CN1059267C - 超纯氮的生产 - Google Patents

超纯氮的生产 Download PDF

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CN1059267C
CN1059267C CN93118416A CN93118416A CN1059267C CN 1059267 C CN1059267 C CN 1059267C CN 93118416 A CN93118416 A CN 93118416A CN 93118416 A CN93118416 A CN 93118416A CN 1059267 C CN1059267 C CN 1059267C
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carbon monoxide
air
nitrogen
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adsorbent
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拉夫·吉英
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Linde LLC
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Abstract

本发明阐述了一种生产含一氧化碳不多于0.5ppm(体积)的氮气或空气的设备和方法。将含一氧化碳约为100ppm(体积)的氮气流或空气流在含有钙交换X型沸石、5A型沸石或13X型沸石的吸附床中经受深冷温度的交替吸附，从氮气流或空气流中除去几乎所有的一氧化碳。

Description

超纯氮的生产
本发明涉及高纯氮的产生，更具体地，涉及通过深冷吸附从高纯氮中除去一氧化碳。
许多应用中需要使用氮气，这种氮气必须基本上不含诸如一氧化碳等杂质。在设计集成电路块制造中这是十分重要的，因为即使杂质非常少，也可能导致集成电路块产量的大大降低。当希望通过空气深冷分馏生产高纯氮时，空气中存在诸如烃类这些一般不可冷凝的高沸点杂质是没有问题的，因为一些高沸点杂质在进入蒸馏系统前可从进料气流在接近室温时吸附除去，而未被吸附除去的烃类和其它高沸杂质和富氧气流离开蒸馏系统。然而，一氧化碳作为杂质存在于空气进料中，并且，在进料气流进入蒸馏系统之前，未能被除去它将最终在富集的氮气流中，因为它的沸点非常接近氮气。传统去除氮气流中的一氧化碳需要采用特殊的技术，诸如高温化学吸附或氧化成二氧化碳。
氧化去除一氧化碳需要采用铂-钯催化剂在高达250℃的温度时反应。通过化学吸附去除一氧化碳包括在30℃-200℃温度之间采用铜或镍基吸气剂/吸附剂。这些方法中的每一种都明显地增加高纯氮生产的总成本。
美国专利4,746,332揭示了采用钠交换的A型沸石在深冷温度下从氮气流中吸附氧。
由于大多数高纯氮是通过深冷蒸馏生产的，在深冷温度下去除一氧化碳是十分需要的，因为这样的步骤可易于一体化于现有的方法中，而本发明提供了这样一种方法。
根据本发明的主要的目的，将空气流或氮气流在一氧化碳选择性吸附剂的床中，于深冷温度下，通过温度交替吸附(TSA)，从空气流或氮气流中除去一氧化碳。在空气净化情况下，该吸附在空气的露点以上的温度，通常在约150℃的温度下进行，而较佳地在约90°-125°K的温度范围中进行，以及在氮净化的情况下，该吸附在氮在大气压力沸点以上的温度下，即77°K，但低于约150°K温度下进行；而较佳地在约90°-150°K的范围中进行。一般地，该吸附在约1-20大气压力的绝对压力下进行。用于本发明的方法中的吸附剂为A型沸石、X型沸石、Y型沸石、丝光沸石或它们的混合物。一般地，吸附剂床在约-20℃到250℃温度范围再生。本发明从氮或空气除去直至约100ppm的一氧化碳尤为有效。
本发明的方法的较佳实施例中，吸附剂是钙交换的X型沸石、5A型沸石、13X型沸石或其混合物。
在本发明的更特殊的实例是，一通过一个二种交替的过程从含一氧化碳的空气生产实质上无一氧化碳的氮气：
