CN104066502B - 含有吸气剂材料组合的吸气装置 - Google Patents

含有吸气剂材料组合的吸气装置 Download PDF

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CN104066502B
CN104066502B CN201280067762.2A CN201280067762A CN104066502B CN 104066502 B CN104066502 B CN 104066502B CN 201280067762 A CN201280067762 A CN 201280067762A CN 104066502 B CN104066502 B CN 104066502B
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卢卡·托亚
马尔科·维斯孔蒂
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Abstract

本发明涉及用于在真空应用中(特别适合用于真空隔热应用)去除氢气和一氧化碳的含有吸气剂材料组合的吸气装置，所述吸气剂材料包含金属钯和氧化铈与氧化铜的混合物。优选将该吸气剂材料组合、组合物添加至有效用于维持隔热系统中的真空的其他吸气剂材料(例如碱金属氢氧化物和干燥剂材料)的粉末。

Description

含有吸气剂材料组合的吸气装置
本发明涉及新的吸气剂材料组合，并且涉及含有所述组合的吸附装置。特别地，本发明涉及适于在不能加热至高于约200℃温度的装置中维持真空的吸气剂组合，特别地涉及诸如真空(热)绝缘板或电子封装材料的应用。
已证明，吸气剂材料在需要维持真空的所有工业和商业应用中极其有利甚至不可或缺。
为了使吸气剂材料得以有效且更广泛地使用，吸气剂材料在去除O2、N2和H2O方面的吸着性能必须优异，从而从存在于必须维持真空的空间内的气体混合物中除去主要的大气气体。
然而，限定必须维持真空的空间的壁中的气相混合物很大程度地依赖于对形成所述壁的材料的脱气，并且在真空板的情况下，依赖于任选地存在的填料，所述填料一般为粉末、泡沫或纤维(wool)的形式(即，具有高比表面积)。例如，在含有由塑料制成的聚合物填料的板腔的情况下，主要的脱气气体是CO和CO2，而例如当使用玻璃棉时，主要存在H2。这些气体的量可能相当可观，尤其在间隔空间的制备过程中使用了加热阶段的情况下更是如此。例如，冰箱的制造就是这种情况，其中隔热板可达到接近100℃的温度，保持数分钟的时间。
已公开的国际专利申请WO 94/18876描述了组合使用贵金属氧化物(特别是氧化钯(PdO))与吸水材料(例如氧化钡(BaO)用于在“杜瓦瓶”、“热水瓶”等的抽成真空的间隔空间中维持真空。然而，通过与氢反应，氧化钯被转化成金属Pd，该金属Pd呈现精细分散的形式，具有自燃性；结果出于安全原因而不提倡使用该材料组合。
本申请人名下的欧洲专利EP 0757920描述了与干燥剂化合物混合的钴氧化物(Co3O4)和氧化铜(CuO)对氢气和一氧化碳CO具有良好的吸附性能，CO是存在于由塑料制成的任选地填充有填料的绝热间隔空间中的主要气体之一。然而，从毒理学观点来看，钴氧化物带来了特别的问题，其被怀疑可能具有致癌性，因此，最近的国际规定强烈限制它的使用，并且预计将在几年内达到明确禁用。考虑到在大规模应用中的使用，在最 终产品使用寿命终结必须进行处理时，该问题特别明显。
Johnson Matthey PLC名下的已公开的国际专利申请WO2006/064289描述了组合物的使用，其中，将钯与选自钴氧化物、铜氧化物、铁氧化物、镍氧化物、铈氧化物以及银氧化物的单一过渡金属氧化物组合使用，并任选地与干燥剂材料组合。然而，所描述的不涉及使用钴氧化物的那些组合虽然对氢气具有降低但可观的吸附能力，但是对一氧化碳的吸附性能并不令人满意。
本发明的一个目的是提供无需热激活并且对一氧化碳具有高吸附能力的改进的吸气剂材料组合，考虑到钴氧化物的高危害性，该组合不使用钴氧化物。
本发明的另一个目的是提供使用所述吸气剂材料组合的吸附装置。
根据本发明，通过吸气装置实现了这些目的和其他目的，所述吸气装置含有吸气剂材料组合，所述吸气剂材料组合包含金属钯与过渡金属氧化物的粉末的混合物，其中所述金属钯的量为按重量计0.2％至2％，其特征在于，所述过渡金属氧化物包含氧化铈和氧化铜，并且还在于氧化铜以5％至50％、优选10％至20％的量存在，其中所有按重量计的浓度都相对于所述过渡金属氧化物的总重量来表示。
