 2010800393369 A CN2010800393369 A CN 2010800393369A CN 201080039336 A CN201080039336 A CN 201080039336A CN 102498058 A CN102498058 A CN 102498058A
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nitrogen
stream
gas
synthetic gas
rich stream
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CN102498058B (zh
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埃尔曼诺·菲利皮
杰弗里·弗雷德里克·斯金纳
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Casale SA
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Ammonia Casale SA
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Abstract

本发明公开了一种用于制取氨补充合成气的方法以及相关设备，其中：转化烃原料，获得粗氨补充合成气的流；在通过在空气分离单元中产生的富氮气流制冷的深冷净化段中净化所述粗合成气；所述深冷段的输出处的富氮气流还用于调节净化过的补充合成气的氢气/氮气比；还在所述空气分离单元中产生富氧气流，并将其送入转化段。

Description

利用深冷净化制取氨补充合成气
技术领域
本发明涉及利用深冷净化制取氨补充合成气。更详细地，本发明涉及通过烃原料(比如天然气)蒸汽转化来制取粗氨补充合成气以及通过深冷净化处理所述粗合成气。
背景技术
已知通过包括比率约为3∶1的氢气和氮气的所谓的氨补充合成气(合成气)在合适的高压合成回路中发生反应来制取氨。
补充合成气通常是通过氨合成设备的前端段中的烃原料发生催化蒸汽转化而产生的。前端段的传统设备是一段转化炉、二段转化炉、冷却/变换炉、脱除CO2段和甲烷化段。所述前端段在不大于60-80巴的压强下工作，通常在15巴到35巴的范围中工作，而氨合成回路在较高的压强下工作，例如大于100巴。因此，前端段的另一组件是主合成气压缩机以向合成回路供料，该主合成气压缩机通常具有多级配置。
合成气的深冷处理在现有技术中也是已知的。US3572046公开了一种用于净化粗合成气的装置，其中，在深冷段中脱除过量氮气，通过合成气膨胀来提供深冷段的制冷。
US5736116公开了一种通过安装空气分离单元的改进方法，所述空气分离单元提供富氧气流和富氮气流。富氧气流用于增加二段转化炉的空气进料及将补充气中的氢气含量增加至基本上在设计的化学计量值及能力之上；富氮气流供应至合成回路，以获得送入氨转化炉中的合成气所需的氢氮比并补偿补充气中的过量氢气。
前端段的产能对整个氨合成设备的产能起决定性作用。关于设备的尺寸和成本，不断地进行努力来提高氨合成设备的与装置的大小和成本相关的生产率，以及因此提高其前端段的生产率。在实现基于烃蒸汽转化的新型氨合成设备以及改进现有的设备中遇到这些问题。
以实质性方式提高一段转化炉的产能可能是非常昂贵的。可以通过安装更换管来改进旧的管式转化炉，所述更换管由更耐腐蚀的材料制成，因此与原始设计的管子相比，更换管具有较大的直径和较小的厚度(因此提供较大的通道截面)。然而，这仅对为数不多的旧式装置而言是可能的。安装附加管子是可能的，但受原始转化炉的尺寸的限制；增大转化炉的尺寸也是可能的，但是当然昂贵且耗时。其他的解决方式是降低蒸气/碳的比率，这仅可以在较旧式设备中有效而且在任何情况下都涉及到将下游的处理段进行相应改进，或者，所述其他的解决方式是安装附加的预转化炉，但这仅获得10％-15％的相对低的生产率优势。
