CN1104618C - 纯氩的回收方法和装置 - Google Patents

纯氩的回收方法和装置 Download PDF

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CN1104618C
CN1104618C CN95102285A CN95102285A CN1104618C CN 1104618 C CN1104618 C CN 1104618C CN 95102285 A CN95102285 A CN 95102285A CN 95102285 A CN95102285 A CN 95102285A CN 1104618 C CN1104618 C CN 1104618C
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A·莫尔
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Abstract

用于纯氩回收的方法和装置。在包含至少一个空气分离柱(9)、粗氩柱(17)和纯氩柱(25)的精馏体系中分离空气。从粗氩柱(17)取出粗氩馏分(24)，并引入纯氩柱(25)的中部。通过间接热交换(29)冷却纯氩柱(25)的上端。从纯氩柱(25)的顶端排出主要含氮的剩余馏分(31)，从其底部取出纯氩馏分(26)。在纯氩柱(25)中的传质至少部分是通过填充物(33，34)而进行的。

Description

纯氩的回收方法和装置
本发明涉及纯氩的回收方法和装置。在本方法中，借助于至少一个空气分离柱、粗氩柱和纯氩柱，在精馏体系中分离空气，粗氩馏分从粗氩柱取出并引入纯氩柱的中部，纯氩柱的上端优选通过与蒸发馏分的间接热交换而被冷却，并从纯氩柱的上部取出主要是含氮的残留馏分，从纯氩柱的下部取出纯氩馏分。
纯氩制备的基本原理已在Hausen/Linde，Tieftemper-aturtechnik(low temperature technology)第二版，1985，第332-334页中叙述。并且，在该介绍中所涉及的这类方法和装置为专利申请EP-B-377117，EP-A-171711和EP-A-331028所已知。进一步的改进披露在德国专利申请P4406049.1和P4406069.6以及欧洲专利申请(         )中，在此以具有相同优先权日期的这些首次申请为基础，作为本申请。狭义地说，在本文中的空气分离通常是在从其低压部分提取用于粗氩柱的进料馏分的双柱中进行的。在另一精馏柱即纯氩柱中，将缺氧的粗氧中的易挥发杂质特别是氮除去。此外，在粗氩柱和纯氩柱之间也可以例如通过用氢的催化氧化(Deoxo apparatus，例如参看EP-A-171711或EP-A-331028)任意设置除氧工段。
粗氩产物通常是在可能最低的压力即大气压以上一点的压力回收。因此在粗氩产物引入纯氩柱前，其压力必须升高，以在纯氩柱的上端仍可获得足够的过压用，以排出其顶端产物，并产生回流(通常是通过与蒸发氮的间接热交换而使顶端气体冷凝)。为此，在许多场合都需要特殊压缩机的中间装备，这涉及相应的资金和操作费用。虽然通过粗氩的液化和使用静压(参见EP-B-377117)可避免这套中间装备，但是在纯氩柱的短程布置上将受到限制，在许多场合，由于空间条件，该纯氩柱只是成本高而已。而且，在省去压缩机时，还常常受某些纯度的限制。例如，要获得氮含量为100ppb或更少的纯氩产物是不可能的。
因此，本发明基于该目的，从而开发上述的方法和装置，其特征在于能以特别好的经济性、特别合适的资金和操作费用、以高得率、高纯度回收纯氩产物。
该目的是根据本发明而实现的，其中，在纯氩柱中的传质至少部分通过填充物完成。
在本文中，术语填充物总是包括无规则填充物以及结构填充物。在此优选使用结构填充物。例如在DE-A-2722424和DE-A-4209132或DE-A-4224068中叙述了结构填充物特定设计的例子。虽然在双柱或空气分离器的粗氩柱中使用这样的填充物来代替常规的精馏浅盘是已知的(EP-A-0321103，EP-B-0377177)，但是在纯氩柱中这样使用在过去一直被认为是不合适的。
