CN106132508B - 制备和纯化合成气体的方法 - Google Patents

制备和纯化合成气体的方法 Download PDF

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CN106132508B
CN106132508B CN201580007391.2A CN201580007391A CN106132508B CN 106132508 B CN106132508 B CN 106132508B CN 201580007391 A CN201580007391 A CN 201580007391A CN 106132508 B CN106132508 B CN 106132508B
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M·朗
C·福斯
B·许雷尔
G·萨拉查杜阿尔特
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Abstract

本发明涉及一种用于制备和纯化合成气体流(S)的方法，其包括以下步骤：在气体制备单元(4)中从含碳氢化合物的进料(5)制备含CO和H2的合成气体流(S)，从合成气体流(S)分离(1)至少CO2，并且从合成气体流(S)低温分离(6)CO。根据本发明，在合成气体流中以在从5体积％到30体积％范围内浓度存在的CO2通过在CO的低温分离(6)的上游的变温吸附(1)从合成气体流(S)分离出来到小于10体积ppm，其中CO2被吸附到无序吸附床形式的吸附剂上，并且在CO2的吸附过程(1)中吸附剂通过从吸附剂间接热传递到热传递介质的方式被冷却，并且负载有CO2的吸附剂至少通过从热传递介质间接热传递到吸收剂被加热，以实现CO2的解吸附。