经过转化炉和后面的设备(比如变换炉和脱除CO2装置)的容积流量通常是可能获得的最大产出的限制因素。很多缺点与经过前端段的较大流量有关，这些缺点可以概括为：需要提高空气流压缩机和合成气流压缩机以及它们的驱动透平机的产能；前端段中有较大的压力损失；需要提高脱除CO2装置的产能。提高经过前端段的容积流量还需要脱除CO2段有较高压降和较高负荷。通常，仅可通过昂贵的改进来降低压降，比如替换一些阀门、将轴向反应器转化为轴径向装置等。而且，脱除CO2段通常需要实质性改进(例如，更换一个或多个塔或者提供新塔)以获得产能显著提高。
第二个问题是增大来自空气压缩机的空气流，以向二段转化炉提供更多的氧气。安装压缩机的新内部构件和可能地安装压缩机的驱动透平机的内部构件本身以及提供与现有的压缩机并联的另一压缩机是有效的，但昂贵。将一增压机即用来提高压强的预压缩机安装在主空气压缩机的入口较不昂贵但效率不高。
主合成气压缩机的产能也是一个关键点。所述压缩机是特殊的且昂贵的装置，尤其是被设计成对合成气进行操作的压缩机。通常优选的是，不安装任何增压机或者与主压缩机并联的附加压缩机，因为任何附加设备的故障可能危害整个设备的可靠性并且可以对主压缩机造成严重损坏。可以通过更换压缩机和透平机的内部构件来改进压缩机，但该改动是相当昂贵的。
概括来讲，从技术和经济的角度看，改善蒸汽转化氨合成设备的前端段面临着很多限制和约束。
要考虑的另一技术问题是杂质的量，比如未转化的甲烷和碳氧化物以及惰性气体，所述惰性气体比如送至合成回路的合成气中含有的氩气。合成回路对所述杂质非常敏感，因此需要实现对合成气进行最佳可能的净化。
US5736116中公开的以上示出的改进方法提供了上述问题的部分解决方案，其公开了与将氮气注入合成回路中相结合的富含空气的转化。然而，其并没有针对所有上述问题提供令人满意的解决方案，且未考虑对下游的氨合成回路的影响以及合成气中包括的杂质的问题。
发明内容
本发明所基于的问题是以成本效率高的方式解决以上列出的限制。根据以下公开内容，该问题是通过一种方法、一种设备和一种改进方法来解决的。
根据本发明，一种用于制取氨补充合成气的方法包括以下步骤：
-转化烃原料，之后进行变换、CO2脱除以及甲烷化的步骤，获得包括氢气和氮气的粗氨补充合成气的流；
-在深冷净化段中处理所述粗氨补充合成气，获得净化过的合成气的流；
-在深冷温度下将液态富氮气流输送至所述深冷净化段；
-在深冷段中提供合成气和所述液态富氮气流之间的间接热交换，所述液态富氮气流至少部分地蒸发以提供所述深冷段的制冷。
所述液态富氮气流优选地是以液态的基本上纯净的氮气，其具有优选地在零下185℃和零下190℃之间的温度(大约88-93K)。优选地，所述液态富氮气流至少部分地蒸发以制冷所述深冷段。
优选地，在通过所述深冷段本身蒸发并加热后，在所述深冷净化段的输出处回收所述富氮气流，并将所述富氮气流与所述净化过的合成气混合以提供调节氨补充合成气的氢/氮比所需的氮气的至少一部分。
所述液态富氮气流优选地从空气分离单元获得。在该方法的优选实施方式中，在空气分离单元中产生所述富氮气流和另外的富氧气流，优选地通过将所述富氧气流注入在所述转化段的二段转化炉中，所述富氧气流用作转化段中的氧化剂，以提高所述补充合成气的产量。
更优选地，所述空气分离单元提供深冷温度的液态氮气以及另外的环境温度的第二氮气流。调节所述氨补充合成气的HN比所需的氮气的量部分由在所述深冷段的输出处回收的蒸发的液态富氮气流提供，以及部分由环境温度的所述富氮气流提供。