在本文中，甚至在单独使用时，术语“填充物”也用来包括在用无结构的和/或有结构的填充物填充的柱内的许多分段。
通过在纯氩柱中使用本发明的填充物，在该柱中的压力损失可减少到这样的程度，就是可省去用于压缩粗氩的特殊措施。〔很显明.在任何场合这并不排除使用存在于粗氩导管中的任何短程落差(geodetic fall)〕。与现有技术的期望值相比，业已发现，在本发明范围内，在许多场合该优点明显地超过增加的开支，结果，总的说来可节省资金和/或操作成本。
业已发现，如果在引入粗氩馏分的中间部位上方的纯氩柱中的传质至少部分或全部由填充物来完成，那么这将是特别合适的。以该方式获得了本发明的主要作用，即粗氩进口和纯氩柱顶端冷凝器之间相对低的压差，无需用昂贵的填充物装填整个纯氩柱。
在本文中，在纯氩柱下部即引入粗氩馏分的中间部位的下面的材料变换可部分地或甚至是全部地由浅盘来完成。这使得绝大部分纯氩柱用成本相对能行的传质元件来填充。在本发明范围内能使用的、在纯氩柱中这样的精馏或变换的浅盘的细节描述于Winnack-er/Kuchler，Chmische Technologie，第7卷第3版(1975)第3.351节，第197-200页中。
作为替换或变通在纯氩柱的上部使用填充物的方法，在引入粗氩馏分的中间部位的下面的纯氩柱的传质可至少部分地或完全地通过填充物来完成。然后，可在相应的大部分柱高上利用填充物的有益作用。
在本文中，通过与在该过程中蒸发的液态的间接热交换，用已知的方式操纵纯氩柱的上端。然而，如果借助用氧含量至少为10％的冷却介质冷却纯氩柱的上端来完成热交换，那么这是特别有益的。以该方式，能在纯氩柱中产生所需的回流，而没有蒸发掉有价值的液态，后者可能在一个或多个空气分离柱中的精馏而损耗掉。
为此，可使用多种液态工艺流作为冷却介质。冷却介质最好是取自一个或多空气分离柱、特别是双柱加压段的下部或中部。特别有益的是使用加压段的底槽液体作为纯氩柱用的冷却介质。
在本发明中，限定的冷却介质的使用并不意味着其它馏分不能同样地对纯氩柱的上端冷却起作用，例如在与冷却介质热交换的上游与上端馏分混合，尽管如此，特意被称为冷却介质的那个馏分所起的作用，对于在纯氩柱上端产生回流来说是决定性的因数。
可以通过显热的交换而对纯氩柱的底槽进行加热，其中，通过与加压柱的液体馏分、特别是在加压柱的下部收集到的底槽液的间接热交换来加热纯氩柱的下部。对纯氩柱的这种加热方式描述于德国专利申请P4406069.G和要求该申请为优先权的欧洲专利申请(       )。在本文中，如果将用于纯氩柱下部加热的间接热交换的加热柱下游至少部分液体馏分用作纯氩柱和/或粗氩柱的上端馏分冷凝用的冷却介质，以便实现对纯氩柱底槽加热和上端冷却的整体化，这是有利的。
此外，本发明还涉及描述于权利要求11和12中的用于实施该方法的装置。
本发明及其进一步的细节将通过下文附图中简要说明的两个工作例而进一步解释。
附图1示出了根据本发明方法和装置的第一实施方案，包括常规的纯氩柱的塔顶冷却。
图2示出了包括新颖的纯氩柱塔顶冷却的特别优选的实施方案。
这两个实施方案彼此在大多数方面是相一致的，因此用相同的参考数来表示相互一致的方法步骤和装置特征。
在1处引入常压空气，在空气压缩机2处压缩，预冷却(3)，在分子筛段4除去二氧化碳和水蒸汽，在主热交换器5处冷却至约露点，最后通过导管6引入到双柱7的加压段8。通过冷凝蒸发器10，双柱7的加压段8和低压段9处于热交换关系。至少将部分加压柱8的底槽液11和液氮12送入低压柱9中。在主热交换器5中，将低压柱的气相产物即纯氮14、掺杂质的氮15和气相氧16与要分离的空气进行热交换加热至约常温。如果需要也能回收液体产物：通过导管13的氮和/或取自低压柱9底槽的氧36。特别是在后者的场合，通常可通过例如在包括一个、两个或多个闪蒸透平(flash tur-bines)、由空气或氮操纵的制冷循环中，通过工艺流的运行产生的减压而产生制冷作用；或通过空气的运行产生的减压至约低压柱的压力而产生制冷作用，并直接将该空气引入低压柱。