Description

制备和纯化合成气体的方法
本发明涉及一种制备和纯化包含CO和至少H2、CO2、CH4、H2O、并 且可能包含N2的合成气体的方法。合成气体通过根据现有技术的蒸汽转化 或部分氧化制备。为了增加合成气体中CO的含量，从合成气体中分离出的 CO2可以在该气体制备之前作为起始原料被再循环。
变温吸附(TSA)方法在现有技术中是已知的。迄今为止这些方法已经 在工业上主要用于除去气体混合物中的痕量成分(小于1体积％)。TSA方 法通常使用至少两个容器(吸附器)进行实施，所述容器填充有吸附性活 性材料(也成为吸附剂)并且交替操作。当一个容器处于吸附模式，热再 生气体通过另一容器，其因此被直接热传递加热，即该再生气体接触吸附 剂。吸附剂的吸附能力随着温度增加而降低，并且因此会发生被保留的成 分的解吸附。解吸附的成分被再生气体稀释并且从吸收剂冲走。再生气体 的使用另外地造成气相中被吸附的成分的分压的降低，并因而促进了被保 留的痕量成分的解吸附。加热时间和冷却时间通常被可获得的或者能够使 用的再生气体的量限制，并且通常在数个小时的范围内(通常多于三个小 时)。这造成通常显著地高于6个小时的循环时间。
在含有CO和H2的合成气体或含氧气体的低温分离以制备一氧化碳或 氢产物时(这里，例如CO被冷凝并且从H2中分离)，二氧化碳和水和可能 存在的甲醇必须被从气流中除去，以防止这些成分在设备的随后冷却部分 中的冻析。吸附过程，称为洗涤(例如胺或低温甲醇洗涤)，主要用于除去 相对大量的二氧化碳。在洗涤(scrub)后，合成气体通常仍然含有痕量的二氧 化碳(例如小于50体积ppm)，并且被含水或含甲醇的洗涤介质饱和。在 低温液化之前，二氧化碳和水或甲醇因此通常通过TSA法分离出去，以防 止低温分离中的冻析。
EP1291067A2描述了基于用于除去痕量二氧化碳和水的热交换器的快 速TSA法。其中描述了合成气体的精细纯化。
现有技术中不知晓以这种方式(称为批量分离)可以分离多大量的二 氧化碳且特别是水或甲醇。因此，例如从转化装置中的合成气体中10体积 ％的CO2通常在传统的洗涤中被除去到小于每体积50ppm并且在传统的 TSA中，CO2含量然后降低到小于0.1体积ppm，(即由通过用热再生气体 处理吸附了的吸附剂的直接热传递的吸附剂的再生)。前述过程(洗涤和随 后的TSA)的进一步的缺点是相对高的成本费用，装置的相对高的花费和 涉及两个单独的分离过程的事实。
本文指出的前述现有技术的缺点至少部分地被下面所述的本发明所克 服。
本发明对于在所制得的合成气体流中在从5体积％到30体积％的浓度 范围中存在的CO2，提供了通过在CO的低温分离的上游的变温吸附减少到 在合成气体流中小于10体积ppm，其中CO2被吸附到吸附剂上(其为特别 是无序吸附床的形式)并且在CO2的吸附过程中吸附剂通过从吸附剂间接 热传递到热传递介质的方式被冷却，并且负载有CO2的吸附剂至少部分地 (特别地仅仅)通过从流体热传递介质间接热传递到吸收剂来加热，以产生CO2的解吸附(该变温吸附也称为RTSA(快速变温吸附))。
本发明的方法特别适合于从所制得的并具有从5体积％到30体积％浓 度的合成气体中分离CO2。通过在CO的低温分离之前的RTSA，使含CO2的进料流小于10体积ppm，特别是小于按体积计1ppm，更特别是小于0.1 体积ppm。这表示存在于合成气体中的至少99.98体积％的CO2被分离出去。 这种高除去度通过在CO2吸附期间被热传递介质冷却的吸附剂实现，使得 吸附剂不会被吸附的热量进一步加热，并且吸附过程可以在相对低的温度 有效进行。
许多合成气体的制备方法是已知的，例如碳氢化合物特别是CH4的蒸 汽转化或天然气的部分氧化。此外，通过自热转化或干法转化制备合成气 体是可行的。本发明的方法不限于单独的合成气体制备过程，其也适用于 组合，例如连续或并行连接的合适过程，只要实现了合成气体的制备。
因此，本发明提供了快速变温吸附(RTSA)方法的用途，其特别地具 有对于至少CO2并且特别地以及水和/或甲醇的除去相对短的循环时间，优 选从1到4小时。本文中吸附剂的加热和冷却是间接实现的，优选地通过 由分隔壁分隔的热传递介质或热流体而不是通过如在传统TSA过程的情况 一样直接流过吸附剂的再生气体，来间接实现的。由此可用单一的快速TSA 过程或具有间接热传递和特别相对短的循环时间的适合的装置来取代以上 提及的用于CO2除去的洗涤和任何下游的传统TSA过程。
在过程的进一步有利的实施方式中，在从10bar到50bar、优选地从15bar 到40bar的表压范围下，在根据本发明的快速变温吸附(RTSA)中，二氧 化碳从合成气体流中被分离，并且特别地以小的压降优选地只有由于流体 动力效应的压降再循环到合成气体制备中。
相比现有技术，本文提出的方法不仅具有上述用于CO2的批量除去的 洗涤的益处，并且另外可以保持管路压力。因此，二氧化碳可以在不需要 大的花费的前提下进行再循环，例如使用相对很少的压缩阶段或甚至仅通 过向合成气体生产使用鼓风机。
在所述过程的进一步有利的实施方式中，根据本发明所使用的RTSA 接着是传统的变温吸附过程，通过CO2并且特别地通过H2O和/或甲醇的除 去对合成气体进行精细纯化。
通过下游的TSA过程也可以除去痕量成分。因此，上游的快速TSA过 程可以仅设计用于批量除去，携带的任何残余成分接着能够在接下来的 TSA过程中被分离出去。
特别的优选在本发明的实施方式中给出，其中合成气体中存在的CO2通过RTSA基本上完全除去到小于1体积ppm的浓度，并且仍然存在于合 成气体的CO2通过传统的TSA被减少，特别地减少到至少0.1体积ppm或 小于0.1体积ppm。
在这样的方案中(首先RTSA接着TSA)，吸附剂可以有益地被更好地 利用，这样可以使RTSA更小地进行。在将CO2从例如10体积％减少到0.1 体积ppm的RTSA中，部分的吸附剂将保持为很大程度上未利用。
根据本发明的一个进一步方面，提出了一种装置，其至少包括：
制备合成气体流的单元；
在合成气体制备的下游的至少一个变温吸附器，其具有无序吸附床形 式的吸附剂以从合成气体流中吸收CO2(并且也特别地吸收H2O和/或甲 醇)，其中变温吸附器被配置为通过将流体传递介质的热间接热传递到吸附 剂来再生吸附剂，同时CO2从吸附器解吸，
在变温吸附器的下游的低温分离单元，其被配置为从合成气体流中低 温地(例如通过冷凝)分离一氧化碳；
从变温吸附器到合成气体制备的回流管路(特别是带有鼓风机)，其被 配置为将解吸附的CO2再循环到合成气体制备中；和
特别的在变温吸附器下游的用于从合成气体流中分离氢气的变压吸附 器。
该合成气体装置优选地安装用于实施上述的过程。气体洗涤，例如胺 洗涤或低温甲醇洗涤(Rectisol scrub)，不是必须的或特别地不是明确地提供 的。相反，上述的变温吸附器替代了气体洗涤单元(参见以上)。二氧化碳 通过回流管路被作为起始原料供给到合成气体制备中。与前述已知装置相 反，本文不需要复杂的压缩阶段，因为CO2可以在高压下(参见以上)在 所述变温吸附器中被回收。因此，仅有由于流体动力效应的压降(例如管路摩擦损失)发生并且这些压降可以通过(简单的)鼓风机得到补偿。再 循环因此被简化并且更经济地进行。在合成气体装置的进一步有益的实施 方式中，吸附剂用热再生气体(参见以上)处理以实现再生的传统变温吸 附器被安装在上述的变温吸附器的下游。痕量的CO2可以通过该下游的用 于实施传统的TSA过程的单独的变温吸附器被除去。这里，所述变温吸附 器可以被配置为仅用于批量清除，携带的任何残余的组分接着能够被在随 后的传统变温吸附器中被分离出去。
本文提出的方法和本文提出的合成气体装置使得更经济地制备合成气 体而不需要使用气体洗涤变成可能。
以上描述的本发明在下面根据相关技术背景参照了显示优选实施方式 的所附附图详细地进行了描述。本发明不被纯示意性的附图以任何方式被 限定，并且应该注意的是附图不是按比例的，并且不适合限定尺寸比例。 附图显示：
图1：用于制备/纯化合成气体的现有技术的已知方法的框图；
图2：本发明的方法或本发明的合成气体装置的第一实施方式的框图； 和
图3：本发明的方法或本发明的合成气体装置的第二实施方式的框图。
图1显示了传统的合成气体装置11，其中含碳氢化合物的进料(例如 天然气)被首先在合成气体制备的单元中转换为含有至少CO和H2和CH4和可能痕量的N2的合成气体流S。合成气体S被送到洗涤9，其中CO2和 水被分离出去。痕量的CO2和可能的水或甲醇在传统的变温吸附器3中接 着被从合成气体流S中分离出去，在变温吸附器3中热再生气体与吸附剂接触以实施到吸附剂的直接热传递，从而使吸附剂再生。最后，一氧化碳 和可能的尾气8(含有例如CO、CH4和可能的H2和N2)在低温分离单元 (也称为冷却箱)6中从合成气体流S中分离出去。在下游，另外，氢气7a 和尾气8a(含有例如CO、CH4和可能的H2和N2)在变压吸附器7中通过 变压吸附从合成气体流S中分离出去。另外，已经在洗涤9中被除去的二 氧化碳通过回流管路14再循环到合成气体制备4中，对于其来说因为对于 洗涤9所需要的压降所以多级压缩机10是必须的。通过该传统的合成气体 装置，合成气体流中的二氧化碳的浓度从10体积％下降到小于50体积ppm。
图2显示了根据本发明的方法的第一实施方式或相关的装置12，如以 上所述的。这里，洗涤9和传统的变温吸附器3(见图1)被快速变温吸附 器1取代，其能够单独地将大量的二氧化碳和水分离出去。在变温吸附器1 中，无序床形式的吸附剂通过被间接热传递加热的方式再生。这里热通过 与吸附剂空间上隔离的流体热传递介质提供。以这种方式在高气压下回收 的二氧化碳可以因此立刻被再循环，仅通过鼓风机2补偿仅由于流体动力 效应造成的压降。通过该过程，合成气体流中二氧化碳的浓度被从例如5 体积％到30体积％降低到小于10体积ppm，特别是降低到至少0.1体积ppm 或小于0.1体积ppm。
图3显示了根据本发明的方法的第二实施方式或根据本发明的合成气 体装置13，其类似于图2中的合成气体装置12。这里，快速变温吸附器1 接着是另外的传统的变温吸附器3，其通过直接热传递(参见以上)再生， 并且承担了痕量CO2和可能的水的除去任务。
附图标记列表
1 变温吸附器(RTSA)
2 鼓风机
3 变温吸附器(TSA)
4 反应器或合成气体制备
5 进料
6 冷却箱或低温分离单元
7 变压吸附器
7a 原始氢气流
8，8a 尾气
9 用于除去CO<sub>2</sub>的洗涤
10 多级压缩器
11 传统合成气体装置
12 第一合成气体装置
13 第二合成气体装置
14 回流管路
S 合成气体流