上述实施方式由于以下原因是优选的。调节HN比所需的氮气的量通常大于需要蒸发以制冷深冷段的液态氮气的量。液态氮气部分越大，空气分离单元的能量消耗越高。则，为了节省能量，优选的是，仅有深冷过程所需的最小量的氮气以液体形式提供，其余的氮气是在环境温度下提供的。
该方法的其它优选方面如下。粗合成气在深冷段的主热交换器中被冷却至深冷温度，从冷的、净化过的合成气以及至少部分地蒸发的富氮气流回收冷量。获得冷却的粗合成气，该冷却的粗合成气送至接触装置，以通过深冷净化分离出杂质。从所述接触装置回收部分净化过的合成气，该部分净化过的合成气在冷凝器中被进一步冷却和净化，该冷凝器由所述富氮气流制冷；在所述冷凝器的输出处获得进一步净化过的合成气和冷凝的部分；接着，通过与输入的粗合成气和来自所述冷凝器的氮气流进行热交换，所述合成气在所述主热交换器中被再加热。
优选地，接触装置是深冷塔。冷凝器可以是塔的一部分或独立装置，该独立装置优选地在该塔之上。通过液态富氮气流的完全或部分蒸发来提供所述冷凝器的制冷。
更详细地，在优选的实施方式中，在用于深冷液化的塔中处理合成气，所述塔是深冷段的一部分，在所述塔的顶部回收的净化过的合成气在冷凝器中进一步冷却，该冷凝器是通过液态富氮气流的部分或全部蒸发而被制冷的。包括甲烷和其他杂质的部分在所述冷凝器中被液化，并输送回所述塔；进一步净化过的合成气在所述冷凝器的输出处获得并且在主热交换器中被再加热，使输入的粗合成气冷却。所述冷凝器的输出处的氮气流和/或在塔的底部回收的包括甲烷、氮气和杂质的液流也可用作另外的热交换介质，例如送至同一主热交换器以对于输入的粗合成气的流进行制冷。
调节氨补充合成气的H/N比所需的氮气(即深冷段中蒸发的液态氮气)和/或由ASU提供的环境温度的第二氮气流，可以在主合成气压缩机上游与净化过的合成气混合，向下游的氨合成回路供料；或者在所述主合成气压缩机的下游与净化过的合成气混合，提供单独的压缩氮气。这两个实施方式是可能的，然而，单独的压缩N2是优选的。以此方式，获得主要由合适的比率3∶1的氮气和氢气以及非常少的杂质组成的纯补充合成气。
烃原料优选地是天然气或代用天然气(SNG)，但可以使用任何合适的可转化烃。
本发明的一方面还是用于生产氨的方法，其中利用上述方法获得补充合成气且补充合成气在本身已知的氨合成回路中发生反应。因此，根据本发明，一种用于合成氨补充合成气的设备至少包括：
-前端段，所述前端段包括适于转化烃原料并产生粗氨合成气的流的转化段；
-深冷净化段，所述深冷净化段处理所述前端中产生的粗合成气；
-将深冷温度的液态富氮气流输送至所述深冷净化段的装置，所述深冷温度的液态富氮气流用作热交换介质以制冷所述深冷净化段；
-在深冷净化段中的所述合成气和所述液态富氮气流之间的至少一个间接热交换器，所述液态富氮气流在所述热交换器中至少部分地蒸发以提供所述深冷净化段的制冷。
根据本发明的优选方面，用于将富氮气流输送至深冷净化段的所述装置至少包括空气分离单元，也称为ASU。所述空气分离单元提供富氮气流，另外地提供富氧气流，该富氧气流优选地用作转化段中的氧化剂。ASU还可以提供环境温度的富氮气流，以调节HN比，具有节省能量方面的以上讨论的优势。该ASU可以使用传统的工艺，比如低温蒸馏。
在优选的实施方式中，前端包括一段转化炉、二段转化炉以及用于变换、CO2脱除和甲烷化的设备。空气分离单元提供的富氧气流优选到输送至转化段的二段转化炉。
根据深冷段的优选布置，所述深冷段至少包括：接触装置，比如深冷冷凝器；冷凝器，其接收所述接触装置中获得的部分净化过的合成气，且其由富氮气流制冷；主热交换器，在所述主热交换器中，输入的粗合成气通过与以下可用流的一个或多个流进行热交换而冷却：氮气流、净化过的合成气和可能地在接触装置中分离的液态部分。
本发明还应用于改进现有氨合成设备或其前端段。
