CN112143537A - 用于生产ch4的低温分离合成气的方法和设备 - Google Patents

用于生产ch4的低温分离合成气的方法和设备 Download PDF

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CN112143537A
CN112143537A CN202010585528.5A CN202010585528A CN112143537A CN 112143537 A CN112143537 A CN 112143537A CN 202010585528 A CN202010585528 A CN 202010585528A CN 112143537 A CN112143537 A CN 112143537A
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heat exchanger
carbon monoxide
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A·埃尔南德斯
B·德莫利安
G·特谢拉
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Abstract

在分离包含氢气，一氧化碳和甲烷的合成气的方法中，将合成气(4)在热交换器(6)中冷却，将冷却后的合成气输送至第一塔(1)，将来自第一塔的塔顶气体(10)进行部分冷凝，并将冷凝气体的至少一部分(17)输送至第一塔的顶部，将来自第一塔的塔底液体(8)输送至第二塔(2)的中间位置和将相对于合成气富含一氧化碳的液体(56)输送至第二塔的顶部。

Description

用于生产CH4的低温分离合成气的方法和设备
本发明涉及用于生产CH4的低温分离合成气的方法和设备。
一氧化碳和氢气的生产单元可以分为两部分：
合成气的生成(基本上包含H2，CO和任选的CH4，CO2，Ar或N2的混合物)。
在各种生产合成气的工业路线中，基于煤气化的路线似乎正在不断扩大，特别是在中国等煤炭资源丰富的国家。还证明天然气的部分氧化方法以单独或以低H2/CO生产比率用于生产CO是有利的。另一路线是蒸汽重整。
合成气的纯化。
找到以下内容：
·利用液体溶剂洗涤的单元，以除去合成气中存在的大多数酸性气体；
·用于在吸附剂床上进行净化的单元；
·用于生产CO的通过低温路线(称为冷箱路线)分离的单元。
下面的文献描述了以下方案：具有用(纯或不纯)CO洗涤的第一步，汽提步骤和用于通过低温蒸馏分离CO/CH4的塔。
·使用CO泵+N2循环用纯CO洗涤：CN101688753。
·在具有顶部冷凝器，循环氢膨胀涡轮机，无循环压缩机的第一塔中用不纯的CO洗涤：FR 2754541。
·用输送至CO/CH4分离塔顶部的CO和液态CO洗涤：WO07/018518。
·用CO进行洗涤，但无汽提塔：FR3018599和US4488890。
·用CO进行洗涤：WO2008/113494。
·用CO进行洗涤：CN105865147。
上述三个文献不包括在汽提塔中用(纯或不纯)CO进行洗涤，并且具有在汽提塔顶部具有CH4损失的缺点。
本发明包括用于进行分离方法的冷箱，该分离方法包括在中等压力下，通常在5至20bar abs之间进行的在汽提塔顶部用不纯的CO洗涤。
用于在汽提塔顶部洗涤的富含CO的液体来自用于在合成气上进行高压洗涤的塔的顶部的分离容器，或者来自汽提塔顶部冷却后的冷凝容器。该特征使得可以将CH4的回收率提高约0.3点。
根据本发明的一个主题，提供了一种分离包含氢气，一氧化碳和甲烷的合成气的方法，其中
i)将合成气在热交换器中冷却；
ii)将冷却的合成气输送至第一塔，其中所述第一塔为洗涤塔，将来自第一塔的塔顶气体部分冷凝，并将至少一部分冷凝气体输送至第一塔的顶部；
iii)将来自第一塔的塔底液体输送至第二塔的中间位置，其中所述第二塔为汽提塔；
iv)将相对于合成气富含一氧化碳的液体输送至第二塔的顶部；
v)将来自第二塔的塔顶气体的至少一部分在热交换器中再加热；
vi)将来自第二塔的塔底液体输送至第三塔的中间位置，其中所述第三塔为具有顶部冷凝器的蒸馏塔；
vii)从第三塔的底部排出富含甲烷的液体并在热交换器中汽化，以形成富含甲烷的气态产物，从第三塔的顶部排出富含一氧化碳的气体并在热交换器中再加热，以形成富含一氧化碳的气态产物。
根据其他可选方面：
·来自第一塔和/或第二塔的塔顶气体的至少一部分被部分冷凝，优选在热交换器中冷凝，并被输送至分相器；
·至少一部分富含一氧化碳的液体来自分相器或来自两个分相器；
·液体/分相器的液体是通过部分冷凝来自第一塔的塔顶气体而产生的，并且在膨胀后被输送至第二塔的塔顶；
·液体/分相器的液体是通过部分冷凝来自第二塔的塔顶气体而产生的，并且未经膨胀而被输送至第二塔的塔顶；
·来自第一塔的塔顶气体的至少一部分被部分冷凝；
