CN1143538A - 从惰性气体中除去微量氧气的吸附剂 - Google Patents

从惰性气体中除去微量氧气的吸附剂 Download PDF

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CN1143538A
CN1143538A CN96106833A CN96106833A CN1143538A CN 1143538 A CN1143538 A CN 1143538A CN 96106833 A CN96106833 A CN 96106833A CN 96106833 A CN96106833 A CN 96106833A CN 1143538 A CN1143538 A CN 1143538A
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T·C·戈登
C·H·约翰逊
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Abstract

本发明提出吸附剂及其用于从惰性气体中除去微量氧气的方法。该吸附剂包括用约10至约90wt％碱金属氧化物或碱土金属氧化物浸渍的多孔还原性载体如活性炭，炭黑，煤，石油焦炭和二氧化钛。

Description

从惰性气体中除去微量氧气的吸附剂
本申请是1994年3月23日提交的美国专利申请序列No.08/216,738的部分继续申请。
本发明涉及可用来从惰性气体中除去微量氧气的吸附剂。
超高纯(UHP)惰性气体如氩气和氮气在某些工业领域是重要的。例如在电子工业领域，UHP氮气和氩气对于成功地制成硅片是很关键的。下表表明在UHP氮气中通常可允许的最大污染物浓度：
    杂质          可允许的最大浓度
    氧气            5ppb
    二氧化碳        10ppb
    一氧化碳        5ppb
    水              100ppb
    甲烷            10ppb
主要任务是开发出能够以有效且廉价的方式生产UHP气体的材料和工艺方法。将杂质去除而达到ppb程度以及为确定达到该程度而精确地取样和分析是极为困难的。
目前已有许多技术可用来从惰性气体中除去微量氧气，但这些技术都受到一定限制。例如由包括锆，铝，钒和铁的各种金属组成的金属合金已用作高温氧气吸气剂。为使该合金活化，可在真空中250-900℃下对其进行加热。活化后优选操作温度为200-400℃。该吸气剂可在室温下应用，但其吸氧能力明显受到限制。这类吸气材料很昂贵并且其吸氧能力亦不能再生。例如US5,194,233就公开了这种吸气剂。
还原后的过渡金属氧化物催化剂如还原态的氧化铜和氧化镍为另一类可用来从气流中除去氧气的材料。生产还原态的催化剂涉及到强放热反应并且要求在还原气氛，通常是氢气中于150-200℃下进行加热。一旦催化剂的吸氧能力耗尽，则该催化剂须在还原性气体中高温下再进行还原。这类催化剂的主要缺点是极易引火的催化剂处于还原态时处理这种催化剂会对安全性造成极大的危险并且要求用氢气进行催化剂还原。
可用脱氧催化剂通过氧气与氢气经催化反应形成水而从气流中除去氧气。这类***要求超过化学计量的氢气，因此须解决除水和保留氢气的问题。
已知用吸附剂从气流中除去杂质。例如，US4,271,133提出氧化锌吸附剂在约室温至约350℃温度下从气流中除去氰化氢。该吸附剂包括氧化锌和不多于5wt％(重量百分比，下同)碱金属或碱土金属氧化物。
US4,433,981提出用吸附剂从气流中除去二氧化碳。将气流与吸附剂接触，而吸附剂制备方法是用可在焙烧时分解的碱金属或碱土金属氧化物或盐浸渍多孔氧化铝载体并随后于约350-700℃下焙烧浸渍过的氧化铝以将浸渍化合物转化成相应的碱金属或碱土金属铝酸盐。在用其除去二氧化碳后，该吸附剂可通过加热到焙烧条件而再生。
US4,579,723公开了从惰性气流中除去ppm数量级杂质如氧气，一氧化碳，二氧化碳，氢气和水的双床***。床层由活性或反应性/吸附性材料构成，例如催化材料如DeOxoA(铬和钼处于γ-氧化铝上构成的混合物)放在第一床中，而吸气材料如Dow Q1(铜，镍和钴与微量银，铬和锰一起置于粒状氧化铝上而形成的混合物)放在第二床中。