具体地，本发明提供了一种用于改进氨合成设备的前端段的方法，所述前端段至少包括用于将烃原料转化为粗氨补充合成气的一段转化炉和二段转化炉以及用于处理粗合成气的深冷段，所述方法至少包括以下步骤：安装与所述前端段并联的空气分离单元；提供用于将在所述空气分离单元中产生的富氮气流输送至所述深冷段的装置，所述富氮气流用作冷却介质；提供将在所述空气分离单元中产生的富氧气流输送给所述二段转化炉的新管线，以提高所述转化段的产能。如果原始设备中不存在深冷段，还可在所述改进中提供新的深冷段。
已发现，将富氮气流用作深冷段的冷却介质是提高设备的产能以及提高该方法的总效率的有效方式。第一优势在于，本发明将富氮气流用作冷却介质以将向深冷段提供制冷，替代在现有技术中所建议的耗能的粗合成气膨胀。然而，本发明并未将使粗合成气的至少一部分膨胀排除在外，如果恰当的话，其可以用作另外的对深冷段制冷的方法。在这样的情况下，冷却的合成气或冷却的合成气的至少一部分在合适的膨胀器或透平机中膨胀。
另一优势是以非常有效的方式使用富氮气流，即首先用作深冷段的冷却介质，接着用于净化过的合成气的H/N比调节，避免了大量的惰性氮气通过转化炉下游的净化设备。因此，获得明显的优势，而不具有转化炉、变换器和CO2脱除装置中处理的容积流量明显增大的缺点。
在前端的下游、优选地提供在主合成气压缩机的入口处的再加热过的氮气流的输送降低了通过整个前端的容积流量增加以及相关问题，包括压降以及CO2脱除段和甲烷化段的负荷。实际上，前端仅接收提高转化产能所需的纯净的氧气流，而基本上会作为惰性气体通过前端的氮气流仅被恰当地送入合成回路，在合成回路中需要氮气流以作为一种反应物来制取氨，以及用于建立补充合成气的合适的HN比。
而且，由于氮气制冷的深冷段中的处理，本发明在从合成气中脱除甲烷以及其它杂质的方面特别有效。较少的惰性物意味着反应物氮气和氢气更有效地转化为氨，以及未反应的合成气的再循环的减少和较低的能量消耗。
集成有空气分离单元是特别有效的，还使得能够获得富氧气流，该富氧气流被有利地注入到二段转化炉中，因此，在粗合成气的生产方面，提高了前端段的产能。
根据优选的实施方式的下列详细描述，优势将更明显。
附图说明
图1是根据本发明运行的氨合成设备的前端的简化框图。
图2是本发明的优选实施方式的更详细的图。
具体实施方式
参照图1，氨合成设备的前端包括转化段1，在转化段1中，烃原料11和蒸汽12反应生成粗合成气的流13，粗合成气的流13包括氢气、氮气以及一定量的CO、CO2、H2O、残余的甲烷、氩气和其他杂质。转化段1例如包括一段转化炉、二段转化炉和用于利用变换、CO2脱除和甲烷化的处理步骤处理转化成的合成气的已知设备。
粗合成气的流13输送至深冷段2，在深冷段2中，粗合成气的流13经受深冷液化并脱除杂质，所述段2提供净化过的合成气17。净化过的合成气17在合成气压缩机中被压缩并输送至氨合成回路。
根据本发明，液态富氮气流(比如基本上纯净的液态氮气32)用作冷却介质以向所述深冷段2提供制冷。液态氮气32至少部分地蒸发以将需要的冷量提供至深冷段，并从深冷段被回收为流34，流34至少部分地用来调节补充合成气的氢/氮比，即与净化过的合成气17混合或者输送入氨合成回路中。
所述基本上纯净的氮气流32的氮气含量大于99％(摩尔浓度)，且优选地在空气分离单元(ASU)3中产生。ASU 3接收空气供料31并提供液态氮气流32和富氧气流35，富氧气流35作为氧化剂被送至段1的二段转化炉。ASU 3还提供环境温度的氮气流32a。调节合成气的HN比所需的氮气部分由流34提供，部分由所述环境温度的氮气32a提供。
图2中示出了深冷段2的以及氮气流32的使用的优选实施方式。
