CN1247445C - 一氧化碳变换方法及反应器 - Google Patents

一氧化碳变换方法及反应器 Download PDF

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CN1247445C
CN1247445C CNB031360742A CN03136074A CN1247445C CN 1247445 C CN1247445 C CN 1247445C CN B031360742 A CNB031360742 A CN B031360742A CN 03136074 A CN03136074 A CN 03136074A CN 1247445 C CN1247445 C CN 1247445C
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T·罗斯特鲁普-尼尔森
E·罗格斯特－尼尔森
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Abstract

一种包含一氧化碳的原料气的等温变换工艺和反应单元，该工艺包括步骤：将原料气引入反应单元中的反应器管，反应器管带有位于反应区的变换催化剂的固定床；在可有效地使一氧化碳与蒸汽反应物生成氢的变换反应条件下使原料气与催化剂接触；冷却介质具有沿反应器管的外壳侧流动的降膜形式，通过冷却介质进行非直接热交换使反应冷却，并从降膜中去除加热的冷却介质；使变换反应生成的氢通过氢选择膜到达渗透区；将氢从渗透区抽出并将耗尽一氧化碳的原料气从反应区排出。

Description

一氧化碳变换方法及反应器
技术领域
本发明涉及一种改进的利用富一氧化碳的工业生产流体在有催化剂的条件下进行一氧化碳变换反应产生氢的一氧化碳变换方法。
具体地，本发明涉及一种方法和反应单元，可进行包含一氧化碳的原料气的等温变换，同时对进行反应的原料气所形成的氢进行膜分离。
背景技术
变换反应 是放热反应，最好在低温下进行。低温可增加C0变换。因此，温度越低，合成气朝CO2和H2方向移动的越多，倘若气体能接触到足够的活性变换催化剂的话。一般将变换反应分为低于300℃(通常为200-300℃，低温变换)和高于300℃(通常为300-500℃，高温变换)。因此，许多生产和/或使用氢气的工厂一般具有高温变换装置进行大规模的CO变换，然后用蒸汽冷却，接着用低温变换装置进行CO变换，以保证更完全的CO变换。
为了控制反应温度和合理的反应速率，反应热量必须去除。传统的变换方法因此分两级进行，在催化剂床之间进行中间热量清除。
传统的方法设计中，变换方法在铁-铬催化剂的条件下在温度为320到380℃的第一高温变换反应器中进行。由于变换反应放热，变换的气体的温度增加了50到80℃，然后冷却到大约200℃，再通过接触铜-锌-铝催化剂进行后续的第二低温变换反应。低温变换反应排出气体中一氧化碳的最后含量一般在0.1到0.3％体积的范围。
通过传统的两级变换方法得到的氢纯度大约在92％。
在某些应用中传统变换方法得到的氢纯度过低，因此在上述方法设计中要增加第三级变换反应。同时还建议通过连续润湿气体来增加方法过程中的水含量，以得到最低浓度的一氧化碳(见WO9961397)。所有的上述措施都以负面方式影响到方法成本。
现有技术中已经提出了对传统高温-低温变换方法的多种改进。
美国专利No.5,525,322公开了一种通过水煤气变换从水和碳氢化合物生产超纯氢的方法，其采用设置在反应器中的钯膜和镍催化剂来驱动反应，并通过从反应混合物中去除产品氢使反应基本完全。
美国专利No.6,033,634显示了一种板式高温变换器，带有变换反应腔，腔中充有高温变换催化剂；冷却腔，具有装填物可促进热传递，冷却气体引入冷却腔；和分隔变换反应腔和冷却腔的隔板。所述变换反应腔具有由多孔板构成的板式隔板分隔的氢气腔，和氢气能渗透的钯膜。因此，只有在变换反应腔产生的氢气可透过氢气渗透膜进入氢气腔。
发明内容
本发明的目的是通过结合等温控制反应温度和用氢选择膜连续去除氢产物对上述已知一氧化碳变换为氢的变换方法进行改进。本发明的另一个目的是提供一种可用于等温膜变换方法的反应单元。
根据上述目的，本发明提供了一种包含一氧化碳的原料气的等温变换方法，该方法包括：
将原料气引入反应单元中的反应器管，所述反应器管带有位于反应区的变换催化剂固定床；
使原料气与催化剂和蒸汽反应物接触以产生氢；冷却介质具有在所述反应器管的外壳侧流动的降膜形式，通过所述冷却介质进行非直接热交换使反应区冷却，并从所述降膜中去除加热的冷却介质；
使变换反应生成的氢通过氢选择膜到达渗透区；
将氢从渗透区抽出并将耗尽一氧化碳的原料气从反应区排出。
本发明还涉及用于进行包含一氧化碳的原料气的等温变换方法的反应单元，其包括：
