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CN1038494C - 氢的低温纯化方法和装置 - Google Patents

氢的低温纯化方法和装置 Download PDF

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CN1038494C
CN1038494C CN94119649A CN94119649A CN1038494C CN 1038494 C CN1038494 C CN 1038494C CN 94119649 A CN94119649 A CN 94119649A CN 94119649 A CN94119649 A CN 94119649A CN 1038494 C CN1038494 C CN 1038494C
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C·丹尼斯
P·高希尔
J·C·维拉德
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Abstract

在使用装有气体轴承的低温涡轮(8)的低温法纯化氢气的本装置中，由这些轴承(17)产生的气体在低温热交换管路(3)中冷却之后供给所述涡轮。在该涡轮中膨胀的气体与本装置的剩余部分混合以便降低烃的分压，并加速他们在所述热交换管路中的蒸发。
运用催化转化气体的纯化，可提高加氢处理烃的反应器的处理能力。

Description

氢的低温纯化方法和装置
本发明涉及不纯氢的低温纯化方法，在该方法中，不纯氢在热交换管路中通过与纯化的氢和含有最初膨胀至低压P1的冷凝杂质的剩余部分进行热交换，在高压P0下冷至足够低的温度以冷凝预定比例的杂质，其余的致冷作用是通过纯化的氢在带有气体轴承的涡轮中膨胀提供的，再将膨胀的氢在热交换管路中的冷端加到膨胀的少量杂质中。
下文涉及的压力为绝对压力。
环境保护标准要求可燃物和燃料中的残留硫含量越来越低对氢提出了附加需求，因而要求增加现有烃(如汽油)加氢脱硫反应器的处理能力。
一种解决办法是通过纯化常规来源的氢，特别是来自催化转化装置的氢，以提高氢的分压。
用低温法纯化(与其它的方法相比)，当纯化氢的能力大时，经济上是有意义的，且其特征在于最终氢的浓度约为98摩尔％，高回收量(约96％)和低能耗。
通过杂质(主要由烃组成)的自由膨胀，基本上能保证本类型方法的低温要求条件。对于催化转化气体而言，其常规组成为：
      H2           84摩尔％
      CH4          6摩尔％
     C2H6            5摩尔％
     C3H8            3摩尔％
     C4H10           2摩尔％由于甲烷含量不足以保证通过自由膨胀达到热交换管路最冷部分所必需的致冷能量，因此必须提供低能量的膨胀涡轮以提供必要的补充。
如果低能量是由其分子量约2kg/Kmole的很小的高纯氢气流膨胀产生的，则使用带有气体轴承的涡轮，因允许很高的转速，所以特别有利。
操作带有轴承的涡轮包括使用所谓的“有用气体”，当该气体取自纯化的氢气流时，可保证如下的两种一般功能：
一方面，使室温下低流速的所谓阻挡气体注入装在转子和轴承间的迷宫式密封层中，其压力稍低于涡轮转子后面由待膨胀气体在转子和定子间逸散而产生的间隙压力。上述阻挡气体限制冷气流的降低，并在其混合物流到支撑转子的轴承之前使它再加热。
另一方面，在室温下将流速较大的所谓轴承气体注入支撑轴承内，在这里使其进行一般的声速膨胀。
然后收集用过的气体并送到所述装置的剩余气体网状系统。
本发明的目的是提供一种方法，该法能使所用气体具有重要价值(Valorization)，且由于纯化氢的损失降至最低，因此使该法的产量增加。
为达此目的，本发明上述类型的方法特征在于离开轴承的气体在热交换管路中冷却之后，供给所述涡轮，并且在压力稍低于该涡轮的转子和定子间产生的间隙压力Pi下，排出该涡轮迷宫式密封层泄漏的氢气流。
所述方法可具有一个或几个下列的特征：
涡轮的供料是通过在膨胀阀中膨胀的纯化氢气流完成的；
泄漏气流，如果需要的话，在膨胀阀中膨胀后在室温下加到剩余气体中；