深冷段2主要包括主间接热交换器201、洗气塔202和冷凝器203。粗合成气13在主热交换器201中被冷却至深冷温度，冷却的粗合成气14被输送至塔202，在塔202中，进行甲烷、氮气和其他杂质的深冷分离。热交换器201从在塔202中获得并且预先在冷凝器203中冷却的净化过的合成气16、气态氮气流33和在所述塔202的底部分离出的液态流20回收冷量。
更详细地，在所述塔202的顶部获得的产出的气体15在冷凝器203中被进一步冷却，冷凝器203通过冷的、至少部分为液态的氮气流32的蒸发而冷却，获得净化过的合成气16并进一步除去另外量的甲烷、氮气和其他杂质，所述另外量的甲烷、氮气和其他杂质通过液态循环流18循环回塔202。
氮气流32通过冷凝器203至少部分地蒸发并作为流33排出，流33通过主交换器201被加热，因此冷却输入的粗合成气13。
主要由甲烷和氮气组成的液态流19在塔202的底部被回收，在装置22中膨胀以及可能地蒸发，获得流20，所述装置22比如为膨胀阀或透平机。所述流20在主交换器201中还被再加热，作为流21排出，流21可以用作燃料。流19在透平机中发生膨胀能够回收一些有用功。
因此，主交换器201由氮气流33、冷的净化过的合成气16以及甲烷流20制冷，氮气流33、冷的并净化过的合成气16以及甲烷流20全部用来制冷输入的粗合成气13。
以大约环境温度离开深冷段2的被再加热过且净化过的合成气17被送至主合成气压缩机40，接着送至氨合成回路。气态被再加热过的氮气流34被输送至合适的氮气压缩机41，并与被压缩且净化过的合成气以及装置3提供的环境温度的氮气32a混合以调节氨合成回路中的H/N比。压缩的氮气35与合成气压缩机40的输出混合，形成具有大约3∶1的合适HN比的合成气的流23。
图2示出了单独压缩实施方式，其中，合成气和氮气分别在压缩机40和压缩机41中被单独地压缩。在本发明的其他实施方式中，氮气也可在主合成气压缩机40的上游(例如，入口处)与净化过的合成气混合。在后一种情况中，当改进现有装置时，可能需要改进现有的合成气压缩机以容纳另外的氮气。
本发明的一个方面是一种用于改进现有的氨合成设备的前端的方法。例如，至少通过下列操作进行改进至少包括一段转化炉和二段转化炉以及用于处理粗合成气的深冷段2的前端段：安装与所述前端并联的空气分离单元3；提供将所述空气分离单元3中产生的液态富氮气流32输送至所述深冷段2的装置，提供将同一单元3中产生的富氧气流35输送至前端的二段转化炉的管线，以提高转化段1的产能。本领域的技术人员明白，以上是基本步骤，将根据具体要求提供其他的装置比如阀门、管线、辅助设备等。

Claims (14)

1.一种用于制取氨补充合成气的方法，所述方法包括以下步骤：
-转化烃原料(11)，之后进行变换、CO2脱除以及甲烷化的步骤，获得包括氢气和氮气的粗氨补充合成气的流(13)；
-在深冷净化段(2)中处理所述粗氨补充合成气，获得净化过的合成气的流(17)；
-将深冷温度的液态富氮气流(32)输送至所述深冷净化段；
-在所述深冷净化段中提供在合成气和所述液态富氮气流之间的间接热交换，所述液态富氮气流至少部分地蒸发以提供所述深冷净化段的制冷。
2.根据权利要求1所述的方法，其中，所述液态富氮气流(32)在通过所述深冷净化段而至少部分蒸发之后在所述深冷净化段的输出处被回收，并与所述净化过的合成气混合以提供调节所述氨补充合成气的氢/氮比所需的氮气的至少一部分。
3.根据权利要求1或2所述的方法，还包括在空气分离单元(3)中处理空气流(31)获得所述液态富氮气流(32)和富氧气流(35)的步骤。
4.根据权利要求3所述的方法，其中，所述空气分离单元(3)提供所述液态富氮气流(32)以及环境温度的且气态的第二富氮气流(32a)，且调节所述氨补充合成气的HN比所需的氮气的量中部分由在所述深冷净化段的输出处回收的蒸发的液态富氮气流(34)提供以及部分由环境温度的所述富氮气流(32a)提供。
