CN1330970A - 气体的纯化 - Google Patents

气体的纯化 Download PDF

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CN1330970A
CN1330970A CN01122670A CN01122670A CN1330970A CN 1330970 A CN1330970 A CN 1330970A CN 01122670 A CN01122670 A CN 01122670A CN 01122670 A CN01122670 A CN 01122670A CN 1330970 A CN1330970 A CN 1330970A
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R·库马尔
邓曙光
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Linde LLC
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Abstract

公开一种从含杂质的气态原料流生产纯化气态产品的方法。在一个包含吸附剂和氧化催化剂层的反应器中,从气态原料流可除去如氢、水蒸气、一氧化碳和二氧化碳的杂质。氢转变为水蒸气的催化剂设置在从原料流除去二氧化碳之后不仅提高了性能,而且提高了气体提纯系统的经济性。

Description

气体的纯化
本发明涉及一种在一变温度吸附(temperature swing adsorption)预提纯单元中除去气体原料流中的气态杂质方法。具体而言，本发明提供一种从气态原料流如空气中除去H2、H2O、CO、CO2和另外的烃和氮的氧化物的方法。
在制造集成电路时为防止提高线路密度后芯片中的缺陷，要求杂质含量小于百万分之一水平的高纯度气体。
要求采用低温蒸馏从进料气中除去杂质生产高纯度氮气。当使用空气作为进料气时，必须除去杂质如H2O和CO2，防止在生产装置的低温部分冻结，而其它杂质如H2和CO也必须除去，防止它们污染氮气产品。
在氮气生产过程中，一直采用两步法从空气中除去这些杂质。第一步中，压缩的进料气加热至150-250℃，然后与催化剂接触，使CO氧化为CO2，H2氧化为H2O。该氧化步骤一般使用铂基贵金属催化剂。第二步中，通过变温吸附或变压吸附方法从压缩气流除去氧化产物CO2和H2O。
这些方法尽管有效，但由于其操作成本高，对工业规模生产高纯化的气体特别是氮气存在缺陷。操作成本高的原因是广泛使用贵金属催化剂。另外，必须使用另外的容器用于催化剂处理步骤和吸附步骤以除去杂质。还需要热交换器来加热通入催化剂容器的气体和冷却从该容器排出的气体。这些在设备和能量方面都需要额外的费用。
本领域已知低温法可从惰性气体流中除去百万分之几的杂质。
本发明人发现使用多层床可提高H2催化剂性能，这种多层床中气态原料流与H2催化剂接触前除去痕量杂质，主要是CO2。这样不仅可以提高总的性能，而且还减少该方法所需要的H2催化剂量。
本发明提供一种显著除去杂质而纯化的气态产品制造方法，该方法包括下列步骤：
a)从含杂质的气态原料流中除去水蒸气；
b)该气态原料流与氧化催化剂接触，使CO转变为CO2；
c)从步骤a)和b)的气态原料流中除去CO2；
d)步骤c)的气态原料流与氧化催化剂接触，使H2转变为H2O；
e)从步骤d)的气态原料流除去H2O，制得明显纯化的气态产品。
或者，在步骤c)和d)之间增加另一个步骤，即从气态原料流除去烃和氮的氧化物。
本发明的另一个实施方案中，通过下列步骤获得显著除去杂质而纯化的气态产品：
a)从含杂质的气态原料流中除去水蒸气；
b)从步骤a)的气态原料流除去CO2；
c)步骤b)的气态原料流与氧化催化剂接触，使CO转变为CO2；
d)步骤c)的气态原料流与氧化催化剂接触，使H2转变为H2O；
e)从步骤c)和d)的气态原料流除去H2O和CO2，制得明显纯化的气态产品。
或者，在步骤b)和c)之间增加另一个步骤，即从气态原料流除去烃和氮的氧化物。
通常，在空气进入空气分离装置(ASU)中的低温蒸馏单元之前，在变温吸附(TSA)法中的空气是获得的气态产品。在常规TSA法中使用的再生气体必须不含H2、CO、CO2、H2O、氮氧化物和烃。
在一个处理区中处理气态原料流，较好在一个包括两个催化剂段和三个吸附剂段的容器中。第一段包含一个或多个除水的吸附剂床如活性氧化铝、硅胶、沸石、或它们的组合。用于将CO转变为CO2的第一催化剂层可以是氧化锰和氧化铜或氧化镍的混合物。
第二吸附段包含用于从气态原料流除CO2的吸附剂。这种吸附剂可以是沸石、活性氧化铝、硅胶或它们的组合。
该容器中用于将H2转变为H2O的段包含氧化催化剂。这种催化剂较好的是贵金属催化剂如负载的钯。最后一层包含用于除水和/或二氧化碳的吸附剂，是沸石、活性氧化铝、硅胶或它们的组合。
下面附图仅用于说明本发明，不构成对本发明范围的限制。
图1所示是本发明生产高纯度气体方法的一个实施方案的示意图。
本发明提供一种制备纯化的气体产品的方法。除去的杂质是H2O、H2、CO和CO2。本发明的另一个实施方案中，还可从制得的气体产品中除去氮氧化物和痕量烃。
参见附图，具体是图1，图1所示为制备纯化气体的方法。进料气流如空气经管道2通入压缩机4，气体被压缩至约50-300 psig。压缩后的气流经管道6送入热交换器8冷却，然后经管道10通入水分离器12，除去液态水。水分离器12的排出物温度约为5-70℃，较好的在约20-45℃范围。
该气体经管道14，通过阀16和管道20送入单一反应器30的处理区25，反应器30包含第一吸附区32、第一催化剂区34、第二吸附区36、第二催化剂区38和第三吸附区40。另一个实施方案中，变换区34和36，使第二吸附区紧跟在第一吸附区32之后。
第一吸附区32含有至少一个除水的吸附剂如活性氧化铝、硅胶、沸石和/或它们的组合的床。压缩后气体中的大多数水蒸气必须除去以防止后面的催化剂层失活。吸附区32较好包括一层活性氧化铝或硅胶和一层沸石如沸石13X或5A(购自UOP公司)。
然后，气流进入第一催化剂区34，一氧化碳转变为二氧化碳。较好的催化剂是金属氧化物如氧化镍或氧化锰和氧化铜的混合物。最好使用hopcalite型催化剂如Carulire-300(Carus制造)。
处理后的气体进入第二吸附层36，从气流中除去CO2。吸附剂选自活性氧化铝、硅胶、沸石和/或它们的组合。处理后的气体二氧化碳含量较好的不超过约1.0ppm。该处理气体进入第二催化剂区38，气体中的氢气转化为水蒸气。该层使用的催化剂包括本领域已知的负载的钯和其它贵金属催化剂。较好的是蛋壳型Pd催化剂如从Engelhard购得的那些催化剂。
最后一层40包括第三吸附区，从处理的气流除去水蒸气。在层34和36交换的实施方案中，在层40中还必须存在二氧化碳的吸附剂。因此，吸附剂可以是活性氧化铝、硅胶、沸石和/或它们的混合物。
另一个实施方案中，在二氧化碳吸附步骤之后增加另一个吸附剂层。该层可以是吸附剂如沸石层。
处理后的气体经管道42和阀44从处理反应器排出，经管道46送入储槽，或通过管道48送去进一步加工，如低温蒸馏单元，可通过管道48到热交换器50，然后通过管道51引入用于低温蒸馏单元的常规进料。
下面参考具体的实施例描述本发明，这些实施例不构成对本发明的范围限制。
实施例1用不含CO2的干空气进料的H2穿透(breakthrough)试验(操作1)
使用内径1英寸的填有13X/Pd-AA/Carulite/AA(从顶部到底部)反应器评价Pd/AA催化剂除去H2的性能。吸附剂和催化剂首先在200℃用不含H2、CO和CO2的空气流再生，随后用同样的再生气流冷却至环境温度。然后，含3186 ppb H2和232 ppb CO的干空气流从床层底部通入18℃和180 psig的反应器。用RGA-5分析仪测定从Pd/AA催化剂层排出的H2和CO浓度，确定H2和CO的穿透时间。
实施例2用含CO2的干空气进料的H2穿透试验(操作2)
按实施例1中所述，用含CO2的干空气进料进行同样的H2穿透试验以表明CO2对催化剂性能的影响。进料空气流含有约400 ppm CO2、3128 ppb H2和214 ppb CO。测定同样的H2和CO穿透曲线。两个试验中所获数据列于下面表I。
    表I
    催化剂性能
    操作1    操作2
    进料压力(psig)     180     180
    进料温度(℃)     18     18
    进料速度(ft/s)     0.47     0.47
    进料中H2O(ppm)     ＜5     ＜5
    进料中CO(ppb)     214     232
    进料中H2(ppb)     3128     3186
    进料中CO2(ppm)     ～400     ＜0.1
    对H2分析器LDL(ppb)     2     2
    H2穿透时间(分钟)     75     400
表I中数据表明，当从进料气体除去二氧化碳时，氢穿透时间长得多。
参考具体实施方案描述了本发明，本领域技术人员应理解本发明有许多其它形式和变动。所附的权利要求书和本发明覆盖了在本发明精神和范围之内的所有形式和变动。

