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CN1118570A - 用于存放液体的热容器的隔热真空套筒 - Google Patents

用于存放液体的热容器的隔热真空套筒 Download PDF

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CN1118570A
CN1118570A CN94191152A CN94191152A CN1118570A CN 1118570 A CN1118570 A CN 1118570A CN 94191152 A CN94191152 A CN 94191152A CN 94191152 A CN94191152 A CN 94191152A CN 1118570 A CN1118570 A CN 1118570A
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克劳迪奥·伯菲托
布鲁诺·费拉里奥
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Abstract

一种适于做存放液体特别是含水的和/或有机的液体的热容器的隔热真空套筒，它包括氧化钡(BaO)与氧化钯(PdO)和/或与由钌、铑、锇，铱和银中挑选一种稀有金属的另一种氧化物的一种组合物作为吸附在所述套筒中在抽真空之后存在的残余气体(主要包括氢气、一氧化碳、二氧化碳和水汽)的材料。

Description

用于存放液体的热容器的隔热真空套筒
本发明涉及适于做存放液体的热容器的隔热真空套筒，所述液体特别是含水的和/或有机的液体，像咖啡，茶，热牛奶，肉汤，果汁，酒类，和如葡萄酒或啤酒的饮料，提神饮料或冷的软饮料，以及需要在比室温高或低的温度下长时间保存的其它饮料。这类液体的其它例子可以是药用和/或生物制品的，防冻制品的样品的，放射性同位素的特殊化合物的溶液或悬浮液(例如含水液体或水醇液体)，等等。从原则上说，按照本发明的套筒也可以用于杜瓦瓶和其它冷冻装置(例如隔热管线)，只要不存在液态氢就可以。
英国专利921,273公布了靠由玻璃或金属制成的一个真空套筒对存放不含水的液体(如液体氧或氮)的容器进行隔热，该套筒包括氧化钯(PdO)与由沸石，焦炭和硅胶中挑选的一种材料的组合物，显示出对氢的吸附活性。
所述组合物的目的是使隔热套筒中的所要求的真空水平能长时间维持，这是靠吸附从一开始(或后来产生的)由从套筒壁脱气而在套筒中已经存在的或透过套筒壁泄漏所造成的残余气体。所述的残余气体主要是氢气，一氧化碳，二氧化碳和水汽。
然而，沸石对二氧化碳的吸附能力有限(并且对一氧化碳和氢气的吸附能力实际上为零)，并且如果含水液体(如咖啡)的温度比外部温度高，对水的吸附能力也不高；此外，沸石的活化要求长时间的热处理，这使得使用它们远远不是便宜的，特别是在大量使用的情况下。这就是为什么直到现在还没有真空瓶(保温瓶)对于含水液体使用包括所述的组合物。
用焦炭和/或硅胶代替沸石也没有任何明显的改善。
授权给申请人的意大利专利1,191,114建议用以锆为基础的特殊合金来代替以氧化钯为基础的所述组合物，只能稍稍改善在真空瓶中有含水液体的情况。然而，即使是这种合金，对水汽和其它残余气体也没有高的吸附能力，还要求高的活化温度(573K或甚至更高)。还有，在这种情况下，为了使气体负载量达到最小，在制作过程中必须在抽空的条件下对保温瓶作长时间的热处理。
现在，上述的缺点被申请人克服了，本申请人发现了以氧化钯为基础的非常好的组合物，可以插入到真空瓶的隔热套筒中。
在其广义上说，本发明涉及适于做存放含水的和/或有机的液体的热容器的隔热真空套筒，并且特别适于做所谓保温瓶，它包括氧化钯(PdO)和氧化钡(BaO)的一种组合物作为吸附在该套筒中存在的残余气体(主要包括氢气，一氧化碳，二氧化碳和水汽)的材料。氧化钯可以选择性地部分或全部由氧化钌，氧化铑，氧化锇，氧化铱或氧化银代替。
氧化钯(或其它稀有金属的氧化物)可以这样直接地使用或以被承载的方式使用；载体可以包括例如矾土，硅土，硅酸盐或硅酸钛，它们的表面积由10至600平方米/克(微孔直径为0.5至100毫微米)，并且放在套筒中的该组合物可以是粉末状的，也可以是小片，颗粒，圆环，马鞍形等形状。
按照一个具体的实施例，首先制备水溶性的钯盐(例如氯化物或硝酸盐)的水溶液，然后，用一种预先确定的技术(例如用浸渍技术，或用所谓干浸渍技术，即按照此技术浸渍溶液的体积等于或小于载体的微孔的总体积的一种技术)对载体(例如矾土)进行浸渍。随后，借助一种碱性溶液(最好由pH7至pH12)实现沉淀，把反应混合物过滤，并在低于500℃的温度下进行干燥。随后，这样得到的粉末(颗粒度为由0.5至200微米)与粉末状的氧化钡(颗粒度为由0.5至500微米)混合，并且可选择性地与痕迹量的粘合剂和/或润滑剂混合；然后把混合物压制成小片，把这些小片放在被抽空的隔热套筒中。