在本发明的一个实施方案中，所述过渡金属氧化物粉末混合物由氧化铈和氧化铜组成。
在下文的描述中以及在权利要求中，氧化铜是指化合物CuO，其中铜以氧化态II存在，而二氧化铈是指化合物CeO2，其中铈以氧化态IV存在。在下文的描述中，还使用缩写MO来一般性地表示过渡金属氧化物的组合，并且缩写MO+Pd表示MO与金属钯的混合物。术语“吸气装置”是指能够吸附气体物质(例如，氢气、氧气、一氧化碳和水汽)而不释放其他气体物质的任何装置，所述装置能够在-80℃至80℃的温度范围内工作。
本发明人出乎意料地发现，当含有金属钯时，使用氧化铈与氧化铜的混合物相比于仅使用其中一种氧化物能够得到对气体(例如氢气和一氧化碳)的令人满意的吸附性能。根据本发明，仅下列这样的组合实现了该吸附性能，所述组合包含相对于氧化物组合之总重量低于50％但高于5％的量的氧化铜，更优选10％至20％的氧化铜。
此外，本发明人已发现，为了改进吸附能力以适应真空(热)绝缘应 用的需求，所述氧化物混合物的一个重要性能够在于适当地选择单位重量的表面积。事实上，优选地选自5m2/g至50m2/g的范围。该表面积范围与在用于汽车应用或燃料电池的催化中通常使用的类似的过渡金属氧化物混合物(例如，在作为US 2003/0186805公开的美国专利申请中所描述的)非常不同。无论如何，所选表面积都允许本发明组合物用于本发明目的的应用，所述组合物对一氧化碳具有持续吸附能力以及对氢气具有出乎意料的额外吸附能力，其中“工作温度”比在催化应用中通常使用的工作温度低得多。在过渡金属氧化物混合物的制备期间，金属钯的前体的添加量使得最终混合物将包含按重量计不多于2％的Pd。可通过以可溶性盐(例如，水合Pd(NO3)2)的形式将钯引入同一溶液中来使钯与过渡金属氧化物的混合物共沉淀。或者，可将钯从溶液中沉积在预先形成的过渡金属氧化物的颗粒上。以粉末形式使用过渡金属氧化物组合，粒径低于500μm，并且优选为0.1μm至100μm。
如上所述，本发明的过渡金属氧化物与钯的组合得到了令人满意的对氢气和一氧化碳的吸附性能。然而，本发明人已发现，如果待吸附的气体混合物的组成要求提高对一氧化碳的反应性和吸附能力的话，则可通过向所述吸气剂材料组合中添加一定量的至少一种碱金属氢氧化物和/或碱土金属氢氧化物(优选氢氧化锂或氢氧化钙)来提高对一氧化碳的反应性和吸附能力。在一个优选的实施方案中，总的所述至少一种金属氢氧化物粉末相对于过渡金属氧化物和金属钯的混合物(MO+Pd)粉末的比率为20∶1至1∶1。
如果在待去除的气体物质中存在H2O，则本发明的吸气剂材料组合可包含吸水材料，所述吸水材料优选地选自根据现有技术通过化学反应以不可逆方式固定水的那些。例如，钙氧化物、锶氧化物、钡氧化物以及磷氧化物适用于本发明的目的。特别优选的是使用氧化钙。优选以具有约0.1μm至20μm粒径的粉末形式使用吸水材料。为了避免湿粉末聚结的问题，可向吸水材料中添加惰性材料粉末，例如氧化铝。
无论在使用氢氧化锂时还是不存在氢氧化锂时，过渡金属氧化物与金属钯的混合物MO+Pd粉末与吸水材料的重量比都可在宽的界限内变动，该重量比还取决于预期用途的类型，特别是实际待去除的气体混合物。然而，一般来说，MO+Pd混合物与吸水材料的重量比可以在约5∶1至1∶120之间变动，优选在1∶20至1∶120之间变动。
最后，在另一个实施方案中，上述组合物可与少量的一氧化锰 (manganese oxide)MnO或氧化亚铁(iron oxide)FeO混合使用，如果待吸收的气体混合物包含氧气，则所述组合物尤其有用。为了本发明预期的应用，MnO或FeO的量可在相对于所有吸气剂材料的总组合按重量计0.5％至20％之间变动。
本发明吸气装置中的吸气剂材料组合优选使用为将其布置在可透过待去除气体混合物的由聚合物材料制成的容器内，所述透气率取决于所述容器壁的孔隙率，或者取决于其构成材料的透气特性。对于所述容器的形式，特别优选的是沿着其一边或更多边热密封的袋的形式。用于该包袋的聚合物材料可选自无纺织物形式的聚乙烯、LDPE、HDPE、EVA、SEBS。
在一个替选的实施方案中，可通过本领域公知的技术来生产挤出聚合物或颗粒化聚合物，使所述聚合物中分散有组合物粉末。在这种情况下，诸如LDPE、HDPE、PP、EVA、SEBS的聚合物基质是特别优选的。
可参照以下实施例来举例说明本发明及其相对于现有技术的技术优点。