Claims (11)

1.一种制造显著除去杂质而纯化的气态产品方法，该方法包括下列步骤：
a)从含杂质的气态原料流中除去水蒸气；
b)使该气态原料流与氧化催化剂接触，将一氧化碳转变为二氧化碳；
c)从步骤a)和b)的气态原料流中除去二氧化碳；
d)将步骤c)的气态原料流与氧化催化剂接触，使氢转变为水蒸气；
e)从步骤d)的气态原料流除去水蒸气，制得明显纯化的气态产品。
2.如权利要求1所述的方法，其特征在于所述气态原料流是空气。
3.如权利要求1所述的方法，其特征在于所述杂质选自氢、水蒸气、一氧化碳和二氧化碳。
4.如权利要求1所述的方法，其特征在于所述方法是一个变温吸附系统。
5.如权利要求1所述的方法，其特征在于所述步骤a)包括使所述气态原料流与除水蒸气的吸附剂接触，所述吸附剂选自活性氧化铝、硅胶、沸石或它们的组合。
6.如权利要求1所述的方法，其特征在于所述步骤b)的氧化催化剂是氧化锰和氧化铜的混合物。
7.如权利要求1所述的方法，其特征在于所述步骤c)包括使所述气态原料流与除二氧化碳的吸附剂接触，所述吸附剂选自活性氧化铝、硅胶、沸石或它们的组合。
8.如权利要求1所述的方法，其特征在于所述步骤d)的氧化催化剂是负载的钯贵金属催化剂。
9.如权利要求1所述的方法，其特征在于所述步骤e)包括使所述气态原料流与除水蒸气的吸附剂接触，所述吸附剂选自活性氧化铝、硅胶、沸石或它们的组合。
10.如权利要求1所述的方法，其特征在于所述方法还包括使所述气态原料流与一种吸附剂接触，除去烃和氮的氧化物。
11.如权利要求1所述的方法，其特征在于所述方法还包括深冷分离步骤e)组分的步骤。
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