附图仅只用作说明的目的，在任何情况下都不限制本发明的范围和精神。附图中：
图1为带有按照本发明的隔热套筒的保温瓶的剖面图；
图2为把所述套筒抽空的方法的布局图；
图3，4和5给出示例的试验中所得到的一些结果。
看图1，一个保温瓶1包括一个由玻璃或金属制作的圆柱形内容器2，它确定了内部容积或有用空间3，适用于存放含水液体，具体地说热的或冷的饮料，它靠一个颈部6(通常被关闭，但不被密封)与外部连通。一个外壁或外罩(壳)4与容器的壁2一起确定了处于真空的一个套筒(空间)5；在制作保温瓶的状态下在抽空的过程中这个套筒与一个在图中未示出的真空泵相接通。在刚抽完真空时，此空间的压力当没有隔热材料时通常等于或低于5×10-3毫巴，最好为10-4至10-6毫巴。如果此空间包括隔热材料，最大容许压力可以高些，例如高到0.1毫巴。把PdO和BaO的组合物(可选择性地为被承载的)设置成与外壳4相接触，该组合物按照PdO/BaO重量比约为1∶1至1∶1000之间(最好由1∶2到1∶200)。可选择的还有，可以把新的组合物(例如Bao＋PdO)包括在一个美国专利5,191,980中所描述的那种类型的热缩性的外壳内。
下面提供的示例仅只为了说明的目的，在任何情况下都不限制，并不以任何方式限制本发明的范围和精神。
示例1(条件与示例2和3相同)
一种适于测量按照本发明的吸附材料的气体吸附性质的装置示于图2。
此图以示意的方式示出测量BaO和PdO的混合物以及其它作比较的混合物的吸附特点的装置100。
一个抽真空系统102靠第一阀104与测量容积106相连接。一系列第二阀110，110’，110″与所述的测量容积相连接，为的是可以输入来自一系列试验瓶112，112’，112″(分别包括氢气，二氧化碳和一氧化碳)的试验气体，一个压力计114也与该测量容积相连。一个包括被试验的样品120的试验瓶118靠第三阀116与该测量容积106相连。
在试验过程中，阀110，110’，110″和116被关闭，并把阀104打开，而抽真空系统102把系统的压力降低到10-6毫巴。
测量容积106对于每次所进行的试验有约0.8升的容积。把装置100经过(关闭着的)阀116连接到包括在试验气体瓶118中的样品120中，该瓶有约0.3升的容积，并处于惰性的氩气的气氛中。
在试验阀116被打开和系统被再一次抽空降到10-6毫巴的过程中，同时把样品在约100℃下保持15分钟，这模拟了与吸附组合物可能遇到的情况类似的一个循环，并且，随后，使样品冷却到室温。然后把阀104和116关闭，并使来自气体瓶112，(112’，112″)的试验气体流进测量容积106一个短时间。在压力计114上记录压力，并把压力控制在约为0.2与0.5毫巴之间，打开阀116之后，使数量作了测量的试验气体进入与样品120接触。
示例2
一克粉末状颗粒度低于125微米的氧化钡与二克由多孔的矾土承载的氧化钯颗粒(平均尺寸低于600微米)(PdO的成色为按重量计2％)混合。
随后，把样品连接到示例1的试验装置上。再把第一种数量被测量过的气体(在这一情况下为来自瓶112经阀110的一氧化碳)带入与样品接触。
借助仪器114测量容器中的压力随时间的变化；结果图在图3中以线1示出。
接着，使其它数量被测量过的气体(氢气，二氧化碳等)顺序地流过样品，遵照相同的步骤。
表示压力随时间变化的相应曲线分别在图3中以线2和3示出。
在每种情况下，与先有技术的吸附材料相比，样品都显示出较高的吸附特点，不管是吸附速度，还是吸附能力都是这样。
示例3(作比较的)
此示例显示常规材料的性能，此材料像通常为了实现隔热的抽空了的空间而采用的那些材料一样。
由Davidson化学品公司提供的直径为1/8英寸(3.2毫米)的(圆柱形)片状的一克13X级(微孔直径为1毫微米)的合成沸石与40毫克粉末状颗粒度低于125微米的氧化钯混合。
然后把样品118连接列示例1的试验装置上。再遵照示例2的步骤，把样品接续地放在数量经过测量的气体中(依序为氢气，一氧化碳和二氧化碳)。表示压力随时间变化的相应曲线分别在图4中以线1，2和3示出。
这些试验的结果表明只在氢气和二氧化碳的情况下能够测到吸附能力。从实际的观点看来，在一氧化碳的情况下(线1)没有测列压力的下降。
示例4
约500毫克粉末状颗粒度低于125微米的氧化钡与250毫克由多孔的矾土承载的氧化钯颗粒(平均尺寸低于600微米)(PdO的成色为按重量计2％)混合。然后把混合物放入如ASTM—F—798—82(关于可以用来确定吸气程度，吸附能力和在分子流领域中非蒸发性的吸气剂(NEG)中的气体浓度的标准)所述的一个系统中。
在使系统在抽真空的条件下在约150℃的温度下脱气7个小时之后，并使样品冷却到室温(大约25℃)之后，开始吸附试验，首先对样品通氢气，接着通一氧化碳。两个试验都在样品上维持等于5×10-5毫巴的常压。这样得到的吸附曲线示于图5。