(a)深冷蒸馏空气，由此产生含一氧化碳的富集的氮气流；然后该富集的氮气流通过一氧化碳选择性吸附剂床在约77-150°K的温度范围，较佳地在约90°-125°K从该富集的氮气流吸附一氧化碳；或者
(b)将空气流通过一氧化碳选择性吸附剂床，在空气的露点以上的温度在吸附剂床温约150°K而较佳地约在90°-125°K范围中，由此产生实质上无一氧化碳的空气；以及深冷蒸馏该实质上无一氧化碳的空气，由此产生实质上无一氧化碳富集的氮气流。
本发明的设备方面包括深冷温度交替吸附系统与分部蒸馏系统按顺序排列或二个交替的排列；
(a)一个具有空气入口装置、富集氧气流出口装置和富集氮气流出口装置的蒸馏柱，以及深冷温度交替吸附装置，它包括含有至少一种吸附一氧化碳强于吸附氮气的吸附剂的吸附剂床，与富集的氮气流出口装置连接的入口装置，非吸附产物气体的出口装置和解吸产物气体的出口装置；以及
(b)深冷温度交替吸附装置，它包括含有至少一种吸附一氧化碳强于吸附氮、氧和氩的吸附剂的吸附剂床，以及具有非吸附产物气体出口装置和解吸产物气体出口装置，和具有空气入口装置与非吸附产物气体出口装置，富集氧气流出口装置和富集氮气流出口装置相连接的蒸馏柱。
在任一的可采用的吸附装置中含有一种吸附剂，它选自A型沸石、X型沸石、Y型沸石、丝光沸石以及其混合物，而较佳的具体例子中的一种吸附剂为选自钙交换的X型沸石、5A型沸石、13X型沸石以及其混合物。
本发明的设备实例中另一较佳的具体例子是蒸馏柱附有一个粗氩旁支管蒸馏柱。
以下，本发明以附图加以说明，其中：
图1为按照本发明的原则描述的从富氮进料气流回收高纯氮的深冷吸附系统；
图2为按照本发明从空气生产高纯氮气系统的第一个具体例子；
图3为按照本发明从空气生产高纯氮系统的第二个具体例子。
所有图中的类似的符号表示类似的或相应的部分，辅助阀门、管线和装备对理解本发明不需的已从图中省略。
在本发明的主要目的中，将含一氧化碳杂质的富集的氮气流通过一吸附剂床，于深冷温度下，从富集的氮气流中优选地吸附一氧化碳，由此从该气流除去相当数量的一氧化碳，该吸附方法在TSA循环中操作。本发明的该目的可以在图1所示的设备中进行。在图1中所示的吸附系统描述了包括二个平行排列的床；然而，本发明并不限定于两床系统，可以采用单床吸附系统，或者该系统可以包括多于两个平行排列的吸附床。对于本发明的操作而言，系统中吸附床的数目并不重要。在附图中所示的两床系统中，一个床为吸附模式，而另一个床为再生模式。
确定吸附器A和B，以及将吸附一氧化碳而不吸附氮的每一种颗粒吸附剂装入床中。合适的吸附剂包括A、X和Y型沸石。丝光沸石等，较佳的吸附剂包括钙交换的2X型沸石、5A型沸石和13X型沸石。
在图1说明的吸附系统中，阀门4A和4B分别控制到床A和B的进料气体流；阀门6A和6B分别控制清洗气体流和从吸附器A和B的解吸气体流；阀门8A和8B分别控制到吸附器A和B的清洗气体流；以及阀门10A和10B分别控制来自吸附器A和B的净化的氮气产物。
该吸附系统的操作将首先说明吸附模式的床A和在再生模式的床B。在这种半循环中，阀门4A、6B、8B和10A打开而4B、6A、8A和10B关闭。进料气体通过管线2进入吸附系统，通过阀门4A并进入吸附器A，当该气体通过吸附器A，一氧化碳优选地被吸附。该贫化的一氧化碳氮气流通常含不多于约0.5ppm体积的一氧化碳通过阀门10A以及通过管线12离开该吸附系统。在图1的具体例子中，纯化的氮送入相当于用户的装备或作为下流工艺的一种氮液化器或贮存容器的单元18。
当在吸附器A中产生高纯氮叶，在吸附器B中再生床的吸附剂，再生期间，将通过管线14、打开阀门8B将温热的清洗气体导入吸附器B中。作为清洗气体较佳地用高纯氮气以避免污染吸附床。通过管线12离开系统的部分产品可用作再生清洗气体。温热清洗气体通过床B，由此解吸并从中吹去一氧化碳，解吸的一氧化碳通过打开阀门6B和管线16从系统中被除去，该气体可以全部通入大气或者部分可重新导入系统用作洗清气体加以回收氮。
在吸附步骤中，在吸附器A中的被吸附气体前沿朝该单元的出口端移动。当该前沿到达床中予定点时，前半循环终止，后半循环开始。