在第二方面，本发明涉及一种真空隔热板，包括在两壁之间限定的内部空间，还包括含有吸气剂材料组合的吸气装置，所述吸气剂材料组合包含金属钯和过渡金属氧化物的粉末的混合物，其中所述金属钯的量为按重量计0.2％至2％，其特征在于，所述过渡金属氧化物粉末混合物包含氧化铈和氧化铜，并且氧化铜以5％至50％、优选10％至20％的量存在，其中所有按重量计的浓度都相对于所述过渡金属氧化物组合的总重量来表示，所述吸气装置插在所述内部空间中或插在与所述内部空间相连通的分开的空间中。
实施例 1-10％CuO-CeO2/1％Pd
将1.5gCu2(CO3)(OH)2(孔雀石)悬浮于5MCe(NO3)3·6H2O的水溶液(10ml)中。然后蒸发水，从而浸渍孔雀石。将所得的固体产物在烘箱中于110℃干燥，接着再将其悬浮于0.1MPd(NO3)2水溶液(10ml)中。再次蒸发水，得到褐色粉末。使所得固体在马弗炉中于300℃至500℃的温度下保持5小时分解。由此得到的产物在本文中定义为样品1，其具有37m2/g的表面积(BET测量)。
实施例 2-20％CuO-CeO2/1％Pd
将2.8gCu2(CO3)(OH)2(孔雀石)悬于4.6MCe(NO3)3·6H2O的水溶液(10ml)中。然后蒸发水，从而浸渍孔雀石。将所得的固体产物在烘 箱中于110℃干燥，接着再将其悬于0.1MPd(NO3)2水溶液(10ml)中。再次蒸发水，得到褐色粉末。使所得固体在马弗炉中于300℃至500℃的温度下保持5小时分解。由此得到的产物在本文中定义为样品2，其具有19m2/g的表面积(BET测量)。
实施例 3-10％CuO-CeO2/1％Pd和LiOH
使10％CuO-CeO2/Pd(按照实施例1所述制备)和LiOH以4∶1的比率进行机械混合1小时。由此得到的产物在本文中定义为样品3。
实施例 4(比较例)-CuO/1％Pd
将13.6gCu2(CO3)(OH)2悬于0.1MPd(NO3)2的水溶液(10ml)中。蒸发水，得到褐色粉末。使所得固体在马弗炉中于200℃的温度下保持5小时分解。由此得到的产物在本文中定义为样品4，其具有26m2/g的表面积(BET测量)。
实施例 5(比较例)-Co3O4/1％Pd
在搅拌下，向2M的Co(NO3)2·6H2O的水溶液中添加PdCl2溶液。五分钟后，添加0.8M的NaHCO3水溶液。释放气体。释放完气体后，添加35％H2O2。添加完H2O2后，将其加热至85℃。通过过滤回收所得固体。最后，将Co3O4在烘箱中于130℃干燥10小时。由此得到的产物在本文中定义为样品5，其具有100m2/g的表面积(BET测量)。
实施例 6( 比较例 )-80％CuO-CeO2/1％Pd
将11.1gCu2(CO3)(OH)2(孔雀石)悬于1.1MCe(NO3)3·6H2O的水溶液(10ml)中。然后蒸发水，从而浸渍孔雀石。将所得固体产物在烘箱中于110℃下干燥，然后再将其悬于0.1MPd(NO3)2水溶液(10ml)中。再次蒸发水，得到绿色粉末。使所得固体在马弗炉中于300℃至500℃的温度下保持5小时分解。由此得到的产物在本文中定义为样品6，其具有12m2/g的表面积(BET测量)。
实施例 7( 比较例 )-10％CuO-CeO2/0.1％Pd
将1.4gCu2(CO3)(OH)2(孔雀石)悬于5.2MCe(NO3)3·6H2O的水溶液(10ml)中。然后蒸发水，从而浸渍孔雀石。将所得固体产物在烘箱中于110℃干燥，然后再将其悬于0.01MPd(NO3)2水溶液(10ml)中。再次蒸发水，得到褐色粉末。使所得固体在马弗炉中于300℃至500℃的温度下保持5小时分解。由此得到的产物在本文中定义为样品7，其具有 26m2/g的表面积(BET测量)。
通过将每个样品暴露于在预先抽成真空的室内具有5托恒压(P测试)的测试气体下进行对氢气和一氧化碳吸附测试来计算前述实施例的样品的吸附能力，所述室与外界隔绝，并且通过阀V来只与进气室连通，调节阀V以将P测试维持在所需的值。进气室内压力的降低成为样品对特定测试气体吸附能力的量度。
当吸气剂去除H2或CO时，P测试降低，为了使其值回到5托，打开V，从而降低进气室内的压力。
结果表示为在暴露于待去除气体不同时间后所吸收的量，其记录于表1中，其中很明显的是，与比较例5(其中所用的过渡氧化物粉末是钴氧化物的粉末)和比较例4(其中不使用氧化铈粉末而仅使用氧化铜)相比，样品1、2和3对两种气体都具有优异的吸附性能。
在氧化物MO+Pd组合中，高CuO含量(样品6)或低Pd含量(样品7)都对H2吸附性能具有不利影响。所有样品均在室温(RT)下测试。
此外，测量温度的升高(样品1在100℃)对H2吸附性能具有不利影响。
表1