泄漏气流，冷却后(如果需要的话膨胀后)，加到所述膨胀过的剩余部分中。
本发明还有一个目的是提供一种适于实施上述定义的方法的装置，该类型的装置包括热交换管路，在该热交换管路的冷端至少有一个相分离器，一个带有气体轴承的氢膨胀涡轮，使不纯氢气流在热交换管路中沿一个方向循环的装置，使来自相分离器的液体膨胀至低压的装置，在低压下将氢加到所述膨胀产生的剩余部分的装置，以及使于低压条件下获得的混合物与不纯氢气逆流循环的装置，该装置的特征在于热交换管路包括供离开涡轮轴承的气体冷却用的通道，这些通道在热交换管路的冷端与涡轮的输入端连接，该装置还包括排放涡轮迷宫式密封泄漏的氢气流的装置，其压力稍低于该涡轮转子和定子间产生的间隙压力Pi。
现按照附图对本发明的实施例进行说明，其中：
图1表明本发明不纯氢气的纯化装置示意图；和
图2表明该装置带有气体轴承的涡轮示意图。
图1所示的装置适合在5MP量级的高压P0下，向氢脱靡反应器1供给比较纯的氢，通常纯度量级为96-98％。为此，向该装置提供催化转化装置2产生的不纯氢，这种不纯氢一般具有如上所示的组成。用低温方法纯化的不纯氢气正是这种气体。
本发明主要包括间接逆流热交换型的热交换管路3，该管路包含热区4和冷区5，本发明还包括“热”相分离器6，“冷”相分离器7和带有气体轴承的涡轮8。为清楚说明起见，使用有用气体的涡轮的设备组件(迷宫式密封和轴承)单独在图1中用9示意地表示。
不纯氢，在生产压力P0(压力降较小)下离开设备2，在4中被冷却至中等温度，然后送进相分离器，在其中除甲烷外的所有杂质基本上完全冷凝。使该分离器产生的蒸气继续在热交换管路的冷端5中冷却，再送入相分离器7中。由相分离器7产生的汽相先在5后中、然后在4中几乎完全被再加热，通过管道10，作为纯化过的氢产品，离开热交换管路的热端。
大部分需要的低温是通过如下的方法获得的，即将分离器7产生的液相在膨胀阀11中膨胀至低压P1，然后使其在5中蒸发，再与分离器6产生的液体合并，该液体事先在P1下的膨胀阀12中膨胀过，最后在4中蒸发和再加热。所得到的气流，经管道13，作为该装置的剩余气体W，从热交换管路的热端排出，并且该气体的压力，例如数量级为300-400KPa，足以在加热场所的气体网状系统内(所谓“可燃气”网状系统)扩散开。
由于不纯氢的甲烷含量低，所以不足以保证该装置的冷区维持低温。因此，由涡轮8提供辅助的冷气，在低压P1为300-400KPa下将其输出，并在热交换管路的冷端注入离开膨胀阀11的液体中，以降低冷端的温度，并为此扩大氮产品纯度的等级。
如图2示意性地表示，涡轮8包含与轴15连接的转子14，该轴通过气体轴承17在定子16中转动。迷宫式密封18装在转子和这些轴承之间，位于轴承外的轴15的一端装有制动压缩机的转子19。后者在装有致冷设备21的外壳20内旋转。维护气由管道10经管道22排出，通入保持在中等压力3MPa的储存室23。
膨胀的支承气体在可调压力下，声速膨胀后经管道24离开组件9，调压用的合适装置未示出，压力调至500-1500KPa的中间值。所述气体在热交换管路3中从热端到冷端冷却之后，被送入涡轮的入口，通过涡轮膨胀至300-400Kpa的低压。
假若如此产生的致冷功率不足时，涡轮的供料可由分离器7产生的纯化氮气流扩大，由装有膨胀阀26的管道25输送。
离开涡轮的低压氢经管道27注入由膨胀阀11排放的液体中。
结果，涡轮的入口压力低于轴承的出口压力(500-1500KPa)，因此它大于间隙压力Pi。以致可避免室温下气体从轴承向低温转子逸出，由迷宫式密封18产生的气流在稍低于所述间隙压力的压力值Pi-ε下放出。这种排放是经装有压力控制阀29的管道28进行的。在从本例中选择的压力值下，该压力大于剩余气体的压力P1，可将由控制阀29出来的气体，或如图所示，在热交换管路的热端，或在变更条件下，在热交换管路中冷却后在冷端注入剩余气体中。
由此可见，所有的支承气体在如下三种情况下均是有价值的：第一，通过它在8中的膨胀而产生大部分必要的冷气；第二，混有甲烷的混合物蒸发降低冷气的温度；第三，可用于“可燃气体”的网状系统。此外，能使送入涡轮的高压氮气量减至最低，这相当于该方法的产量达到最高。
若需要的话，经济条件允许，不管使用的流速如何低，可使由28排出的气体先在4中、然后在5中冷却，然后再注入11中膨胀的甲烷中。