在后半吸附循环期间，吸附器B处于吸附操作而吸附器A中的床被再生。在此半循环期间，阀门4B、6A、8A和10B打开而阀门4A、6B和10A关闭。进料气体通过管线2进入吸附系统并通过阀门4B和10B、管线12经过吸附器B。意即：在吸附器A中的床处在再生中，吸附器A中的床再生期间，温热的清洗气体通过管线14经阀门8A、阀门6A和管线16通过吸附器A。当在吸附器B床中的吸附作用前移达到该床的预定点时，后半循环终止，而重复此循环。典型地是温度在氮的露点(77°K，一个大气压下)和150°K之间和绝对压力约1.0-20.0大气压的进料进入吸附器A和B。再生气流速率标准以5-15％之间的进料流速通过该系统。再生气体的温度典型地在-20℃和250℃之间。在进料气中一氧化碳杂质的浓度典型地小于100ppm，在氮气净化开始之前，在吸附器A和B中的床加热至300℃，以除去任何残留在其中的水分。在正规操作中不必重复此步骤。典型的循环工艺在下表1中给出：
                         表1
          本发明的涂冷TAS工艺的典型循环顺序
               步骤                               时间.小时密封床A，用床B净化0.5用床A净化，床B通大气0.5用床A净化，用温热清洗气体再生床B                      8.0用床A净化，用冷的清洗气体冷却床B                      15.0密封床B，用床A净化                                    0.5用床B净化，床A通大气                                  0.5用床B净化，用温热清洗气体再生床A                      18.0用床B净化，用冷的清洗气体冷却床A                      15.0总计                                                  48.0小时
本发明的具体目的在图2中加以说明。将含一氧化碳的空气流在蒸馏柱中蒸馏以产生含一氧化碳的富集的氮气产品气流，然后将它经受上述的深冷温度交替吸附工艺过程。
参照图2，该系统中包括深冷蒸馏单元102，它包括高压柱104和低压柱106，支路氩蒸馏单元108(可选择的)，深冷吸附系统110(相同于在图1中已说明的系统)以及空气预净化单元112。当买来的氮是所需的产品，仅仅使用高压柱，以及空气进料在接近该柱的底部。
在图2系统的操作中，将压缩空气气流通过管件114导入预净化单元112，典型地，单元112是一种吸附净化单元或一种反式热交换器，当它是一种吸附净化单元时，它含有从空气流中较佳地吸附水份和二氧化碳的吸附剂的床。当空气流通过单元112时，不饱和的烃，例如：乙烯、丙烯等，以及较高分子量的饱和烃例如：C4和较高级烷烃类，通常从空气流中也被吸附。较低级烃类包括甲烷、乙烷和痕量乙烯和丙烯可能留在单元112的气流中。当被用作一种反热交换器时，水和二氧化碳(但一般不是烃类)，当空气通过该单元时经冷冻从进料空气中被除去。该离开单元112的预净化过的空气流被冷却然后通过管线116导入单元102的高压柱104中。液化的富氧底流从高压柱通过管线118被除去，并导入低压柱106。在柱106中该富氧流被净化导入氮产品气流中通过管线2离开柱106，以及氧气产品气流通过管线120离开柱106。进入单元102的任何存在于系统中的烃类用氧气产品气流从系统中被除去。
当单元102装有氩支管蒸馏柱108时，富集氩气流从低压柱106通过管线122在氮产物气流除去管线2和氧产物气流除去管线120中间的一点被除去。在柱108中，在一粗氩气流中的被净化的富集氩气流通过管线124离开柱108，而富集氧气再循环气流通过管线126再返回到柱106。