在低压柱9的中间部位，取出含氩的氧馏分37，并在粗氩柱17中分离成在该柱上端收集的粗氩18和被返回(也可以借助泵20)至低压柱的残留液19。在粗氩冷凝器21中，在与加压柱蒸发底槽液的热交换中，至少将部分的粗氩馏分19冷凝。冷凝物一部分作为回流物送至粗氩柱17，另一部分取出作为中间产物22，24。图1中示出，可在热交换器23中，在与随后要与粗氩馏分24的取出液部分22结合的液体馏分(在该场合为氮)的热交换中，冷凝该非冷凝的粗氩。在两个工作例中均构成纯氩柱进料的该粗氩馏分24仍含有约0.1-1000ppm、优选低于10ppm的不易挥发性组分(特别是氧)，和约0.1-5％、优选0.1-1％的极易挥发性杂质(特别是氮)。
优选从纯氩柱25的底槽取出液态的纯氩产物26。纯氩产物26仍含有作为介质的0.1-1000ppm、优选低于约1ppm的氧，和0.05-100ppm、优选约1ppm或更低的氮。
根据本发明，该纯氩柱包含有填充物，优选为有结构的填充物。在该说明性例子中，在粗氩柱进料口24上方说明了两个填充物工段33，34。也可以例如在那里只提供一个的填充物工段，在该工段的上面和/或下面通过常规的精馏浅盘来补充。在纯氩柱中粗氩馏24进料部上方的材料交换元件相当于2-15、优选约8-10块理论塔板。
在粗氩进口下面提供了30-50、优选约40-45块理论塔板。在该附图的例子中，这些完全由浅盘35来表示，但是，在本发明范围内，也能部分地或基本上完全地或完全地使用填充物，特别是结构填充物。
在该精馏体系余下的柱中可包含浅盘和/或填充物和/或这两种材料交换元件的组合。如图所示，特别是在粗氩柱中，优选使用结构填充物是有利的，因为它能通过精馏完全除去氧(参见EP-B-377117)。然而，双柱特别是低压柱9也可包含填充物，特别是结构型的填充物。
在图1中，结合纯氩柱25的常规的冷却和加热说明了本发明：底槽的加热27是由加压柱8的上端产生的气相氮28操纵的。在用氮(底糟加热27的冷凝物和/或加压柱8的液体30)冷却的上端冷凝器29中部分地冷却由20-80％、优选约40-60％的氮组成的纯氩柱25的塔顶气28，并排出作为剩余气31的剩余部分。后者例如可排空至大气中，或例如与上端冷凝器29收集的蒸汽32一起被送入低压柱9的掺杂氮流15中。
图2显示出了纯氩柱25排热和加热形式的改进，借此，能特别有效地实现本发明的优点。
在用于将热引入纯氩柱25下部的热交换器27中，在与保持在例如1-3巴、优选1.2-2.0巴压力的液体底槽馏分11的热交换中，蒸发一部分纯氩柱的底槽液。在此过程中载热体11被过冷。
该过冷载热体11a随后被用作冷却介质，用于使粗氩柱和纯氩柱产生回流。粗氩柱上端的冷却是在冷凝蒸发器39中进行的，基本上所有的加压柱8的底槽液(在流过底槽蒸发器27后)都引入到该冷凝蒸发器中。(较少部分的加压柱的底槽馏分可以不同的方式例如通过安全管取出)。借助通过过冷逆流装置38和热交换器27的导管11，将该该中压柱液送入冷凝蒸发器的蒸发空间。借助导管18，将粗氩柱上端得到的气相粗氩通过安装在冷凝蒸发器液浴中的热交换器21。在热交换器21中形成的一部分冷凝物以回流形式送至粗氩柱，而另一部分作为中间物24排出。
液体通过导管13流至另一个作为纯氩柱25上端冷凝器的热交换器29中。在热交换器29中蒸发的冷却介质可通过导管32循环入冷凝蒸发器39的蒸发器空间。纯氩柱的上端馏分通过导管28而与冷却介质进行间接热交换。由此形成的冷凝物通过接管28a再次流回纯氩柱25中。残气在31排出。关于粗氩柱和纯氩柱上端冷却的作用方式的确切说明，以及本发明方法进一步改进的细节，请参考德国专利申请P4406049.1和相应的欧洲专利申请(这两份申请均有相同的作为本申请的优先权日期)。在替代上述实施方案的另一方案中，能彼此独立地操纵粗氩柱和纯氩柱的上端冷凝器21和29，其中导管11被直接连接至顶端冷凝器29的蒸发器侧。
在脱离这两个附图的附图说明的情况下，还能以气相形式取出粗氩柱的上端产物，并以气相形式送入纯氩柱，其中，例如导管l8和24在热交换器21的上游连接。
作为附图说明中纯氩柱25底槽加热的替代方案，本发明甚至还能使用气相空气，用以使纯氩柱沸腾，例如，如德国专利申请P44060649.1和相应的欧洲专利申请(         )中所示。