Claims (13)

1.含有吸气剂材料组合的吸气装置，所述吸气剂材料组合包含金属钯与过渡金属氧化物的粉末的混合物，其中相对于所述过渡金属氧化物的总重量，所述金属钯的量为按重量计0.2％至2％，其特征在于，所述过渡金属氧化物的粉末具有5m2/g至50m2/g的表面积并且包含氧化铈和氧化铜，并且还在于，相对于所述过渡金属氧化物的总重量，氧化铜以5％至50％的量存在。
2.根据权利要求1所述的吸气装置，其中所述过渡金属氧化物的粉末包含相对于所述过渡金属氧化物总重量的10％至20％的量的氧化铜。
3.根据权利要求1所述的吸气装置，其中所述过渡金属氧化物的粉末的粒径小于500μm。
4.根据权利要求3所述的吸气装置，其中所述粒径在0.1μm至100μm之间。
5.根据权利要求1所述的吸气装置，其中所述吸气剂材料组合还包含选自氢氧化锂和氢氧化钙中的至少一种金属氢氧化物的粉末。
6.根据权利要求3所述的吸气装置，其中所述至少一种金属氢氧化物的粉末相对于所述金属钯与过渡金属氧化物的粉末的混合物的重量比在20:1至1:1之间。
7.根据权利要求1所述的吸气装置，其中所述吸气剂材料组合还包含吸水材料粉末，所述金属钯与过渡金属氧化物的粉末的混合物相对于所述吸水材料粉末的重量比在5:1至1:120之间。
8.根据权利要求7所述的吸气装置，其中所述重量比在1:20至1:120之间。
9.根据权利要求1、3或6所述的吸气装置，其中所述吸气剂材料组合还包含相对于所述吸气剂材料组合的总重量按重量计为0.5％至20％的量的一氧化锰粉末和/或氧化亚铁粉末。
10.根据权利要求1-8中任一项所述的吸气装置，其中所述吸气剂材料组合被封闭在聚合物容器中。
11.根据权利要求10所述的吸气装置，其中所述容器是热密封包袋形式。
12.根据权利要求1至8中任一项所述的吸气装置，其中所述吸气剂材料组合分散在复合聚合物或颗粒化聚合物形式的聚合物基质中。
13.真空隔热板，其包括在两壁之间限定的内部空间，还包括根据前述权利要求中任一项所述的吸气装置，所述吸气装置插在所述内部空间中，或插在与所述内部空间相连通的分开的空间中。
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