Claims (14)

1.氢气的低温纯化方法，该方法包括，将不纯氢气在高压PO下冷却到冷凝预定比例杂质的温度，所述冷却通过在热交换管路(3)中通过与纯化的氮和含有予先膨胀至低压P1的冷凝杂质(在11、12中)的剩余部分热交换进行，其余的冷气是由纯化的氢在带有气体轴承的涡轮(8)中膨胀提供的，再使膨胀的氢加入在热交换管路的冷端膨胀过的少量杂质中，其特征在于，离开气体轴承(17)的气体，在热交换管路中冷却之后，供给涡轮(8)，并且在稍低于间隙压力Pi的压力下排放涡轮的迷宫式密封(18)层泄漏的氢气流，所述Pi压力产生在该涡轮的转子(14)和定子(16)之间。
2.按照权利要求1的方法，其特征在于，涡轮(8)的进料是由膨胀阀(26)中的纯化氢气流完成的。
3.按照权利要求1或2的方法，其特征在于，泄漏气流在室温下加到剩余气体中。
4.按照权利要求3的方法，其特征在于，所述泄漏气流在膨胀阀中膨胀后加到剩余气体中。
5.按照权利要求1或2的方法，其特征在于，泄漏气流在冷却后加到所述膨胀过的剩余部分中。
6.按照权利要求5的方法，其特征在于，所述泄漏气流在膨胀后加到所述膨胀过的剩余部分中。
7.按照权利要求1或2的方法，其特征在于，不纯氢气是催化转化气。
8.按照权利要求1或2的方法，其特征在于，纯化的氢用于烃(1)的加氢处理中。
9.氢气低温纯化所用的装置，该装置包括，热交换管路(3)，在所述热交换管路的冷端的相分离器(7)，带有气体轴承的氢膨胀涡轮(8)，使不纯氢气流在热交换管路中沿一个方向循环的装置，使相分离器(7)产生的液相膨胀至低压的装置，将氢气在低压条件下加到由所述膨胀产生的剩余部分中的装置，以及使低压下获得的混合物逆流与不纯氢气循环的装置，其特征在于，热交换管路包括用于使离开涡轮(8)的轴承(17)的气体冷却的通道，这些通道在热交换管路的冷端与涡轮的输入端连接，其特征还在于，该装置包括，在稍低于该涡轮的转子(14)和定予(16)间的间隙压力Pi条件下，排放涡轮的迷宫式密封(18)的泄露氢气流的装置(28，29)。
10.按照权利要求9的装置，其特征在于，相分离器(7)的顶部经膨胀阀(26)与涡轮(8)的输入端连接。
11.按照权利要求9或10的装置，其特征在于，所述装置包括用于所述泄漏气流的膨胀阀(29)，在热交换管路(3)的热端与下游供该装置剩余气体用的管道连接。
12.按照权利要求9或10的装置，其特征在于，该装置包括用于所述泄露气流的膨胀阀(29)，经所述热交换管路的冷却通道，在下游与输送所述膨胀过的剩余部分的管道连接。
13.按照权利要求9或10的装置，它与供催化转化用的设备(2)连接。
14.按照权利要求9或10的装置，其供产生纯化氮气的管道(10)，在热交换管路(3)的热端，与烃的加氢脱硫设备(1)连接。
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