Claims (7)

1.一种用于制备和纯化合成气体流的方法，其包括以下步骤：
-在气体制备单元(4)中从含碳氢化合物的进料(5)制备含CO和H2的合成气体流(S)，
-从合成气体流(S)分离至少CO2，并且
-从合成气体流(S)低温分离(6)CO，
其特征在于，
将在合成气体流(S)中以在从5体积％到30体积％的范围内的浓度存在的CO2通过在CO的低温分离的上游的变温吸附(1)减少到在合成气体流(S)中小于10体积ppm，其中CO2被吸附到吸附剂上并且在CO2的吸附(1)期间通过从吸附剂到热传递介质的间接热传递方式将吸附剂冷却，并且负载有CO2的吸附剂至少部分地通过从热传递介质到吸收剂的间接热传递被加热，以实现CO2的解吸附，并且其中被吸附的CO2在5bar-90bar的压力范围内解吸附，并作为合成气体制备的起始原料再循环至气体制备单元(4)。
2.根据权利要求1的方法，其特征在于所述吸附剂被配置为无序吸附床。
3.根据权利要求1或2的方法，其特征在于CO2通过变温吸附(1)的方式被除去至小于1体积ppm。
4.根据权利要求1或2的方法，其特征在于被吸附的CO2在15bar-60bar的压力范围内解吸附，并作为合成气体制备的起始原料再循环至气体制备单元(4)。
5.根据权利要求1或2的方法，其特征在于合成气体流(S)在10-50bar范围内的压力下引入到变温吸附(1)中。
6.根据权利要求1或2的方法，其特征在于在变温吸附(1)的下游实施另一个变温吸附(3)，以从合成气体流(S)中分离出仍然存在于合成气体流(S)中的CO2，其中CO2被吸附到吸附剂上，并且负载了CO2的吸附剂用再生气体处理，使得再生气体的热量直接传递到吸附剂上而实现CO2的解吸。
7.根据权利要求3的方法，其特征在于CO2通过变温吸附(1)的方式被除去至小于0.1体积ppm。
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