通过管线2离开柱106的富氮产物气流含有存在于空气进料气流中的一氧化碳。该一氧化碳从在单元110中的氮产物气流中被除去，(参考图1的上述说明)，由此产生贫化的一氧化碳的氮气流，它通过管线12离开单元110，以及废气流通过管线16离开单元110。如果需要，部分废气流可重返到蒸馏柱102以增加氮的回收。为了有效操作单元110，气流应以蒸汽形态进入该单元。在该具体例子中，深冷吸附系统110的操作条件包括温度在约77°至150°K之间，较佳地在约80°至125°K之间，而压力在101.3-2026.5KPa(1.0-20.0大气压)之间。
除了省略图2中的深冷吸附单元110，并用图3的深冷吸附单元130代替外，图3的系统类似于图2的系统。单元130可以是图1中所说明的吸附系统，而且通常包含相同的吸附剂。在深冷温度下，这些吸附剂吸附一氧化碳和烃类强于对氮、氧和氩的吸附。
在图3的系统的操作中，压缩空气流通过管线114导入预净化单元112中，将离开单元112的预净化的空气冷却，以及然后导入深冷吸附单元130。在预净化的空气流中的一氧化碳从单元130被除去(参考图1的上述说明)，由此产生的贫化的一氧化碳的空气流通过管线132离开单元130，而废气流通过管线134离开单元130。贫化的一氧化碳的预净化的空气流接着进入单元102的高压柱104。除了存在于低压柱106的该富集的氮产物现在是一高纯产物以及由此无需进一步净化外，在图3中单元102的操作相同于在图2中该单元的操作。
为了单元130的有效操作，该净化的空气流应以蒸汽形态进入该单元。另外，到单元130的空气进料流的温度应在它的露点(在现场压力下)和150°K之间。在具体例子中的深冷吸附系统130的较佳操作条件包括温度在90℃-125℃之间，而压力在404.3-2026.5KPa(4.0-20.0大气压)之间。
在图2和3的具体例子中，通常深冷蒸馏步骤在90°-125°K进行。
本发明将通过以下实施例作进一步的说明，除了另有声明外，其中份数、百分数和比例均以体积为基准。
实施例1
采用一种吸附微量天平评价市场上可以买到的5A型沸石、铜交换的Y型沸石、13X型沸石和钙交换的X型沸石的一氧化碳和氮分离的选择性。在测量一氧化碳和氮吸附等温线的试验中于0至703千克/平方米(0至1磅/平方英寸绝对压力(pound per square inch absolute，psia))下以及于87°K温度下进行。所有的吸附剂吸附一氧化碳而不吸附氮气。5A型沸石具有最大的一氧化碳吸附容量和最佳的一氧化碳对氮的选择性。
实施例2
在一个50.8毫米(2英寸)直径的吸附容器中，它含有950克5A型沸石(已用无一氧化碳的氮于250℃的温度再生过)以去除残留的水份。然后，将该容器浸入液氩中(保持在101.3KPa(1个大气压)的绝对压力下)，由此冷却至87°K。将含有6ppm一氧化碳的氮以21标准立升/分(slpm)的平均流速在2.1千克/平方厘米(表压)(30磅/平方英寸(psig))通过该床。标准状况为101.3KPa(1绝对大气压)和21℃(70°F)，用RGA-3型分析仪(由Trac Anglytical Corporation生产)连续测量在容器流出物中一氧化碳浓度。该分析仪具有0.4ppb一氧化碳的检出极限。该试验连续进行了266小时，检出的一氧化碳才达到1ppb而突破。
实施例3
将含约0.7ppb一氧化碳的空气于绝对压力608.0KPa(6个大气压)和流速15slpm通过在实施例2的容器。在该容器中的床保持在105°K温度(通过浸渍在476.2KPa(4.7绝对大气压)下的液氩浴中)。在流出物中一氧化碳的浓度在14小时前维持低于1.0ppb。
上述实施例说明本发明采用各种吸附剂从氮气中于深冷温度下吸附一氧化碳以及采用5A型沸石从空气中吸附一氧化碳的效果。
虽然本发明通过具体的实施例作了详细描述，可以预料这些具体例的变化，例如两种或多种吸附剂可以结合成混合的形式或者成为串联的床，而本发明的范围的限定仅在权利要求书中体现。

Claims (20)

1.一种从含一氧化碳杂质的气体氮气流中除去一氧化碳的温度交替的吸附方法，其特征在于包括将所述的气体氮气流通过一个温度低于150°K的一氧化碳选择性吸附剂的床，由此产生基本上没有一氧化碳的氮气流。
2.一种从含一氧化碳杂质的空气气流中除去一氧化碳的温度交替的吸附方法，其特征在于，包括将所述的空气气流通过一个温度在所述床的压力下的露点和150°K之间的一氧化碳选择性吸附剂的床，由此产生不含一氧化碳的空气气流。