US4,594,231提出从气体中除去卤素和/或卤化氢，其中将气体与吸附剂接触，而吸附剂包括活性炭载体，该载体上沉积了两种或多种选自下列三组的组分和一或两种选自余下两组的组分：(1)铜化合物；(2)锌化合物；以及(3)碱金属或碱土金属化合物，或者铝，钛，钒，铬，锰，铁，钴，镍，铬或铅的化合物。若活性炭上沉积的是氧化物之外的化合物，优选在沉积后进行热处理如干燥或焙烧。
US4,859,438公开了从烟道气体中分离杂质如含量低的二氧化硫，氯化氢和氮氧化物，其中将气体与至少一种包括NaHCO3的基本上干燥的粒状吸附剂接触，而该吸附剂在低于400℃的释放温度下可分解而形成包括Na2CO3的活性吸附剂。
US5,015,411公开了从惰性气体中除去路易斯酸和氧化剂杂质的净化剂，其中包括惰性无机载体和载体上的活性净化物质。在载体上沉积有机金属前体后将该有机金属前体热解成作为载体上的活性净化物质的金属氢化物和/或活性金属即可制成该净化剂。
US5,081,097公开了在最高约200℃温度下选择性除去气体中各种浓度的氧气并在最高约600℃温度下选择性除去气体中微量氧气的铜改性的碳分子筛。该碳分子筛可经氢气还原而再生。
本发明涉及吸氧材料及其从惰性气流中除去微量氧气的用途。该吸氧材料是由碱金属氧化物或碱土金属氧化物沉积在多孔还原性载体上而构成的固体吸附剂。该吸附剂制备方法是用碱金属盐或碱土金属盐的水溶液或非水溶液浸渍多孔还原性载体，在空气中将被浸渍载体干燥后在惰性气氛中200-500℃下将被浸渍载体热处理而使其活化。热处理使金属盐分解成相应的氧化物。还原性载体有利于形成对清除氧气而言活性极高的低价氧化物。
本发明主要优点是：
●吸附剂易于制备和使用；
●吸附剂可用相当廉价的组分得到；
●吸附剂可除去微量氧气而达到ppb数量级；
●吸附剂再生不要求用氢气，因为载体已提供了还原潜力；以及
●吸附剂可在室温下有效地除去微量氧气。
图1示出了用载带甲酸铯的活性炭得到的氧气和氮气等温吸附线。
图2示出了用载带乙酸钠的活性炭得到的氧气和氮气等温吸附线。
图3示出了用载带乙酸钾的活性炭得到的氧气和氮气等温吸附线。
图4示出了用载带乙酸铯的炭和镍/氧化铝材料得到的氧气等温吸附线。
图5和6示出了确定用甲酸铯浸渍的炭吸氧能力的热解重量分析结果。
让气流通过包括用碱金属氧化物或碱土金属氧化物浸渍的固体还原性载体的吸附剂即可从惰性气流如氩气和氮气中除去微量氧气。本文中“微量”氧气指约10ppm或更少氧气。
将碱金属氧化物或碱土金属氧化物如氧化钠，氧化钾，氧化铯和氧化钡载于多孔还原性载体上的方法是用相应金属盐的水溶液或非水溶液浸渍载体。合适盐的例子包括硝酸盐，草酸盐，苯甲酸盐，乳酸盐，酒石酸盐，乙酸盐，琥珀酸盐和甲酸盐。
虽然优选用水，但可用来溶解金属盐的其他溶剂还包括甲醇，乙醇，丙酮和***。盐的重量含量为约10至约90wt％，优选为30-40wt％。
合适的固体还原性载体例子包括气相活性炭，液相活性炭，炭黑，煤，石油焦炭和二氧化钛。优选载体为多孔炭如活性炭。该载体表面积至少10m2/g，优选1000m2/g。
浸渍可用本技术领域已知的方法进行，如用早期润湿技术，喷雾浸渍和加热瞬时分散法。浸渍之后载体—盐组合物在约50-120℃下干燥约2-16小时。
干燥后的浸渍载体在流动惰性气体中加热到约200-500℃温度，使盐分解成相应的氧化物，从使该浸渍载体活化。流动惰性气体在活化期间的停留时间为约0.5-30秒，优选10秒。将该复合材料在金属盐分解点或之上保持至少约1小时即可保证金属盐成功地分解成氧化物。然后就可用该吸附剂从惰性气流中除去微量氧气。
碱金属氧化物以及某些碱土金属氧化物可形成更高级的氧化物，包括过氧化物和超氧化物，其中通常将该金属氧化物与氧化剂如空气在高温下反应。本发明中将含微量氧气的惰性气体如氮气优选于室温(如20℃下)通过氧化物浸渍的载体。压力范围为约1至约10大气压(atm)，优选5atm。可以相信，吸附剂中的氧化物可与惰性气体中的微量氧气一起形成更高级的氧化物如过氧化物或超氧化物。本发明吸气材料的吸氧能力为约0.6wt％。
在惰性气氛如氮气中约200-500℃下将该吸气材料处理约16小时，优选24小时即可使其再生。该载体提供可使过氧化物或超氧化物再转化为碱金属或碱土金属氧化物形式的还原潜力。