带有外壳的反应器，在所述反应器外壳中，一个或多个反应器管设置成带有变换催化剂固定床，并且设置成冷却介质以降膜形式沿所述反应器管的外壳侧流动与之进行间接热接触进行热交换，在外壳侧的所述反应器管的上端设置了冷却介质分配器，所述分配器具有同心地设置在外壳侧并与所述管壁间隔开的带孔套管的形式；并且设置了具有套管形式的定量分配机构，其带有与管壁同心的锥形出口端；
氢渗透薄膜管，同心地设置在所述反应器管内，所述薄膜管的外壳侧与催化剂床接触；和在所述薄膜管的管侧的渗透区；
在反应器外壳上，包含一氧化碳的原料气的入口装置与所述催化剂床的入口连接，消耗完一氧化碳的原料气的出口装置连接到所述催化剂床的出口；
氢的渗透气的出口装置连接到所述薄膜管的渗透区；
冷却介质的入口和出口装置，所述入口装置可将所述冷却介质引入所述反应器管的外壳侧。
用于所发明方法的适合催化剂包括已知的高温或低温变换催化剂，可以是铜-锌-铝氧化物，铜-锌-铬氧化物和铁-铬氧化物，这些催化剂可循商业途径从Haldor Topsøe A/S得到。
在本发明的优选实施例中是通过蒸发的方式来使反应区冷却，其利用沸腾的水作为冷却介质。在这个实施例中，水以降膜形式用于反应器管，反应器管包含变换催化剂并构成反应区。
使用水降膜作为冷却介质具有一个优点，对热的反应器管进行冷却产生的蒸汽的一部分可用作变换反应的反应物。因此，原料气通过反应器管的外壳侧时，被降膜水冷却介质形成的蒸汽润湿。
润湿的原料气接着被引入反应器管的管侧进行反应，如下面所作详细介绍。包含一氧化碳的原料气可以含有蒸汽，原料气中的蒸汽数量可通过用水降膜形成的蒸汽润湿原料气来增加，如上所述。原料气被沸腾水冷却反应的过程中形成的蒸汽饱和。
沸腾水冷却的另一优点是所产生蒸汽的一部分可以用作渗透区的吹扫气体。吹扫气体降低了氢分压，从而增加了氢从催化剂床到渗透区的渗透率，并提高了氢气的回收率。
在用沸腾水冷却反应的过程中形成的部分蒸汽用作吹扫气体和/或进行反应的蒸汽反应物。
附图说明
对本发明的上述和其他特征及优点从下面参考附图所作详细介绍可以得到清楚了解，其中：
图1是根据本发明一个实施例的反应单元的剖视图；和
图2详细地显示了反应单元中的反应器管的上部，其中冷却介质分配组件安装于本发明的反应单元。
具体实施方式
现在参考图1，等温膜变换反应器2包括设置在顶管板8和底管板10之间的圆柱薄壳反应器管6。
通过位于反应器2顶部的原料气输入管12和各个管6顶部的入口14向各个管6提供包含一氧化碳的原料气。反应完的原料气通过位于管6的出口16和反应器外壳的主出口管18抽出。
各个管6还设置了适当的变换催化剂的催化剂床20，催化剂床20支撑于支撑板22。在反应器管的管侧设置了同心的氢渗透膜管24。膜管通过中间支撑件26刚性固定在适当位置。
原料气如上所述通过接触催化剂床20的变换催化剂在管6内进行反应。变换反应产生的氢气通过渗透从催化剂床20到达膜管24的渗透侧28连续地抽出，通过在反应器管6顶部的与各个膜管相连的氢气出口管30回收。
为了增加反应速率，采用前面介绍的吹扫气体将氢气从渗透侧28带走。吹扫气体通过连接到各膜管24底部的入口32引入膜管及膜管的渗透区。
如上所述，变换反应强烈放热，需要冷却以实现合理的原料气变换。本发明的变换反应器中的反应用液体冷却介质冷却反应器管基本上是等温进行。冷却介质通过管34提供到反应器管的外壳侧，冷却介质与反应气体进行非直接热交换。加热的冷却介质从管36抽出，在通过入口34重新循环进入反应器之前在外部进行冷却(未显示)。
所述反应单元还包括连接加热的冷却介质的出口装置和所述原料气的入口装置的管路，和/或连接所述加热的冷却介质的出口装置和所述吹扫气体的入口装置的管路。
在本发明的特定实施例中，反应是通过降膜反应器中沸腾的水进行冷却的。因而冷却水在反应器的顶部通过分配盘上面的管36引入，通过将在下面参考图2详细介绍的分配组件40分流到各个反应器管6。通过降膜反应器，引入反应器的原料气当进入反应器管之前可被蒸汽反应物润湿。本发明的这个实施例中的干燥原料气通过入口42进入反应器，沿反应器管的外壳侧向上到达分配盘38，润湿的气体经过烟囱9(未显示)在管44中抽出反应器，其中烟囱设置在盘38用于传输润湿的气体。润湿的气体最后如上所述输入反应器。
图2是放大的剖视图，显示了设置在分配盘38的反应器管6的上部，和分配组件40。
组件40包括带有孔44的分配套管42和安装在定量分配套管48的锯齿状的滴水板46。
通过上述组件，冷却介质，比如水，从盘38经过套管42中的孔44沿管6的外壳侧以降膜的形式供应。为了使冷却介质在管的整个圆周上有更均匀的分布，套管48的出口端50安装到管6的壁上，冷却介质通过定量分配套管48边上的切口52进行分配。
离开套管48的冷却介质通过至少设置在管壁上部的槽54在管6的壁上沿圆周向分布。