·通过汽化富含甲烷的液体而形成的一部分气体被压缩并送回到第三塔的底部，以便在其中分离。
·第二塔不具有顶部冷凝器；
·第一塔包含用于交换材料和热量的装置；
·第二塔包含用于交换材料和热量的装置；
·第一塔从分相器接收包含至少80摩尔％一氧化碳的液体；
·第二塔从分相器接收包含至少80摩尔％一氧化碳的液体；
·来自第一塔的塔顶气体在热交换器中部分冷凝。
根据本发明的另一方面，提供了一种用于分离包含氢气，一氧化碳和甲烷的合成气的设备，该设备包括：第一塔，其为洗涤塔，第二塔，其为汽提塔，第三塔，其为具有塔顶冷凝器的蒸馏塔，热交换器，用于将合成气输送至热交换器中进行冷却的装置，用于将冷却的合成气输送至第一塔的装置，用于将来自第一塔的塔顶气体部分冷凝的装置，用于将至少一部分冷凝气体输送至第一塔的顶部的装置，用于将来自第一塔的塔底液体输送至第二塔的中间位置的装置，用于将相对于合成气富含一氧化碳的液体输送至第二塔的顶部的装置，用于将来自第二塔的至少一部分塔顶气体输送至热交换器中进行再加热的装置以及用于将来自第二塔的塔底液体输送至第三塔的中间位置的装置，用于从第三塔的底部排出富含甲烷的液体的装置，用于将所排出的液体输送至热交换器中汽化以形成富含甲烷的气态产物的装置，用于从第三塔的顶部排出富含一氧化碳的气体的装置，以及用于将富含一氧化碳的气体输送至热交换器中进行再加热以形成富含一氧化碳的气态产物的装置。
根据本发明的另一方面，该设备包括用于部分冷凝来自第一塔和/或来自第二塔的塔顶气体的至少一部分的装置，优选地由热交换器构成。
将参考代表根据本发明的分离方法的附图更详细地描述本发明。
·[图1]表示使用第一塔1，第二塔2和第三塔3的方法，其中第一塔1包含用于交换材料和热量的装置，其中用不纯的一氧化碳进行洗涤，第二塔2包含用于交换材料和热量的装置，其为并入用不纯一氧化碳洗涤的汽提塔，第三塔3为在低温下蒸馏的塔。
在热交换器6中冷却包含一氧化碳，氢气和甲烷以及任选地氮气的合成气4。将气体4冷却至热交换器的中间温度，并将其输送至第一塔1的底部。从第一塔的底部排出贫氢液体8。富氢塔顶气体10在热交换器6中被冷却，其中其在被输送至第一分相器12之前部分冷凝。富氢气体14从第一分相器12中被排出并在交换器6中再加热。来自分相器12的液体17包含至少80摩尔％的一氧化碳，并且被送回到塔1的顶部以形成回流。
液体8在阀V1中膨胀，并输送至区段2A下方的汽提塔2的中间位置。塔底液体16在再沸器14中被循环气体30加热。从区段2A上方在塔2的顶部取出的塔顶气体22在热交换器6中被冷却，在热交换器6中部分冷凝并被输送至第二分相器20，其液体被送回到塔2的顶部。气体22的仅一部分可以部分冷凝和/或形成的液体的仅一部分可以被输送至该塔中。该液体将塔2的顶部转化为洗涤段，从而可以减少甚至消除气体22中甲烷的损失。来自分相器20的气体24在热交换器6中被再加热。
来自汽提塔2的塔底液体18在阀V3中膨胀并输送至蒸馏塔3的中间位置。来自蒸馏塔的塔顶气体在被圆柱形壁包围的再沸器-冷凝器中冷凝以产生围绕再沸器的液体浴。
塔底液体38是该方法的富含甲烷的产物。它在阀V5中膨胀，在热交换器6中汽化，并在压缩机C3中压缩，并优选分成两部分。压缩流40在热交换器6中冷却并分成两部分；将处于交换器的中间温度的部分42输送至塔3的底部以在其中分离。剩余部分44继续其冷却至较低的中间温度，在阀V6中膨胀并且重新结合流38以被再加热。
因此，在塔3中底部再沸器不是必需的。但是，应当理解，本发明不限于以这种方式对塔3的底部进行再加热的方法。
在压缩机C3中压缩的流50在压缩机C4中被压缩，从而形成富含甲烷的气态产物。
该方法包括封闭循环，例如氮气循环。氮气在压缩机C1中然后在压缩机C2中被压缩，以形成气流28。气流28在热交换器6中被冷却并且被分成两部分。从热交换器6以中间温度离开的馏分30用于通过热交换器14再沸腾汽提塔，在热交换器14中冷凝的馏分30在阀V4中膨胀并被输送至塔3的顶部冷凝器。
来自压缩机C2的氮气28的剩余部分32在热交换器6中完全冷却，在阀V6中膨胀并被输送至顶部冷凝器。
从塔3的顶部冷凝器中排出液体34，使其在阀V7中膨胀并在热交换器6中再加热。塔3的顶部冷凝器的顶部的气体46与汽化液体34混合，形成气体48。气体48被热交换器6再加热到其热端，并被输送至压缩机C2的上游和压缩机C1的下游。
在第三塔3的顶部排出富含一氧化碳的气体36，并在热交换器6中再加热，以形成最终的气态产物。
在涡轮机中，没有该方法的流被膨胀。没有产生液体形式的产品。
[图2]示出了与[图1]非常相似的方法。但是，它通过以下几点有所不同：
·[图1]的第二分离容器20被取消。
·第二塔2的区段2A被供给有来自分离容器12的液体的一部分56，其通过阀V8膨胀。
因此，以与先前附图相同的方式，输送至第二塔2的顶部的液体56用于减少来自第二塔2的塔顶气体22中的甲烷损失。
塔顶气体22在热交换器6中完全再加热而没有部分冷凝。