Claims (12)

1.一种纯氩的回收方法，其中，在借助至少一个空气分离柱(9)、粗氩柱(17)和纯氩柱(25)的精馏体系中分离空气，粗氩馏分(24)取自粗氩柱(17)，并引入纯氩柱(25)的中部，该纯氩柱的上端通过间接热交换(29)冷却，并且其中从纯氩柱(25)的上部取出主要是含氮的剩余馏分(31)，从纯氩柱(25)的下部取出纯氩馏分(26)，其特征在于，在纯氩柱(25)中的传质至少部分是通过在粗氩柱进料口上方的纯氩柱工段使用填充物(33，34)而进行的。
2.根据权利要求1的方法，其特征在于，在引入粗氩馏分(24)的中部上方，在纯氩柱(25)中的传质至少部分是通过填充物(33，34)而进行的。
3.根据权利要求2的方法，其特征在于，在引入粗氩馏分(24)的中部的上方，在纯氩柱(25)中的传质基本上完全是通过填充物(33，34)而进行的。
4.根据权利要求1-3任一项的方法，其特征在于，在引入粗氩馏分(24)的中部的下方，在纯氩柱(25)中的传质基本上完全是通过浅盘(35)而进行的。
5.根据权利要求1-3任一项的方法，其特征在于，在引入粗氩馏分(24)的中部的下方，在纯氩柱(25)中的传质至少部分是通过填充物而进行的。
6.根据权利要求1-3任一项的方法，其特征在于，在整个纯氩柱(25)中的传质基本上完全是通过填充的而进行的。
7.根据权利要求1-3任一项的方法，其特征在于，用于冷却纯氩柱(25)上端的间接热交换是通过氧含量至少为10％的冷却介质(11，30)而进行。
8.根据权利要求7的方法，其特征在于，冷却介质(11)取自一个或多个空气分离柱(9)的下部或中部。
9.根据权利要求8的方法，其特征在于，粗馏体系包括含加压柱(8)和低压柱(9)的双柱(7)，冷却介质取自加压柱(8)的下部或中部。
10.根据权利要求9的方法，其特征在于，在加压柱(8)的下部收集到的底槽液(11)用作冷却介质。
11.实施根据权利要求1-10任一项方法的装置，包括一精馏体系，该体系包括至少一个空气分离柱(9)、粗氩柱(17)和纯氩柱(25)；通过粗氩管(24)连接粗氩柱(17)和纯氩柱(25)的中部，其特征在于，至少一种填充物(33，34)设置在粗氩柱进料口上方的纯氩柱(25)中。
12.根据权利要求11的装置，其特征在于，通过蒸汽管(28)和冷凝管(28a)，将热交换器(29)连接至纯氩柱(25)的上部，并且该热交换器(29)包含冷却介质导管(11，30)，该冷却介质导管(11，30)连接至含氧量至少为10％的冷却介质源。
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