3.如权利要求1或2所述的方法，其特征在于所述的一氧化碳选择性吸附剂选自A型沸石、X型沸石、Y型沸石、丝光沸石以及其混合物。
4.如权利要求1或2所述的方法，其特征在于所述的一氧化碳选择吸附剂为选自钙交换的X型沸石、5A型沸石、13X型沸石以及其混合物。
5.如权利要求1或2所述的方法，其特征在于进一步包括在-20℃-250℃的温度范围内再生所述的吸附剂，由此从所述的吸附剂解吸所述的一氧化碳。
6.如利要求1所述的方法，其特征在于所述的氮气流含有直至100ppm的一氧化碳。
7.如权利要求2所述的方法，其特征在于所述的空气流含有直至100ppm的一氧化碳。
8.如权利要求1或2所述的方法，其特征在于所述的吸附方法在1.0-20大气压的绝对压力下进行。
9.如权利要求1或2所述的方法，其特征在于至少在一个床进行吸附而至少在另一个床进行解吸的分阶段操作的复合床中进行。
10.一种从一氧化碳杂质含量最多为100ppm的空气生产一氧化碳含量少于0.5ppm的氮气产品的温度交替吸附方法，该方法包括以下步骤：
(a)深冷蒸馏所述的空气，由此产生含有所述一氧化碳的富集氮气的气流；
(b)将所述的富集氮气的气流通过温度为77-150°K的一氧化碳选择吸附剂的床，从所述的富集氮气的气流中吸附一氧化碳。
11.一种从含一氧化碳杂质为100ppm的空气生产含一氧化碳小于0.5ppm的氮气产品的温度交替的吸附方法，该方法包括以下步骤：
(a)将所述的空气流通过在90-150°K温度的一氧化碳选择吸附的床，由此产生不含一氧化碳的空气；
(b)深冷蒸馏不含一氧化碳的空气，由此产生不含一氧化碳的富集氮气的气流。
12.如权利要求10或11所述的方法，其特征在于深冷蒸馏步骤在90°至125°K的温度范围进行。
13.如权利要求10或11所述的方法，其特征在于所述的深冷蒸馏在101.3-2026.5kPa(1-20大气压)的绝对压力下进行。
14.如权利要求10或11所述的方法，其特征在于所述的吸附剂选自A型沸石、X型沸石、Y型沸石、丝光沸石及其混合物。
15.如权利要求10或11所述的方法，其特征在于所述的吸附剂选自钙交换的X型沸石、5A型沸石、13X型沸石及其混合物。
16.用于从含有一氧化碳杂质的空气生产高纯氮气的设备，所述设备包括：
(a)一个具有空气入口装置、富集氧气流出口装置和富集氮气流出口装置的蒸馏柱；以及
(b)深冷温度交替吸附装置，它包括：含有至少一个吸附一氧化碳强于吸附氮气的吸附剂的吸附剂床，与所述富集氮气流出口装置连接的入口装置、非吸附的产物气体出口装置和解吸产物气体出口装置。
17.从含有一氧化碳杂质的空气生产高纯氮气的设备，所述设备包括：
(a)温度交替吸附装置，它包括：含有至少一种吸附一氧化碳强于吸附氮、氧和氩的吸附剂的吸附剂床、具有非吸附产物气体出口装置和解吸产物气体出口装置；以及
(b)一个具有与所述的非吸附产物气体出口装置连接的空气入口装置、富集氧气流出口装置以及富集氮气流出口装置的蒸馏柱。
18.如权利要求16或17所述的设备，其特征在于所述的至少一种吸附剂选自A型沸石、X型沸石、Y型沸石、丝光沸石及其混合物。
19.如权利要求16或17所述的设备，其特征在于所述的至少一种吸附剂选自钙交换的X型沸石、5A型沸石、13X型沸石及其混合物。
20.如权利要求16或17所述的设备，其特征在于所述的蒸馏柱具有附加的粗氩分支蒸馏柱。
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AU668754B2 (en) 1996-05-16
CN1101118A (zh) 1995-04-05
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US5551257A (en) 1996-09-03
KR940009061A (ko) 1994-05-16

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