Claims (8)

1.一种包含一氧化碳的原料气的等温变换方法，所述方法包括步骤：
将原料气引入反应单元中的反应器管，所述反应器管带有位于在反应区的变换催化剂固定床；
使所述原料气与催化剂和蒸汽反应物接触以产生氢；以及冷却介质具有沿所述反应器管的外壳侧流动的降膜形式，通过所述冷却介质进行非直接热交换使反应区冷却以及从所述降膜中去除加热的冷却介质；
使变换反应生成的氢通过氢选择膜到达渗透区；
将氢从渗透区抽出并将耗尽一氧化碳的原料气从反应区排出。
2.根据权利要求1所述的方法，其特征在于，所述冷却介质是沸腾的水。
3.根据权利要求1所述的方法，其特征在于，利用吹扫气体来增加氢从催化剂床到所述渗透区的渗透率。
4.根据权利要求2所述的方法，其特征在于，在用沸腾水冷却反应的过程中形成的部分蒸汽用作吹扫气体和/或进行反应的蒸汽反应物。
5.根据权利要求2所述的方法，其特征在于，所述原料气被沸腾水冷却反应的过程中形成的蒸汽饱和。
6.一种进行权利要求1到5中任一项所述方法的反应单元，其包括：
带有外壳的反应器，在所述反应器外壳中，一个或多个反应器管设置成带有变换催化剂固定床，并且设置成冷却介质以降膜形式沿所述反应器管的外壳侧流动与之进行间接热接触进行热交换，在外壳侧的所述反应器管的上端设置了冷却介质分配器，所述分配器具有同心地设置在外壳侧并与所述管壁间隔开的带孔套管的形式；并且设置了具有套管形式的定量分配机构，其带有与管壁同心的锥形出口端；
氢渗透薄膜管，同心地设置在所述反应器管内，所述薄膜管的外壳侧与催化剂床接触；和在所述薄膜管的管侧的渗透区；
在反应器外壳上，包含一氧化碳的原料气的入口装置与所述催化剂床的入口连接，消耗完一氧化碳的原料气的出口装置连接到所述催化剂床的出口；
氢的渗透气的出口装置连接到所述薄膜管的渗透区；
冷却介质的入口和出口装置，所述入口装置可将所述冷却介质引入所述反应器管的外壳侧。
7.根据权利要求6所述的反应单元，其特征在于，所述反应单元还包括吹扫气体的入口装置，其连接到所述薄膜管的所述渗透区。
8.根据权利要求6所述的反应单元，其特征在于，所述反应单元还包括连接加热的冷却介质的出口装置和所述原料气的入口装置的管路，和/或连接所述加热的冷却介质的出口装置和所述吹扫气体的入口装置的管路。
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