进行本发明的优选方法是用一个以上的并列吸附剂床，其中一个床再生时，另一床正用于进行吸附。这种两床操作方案如下所示：
床
1                吸附 D 热冲洗 冷却     P
2     D 热冲洗 冷却     P           吸附
D＝减压    P＝增压
如上所列，在每一床中均进行一系列的步骤，其中包括：高压吸附；减压；为使吸附剂床再生而相对于吸附步骤而逆流进行的热冲洗；冷却；以及另一吸附步骤开始之前的床层再增压。可用部分富含氮气的产品物流作为反冲气流或另外用单独的冲洗气流进行冲洗步骤。
实施例1
采用早期润湿技术操作，其中20g Sorbtech SL活性炭用10g甲酸铯溶于14ml蒸馏水中形成的溶液浸渍，以炭和甲酸铯总重量计甲酸铯的重量含量为33wt％。浸渍后的炭在110℃干燥16小时。干燥后的浸渍炭再在流动氮气(停留时间为0.5秒)中200℃加热16小时，从而使其活化。金属和金属氧化物含量为25wt％铯或27wt％氧化铯。用标准容量吸附单元30℃下测定氮气和氧气的吸附率。同于上述活化步骤在氮气中300℃使该吸附剂再活化并重复吸氧测定操作。图1示出了测定结果。吸氧量明显高于吸氮量。按亨利定律(初期吸氧相对于吸氮的等温线斜率之比)确定的该温度下氧气相对于氮气的选择性为约3000。图1还表明在300℃下再生后可再获得吸氧能力。
实施例2
10g乙酸钠溶于14ml蒸馏水中。再采用早期润湿技术进行操作，其中用乙酸钠溶液浸渍20g Sorbtech SL活性炭，以炭和乙酸钠总重量计达到33wt％乙酸钠。混合物在空气中110℃下干燥16小时。干燥后的材料再同于例1在流动氮气中于400℃活化16小时。金属和金属氧化物含量为9wt％钠或13wt％氧化钠。活化后用容量吸附装置30℃下测定氮气和氧气吸附率。图2的等温吸附线表明该吸附剂的吸氧量远高于吸氮量。按亨利定律确定的氧气相对于氮气的选择性为约2000。该材料吸氧能力的再生要求同于上述活化步骤在氮气中400℃下进行处理。
实施例3
10g乙酸钾溶于15ml蒸馏水中。再采用早期润湿技术操作，其中用乙酸钾溶液浸渍20g BPL活性炭，以乙酸钾和炭总重量计达到33wt％乙酸钾。该混合物在空气中110℃下干燥16小时。干燥的材料再在流动氮气中500℃下活化16小时。金属或金属氧化物含量为13wt％钾或16wt％氧化钾。活化之后用容量吸附装置30℃下测定氮气和氧气吸附量。图3所示相应的等温吸附线表明吸氧量远高于吸氮量。为了使该吸附剂再生，要求在氮气氛中达到500℃温度。
实施例4
图4表明了氧化铯载于活性炭上构成的吸附剂和市售镍载于氧化铝上构成的吸附剂(Harshaw Nickel 0104T)的等温吸附线。同于例1用甲酸铯浸渍活性炭而得到氧化铯载于炭上构成的吸附剂。氧化铯载于炭上的吸附剂30℃下吸氧量远高于市售镍载于氧化铝上的材料。在吸氧之前，镍载于氧化铝上的吸附剂在氮气中200℃和存在1％氢气的情况下活化。
热解重量分析
为了说明本发明吸附剂的吸氧能力，已对氧气和氮气的二元混合物进行了热解重量分析(TGA)。TGA试验按下述进行：将35mg例1所得甲酸铯浸渍的炭放在TGA设备中。样品在氮气中加热到300℃后于该温度下保持20分钟。然后在氮气中让样品冷却约1小时，之后将其放在约50℃空气中并测定吸氧量。图5表明了300℃下热处理达到14％的失重量，这可能是由于失水和甲酸根阴离子分解成氧化物阴离子所致。样品在氮气中冷却表明因吸氮而略为增重。引入空气(80分钟时)而使样品增重约0.6wt％，这已在图6中详细列明了。增重是由于相对于氮气而选择性吸附氧气所致，增重量对应于0.2atm氧分压下约0.2mmol/g的吸氧能力。该值低于图1所示值，图为TGA试验在更高温度下进行，并且在使用二元混合物时，氮气抑制吸氧能力。
工业用途的样品计算
为了估计例1所得吸附剂在工业操作时的有效性，已计算除去微量氧气的吸附床尺寸。已假定如下入口条件：
T＝室温(30℃)
P＝7.8atm(100psig)
气流速度＝300000scfh
入口氧杂质＝5ppm
估计吸氧能力＝0.6wt％
在这些入口条件下，对于一星期的吸附循环时间将要求约1600Kgs的吸附剂。这一吸附剂装填量对于工业操作是合理的。
工业用途说明
由金属氧化物浸渍还原性载体而构成的吸附剂可用来生产半导体和电子工业所需的超高纯惰性气体。