Claims (10)

1.分离包含氢气，一氧化碳和甲烷的合成气的方法，其中：
i)将合成气(4)在热交换器(6)中冷却；
ii)将冷却的合成气输送至第一塔，其中所述第一塔为洗涤塔(1)，将来自第一塔的塔顶气体(10)进行部分冷凝，并将冷凝气体的至少一部分(17)输送至第一塔的顶部；
iii)将来自第一塔的塔底液体(8)输送至第二塔的中间位置，其中所述第二塔为汽提塔(2)；
iv)将相对于合成气富含一氧化碳的液体(56)输送至第二塔的顶部；
v)将来自第二塔的塔顶气体(22、24)的至少一部分在热交换器中再加热；
vi)将来自第二塔的塔底液体(18)输送至第三塔的中间位置，其中所述第三塔为具有顶部冷凝器的蒸馏塔(3)；
vii)从第三塔的底部排出富含甲烷的液体(38)，并在热交换器中汽化，以形成富含甲烷的气态产物(50)，从第三塔的顶部排出富含一氧化碳的气体(36)并在热交换器中再加热，以形成富含一氧化碳的气态产物。
2.根据权利要求1所述的方法，其中来自第二塔(2)的塔顶气体(10、22)的至少一部分被部分冷凝，优选在热交换器(6)中冷凝，并被输送至分相器(20)。
3.根据权利要求2所述的方法，其中至少一部分富含一氧化碳的液体来自分相器(12)或来自两个分相器(12、20)。
4.根据权利要求2或3所述的方法，其中通过部分冷凝来自第一塔(1)的塔顶气体(10)来生产所述分相器(12)的液体(17，56)，并且在膨胀(V8)后将所述液体输送至第二塔(2)的顶部。
5.根据权利要求2或3所述的方法，其中通过部分冷凝来自第二塔(22)的塔顶气体来生产分相器(20)的液体，并且将液体输送至第二塔(2)的顶部，而无需进行膨胀。
6.根据前述权利要求中任一项所述的方法，其中通过汽化富含甲烷的液体(38)而形成的气体的一部分(40)被压缩并送回到第三塔(3)的底部，以便在其中分离。
7.根据前述权利要求中任一项所述的方法，其中第二塔(2)不具有顶部冷凝器。
8.根据前述权利要求中任一项所述的方法，其中所述第一塔从所述分相器(12)接收包含至少80摩尔％的一氧化碳的液体(17)。
9.用于分离包含氢气，一氧化碳和甲烷的合成气的设备，其包括第一塔(1)，其为洗涤塔，第二塔(2)，其为汽提塔，第三塔(3)，其为具有顶部冷凝器的蒸馏塔，热交换器，用于将合成气(4)输送至热交换器(6)中进行冷却的装置，用于将冷却的合成气输送至第一塔(1)的装置，用于部分地冷凝来自第一塔的塔顶气体(10)的装置，用于将冷凝气体的至少一部分(17)输送至第一塔的顶部的装置，用于将来自第一塔的塔底液体(8)输送至第二塔(2)的中间位置的装置，用于将相对于合成气富含一氧化碳的液体(56)输送至第二塔的顶部的装置，用于将来自第二塔的塔顶气体(22，24)的至少一部分输送至热交换器中进行再加热的装置和用于将来自第二塔的塔底液体(18)输送至第三塔(3)的中间位置的装置，用于从第三塔的底部排出富含甲烷的液体(38)的装置，用于将排出的液体输送至热交换器中汽化以形成富含甲烷的气态产物(50)的装置，用于从第三塔的顶部排出富含一氧化碳的气体(36)的装置，以及用于将富含一氧化碳的气体输送至热交换器中进行再加热以形成富含一氧化碳的气态产物的装置。
10.根据权利要求9所述的设备，包括用于部分冷凝来自第二塔(2)的塔顶气体(22)的至少一部分的装置，优选地由热交换器(6)构成。
CN202010585528.5A 2019-06-26 2020-06-24 用于生产ch4的低温分离合成气的方法和设备 Pending CN112143537A (zh)

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