5.根据权利要求3所述的方法，其中，通过将所述富氧气流(35)注入到转化段(1)的二段转化炉中，所述富氧气流用作转化过程中的另一氧化剂。
6.根据前述权利要求中任一项所述的方法，其中：
-所述粗合成气(13)在所述深冷净化段(2)的主热交换器(201)中冷却至深冷温度，获得冷却的粗合成气(14)；
-所述冷却的粗合成气(14)被输送至接触装置(202)，在该接触装置(202)中，通过深冷净化获得包括杂质的液态部分(19)，并且该液态部分(19)与合成气分离；
-从所述接触装置(202)回收净化过的合成气(15)，该净化过的合成气(15)在冷凝器(203)中被进一步冷却和净化，所述冷凝器(203)通过所述液态富氮气流(32)的至少部分蒸发而被制冷；
-在所述冷凝器的输出获得进一步净化过的合成气(16)，通过与输入的粗合成气(13)和获自所述冷凝器的蒸发的氮气流(33)进行热交换，所述合成气(16)在所述主热交换器(201)中被再加热。
7.根据权利要求6所述的方法，其中，包括杂质的所述液态部分还用作所述深冷净化段(2)的主热交换器(201)的冷却介质(20)。
8.根据前述权利要求中任一项所述的方法，其中，所述液态富氮气流和/或环境温度的所述富氮气流是基本上纯净的氮气。
9.一种用于制取氨补充合成气的设备，所述设备包括：
-前端段，所述前端段包括适于转化烃原料并产生粗氨合成气的流的转化段(1)；
-深冷净化段(2)，所述深冷净化段(2)处理所述前端段中产生的所述粗氨合成气；
-将深冷温度的液态富氮气流(32)输送至所述深冷净化段的装置，所述液态富氮气流(32)用作热交换介质以制冷所述深冷净化段；
-在所述深冷净化段(2)中的所述合成气和所述液态富氮气流之间的至少一个间接热交换器(203，201)，所述液态富氮气流在所述热交换器中至少部分地蒸发以提供所述深冷段的制冷。
10.根据权利要求9所述的设备，所述设备还包括用于回收所述深冷净化段的输出处的蒸发的富氮气流(34)以及用于使所述蒸发的富氮气流与净化过的合成气(17)混合的装置，以提供调节所述氨补充合成气的氢/氮比所需的氮气的至少一部分。
11.根据权利要求9或10所述的设备，所述设备包括空气分离单元(3)，所述空气分离单元(3)提供所述液态富氮气流(32)和用于调节HN比的环境温度的第二氮气流(32a)，以及另外提供富氧气流(35)，该富氧气流(35)被作为氧化剂输送至所述转化段(1)。
12.根据权利要求11所述的设备，其中，所述前端段包括一段转化炉、二段转化炉以及用于变换、CO2脱除和甲烷化的设备，所述富氧气流(35)被输送至所述转化段的所述二段转化炉。
13.根据权利要求9到12中任一项所述的设备，其中，所述深冷净化段(2)包括：接触装置，该接触装置例如为深冷冷凝塔(202)；冷凝器(203)，该冷凝器接收在所述接触装置中获得的部分净化过的合成气(15)，所述冷凝器由所述液态富氮气流(32)制冷；主热交换器(201)，在该主热交换器(201)中，输入的粗合成气(13)通过与以下物质中的一个或多个进行热交换而冷却：在所述冷凝器中蒸发的氮气流(33)、净化过的合成气(16)、所述接触装置的底部流出物(20)。
14.一种用于改进氨合成设备的前端段的方法，所述前端段包括用于将烃原料转化为氨粗补充合成气的至少具有一段转化炉和二段转化炉的转化段(1)，所述方法至少包括以下步骤：
-安装与所述前端段并联的空气分离单元(3)；
-如果原设备中不存在深冷段，提供用于处理所述粗补充合成气的深冷段；
-提供将在所述空气分离单元中产生的液态富氮气流(32)输送至所述深冷段以用作冷却介质的装置；
-提供将在所述空气分离单元中产生的富氧气流(35)输送给所述二段转化炉的管线，以提高所述转化段的产能。
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