Claims (8)

1.从惰性气体中除去微量氧气的吸附剂，该吸附剂包括用碱金属氧化物或碱土金属氧化物浸渍的多孔还原性载体，其中所述吸附剂中所述碱金属氧化物或碱土金属氧化物含量为约10至约90wt％。
2.权利要求1的吸附剂，其中所述碱金属氧化物或碱土金属氧化物含量为约10至约30wt％。
3.从惰性气体中除去氧气的方法，其中包括让含氧气的惰性气流在除氧条件下通过吸附剂床，对该方法的改进包括用由约10至约90wt％碱金属氧化物或碱土金属氧化物浸渍多孔还原性载体而构成的吸附剂从惰性气流中除去微量氧气。
4.权利要求3的方法，其中所述多孔还原性载体为含碳材料。
5.权利要求3的方法，其中所述多孔还原性载体选自活性炭，炭黑，煤，石油焦炭和二氧化钛。
6.权利要求5的方法，其中所述碱金属或碱土金属盐选自硝酸盐，乙酸盐，甲酸盐，苯甲酸盐，草酸盐，酒石酸盐，乳酸盐和琥珀酸盐。
7.权利要求6的方法，其中所述碱金属或碱土金属选自铯，钠，钾和钡。
8.权利要求7的方法，其中所述碱金属氧化物或碱土金属氧化物含量为约10至约30wt％。
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