Claims (10)

1.一种适于做存放液体特别是含水的和/或有机的液体的热容器的隔热真空套筒，它包括氧化钡(BaO)与氧化钯(PdO)和/或与由钌、铑、锇、铱和银中挑选的令一种稀有金属氧化物的一种组合物作为吸附在所述套筒中存在的残余气体(主要包括氢气，一氧化碳，二氧化碳和水汽)的材料。
2.按照权利要求1的套筒，其特征在于，所述的氧化钯或其它稀有金属的氧化物为被承载的方式。
3.按照权利要求1的套筒，其特征在于，所述的与氧化钯不同的稀有金属氧化物是氧化钌。
4.按照权利要求2的套筒，其特征在于，担体由矾土，硅土，硅酸盐或硅酸钛中挑选，并且担体的表面积由10至600平方米/克(微孔直径为1至100毫微米)。
5.按照权利要求2的套筒，其特征在于，所述的组合物以粉末的形状存在。
6.按照权利要求2的套筒，其特征在于，所述的组合物以由小片，颗粒，圆环和马鞍形中挑选的一种形状存在。
7.按照权利要求2的套筒，其特征在于，所述的被承载的氧化钯以由这样得到的一种形态存在：由水溶性的钯盐(具体地说氯化物或硝酸盐)的水溶液，借助一种碱性溶液在担体存在的情况下进行沉淀。
8.制备按照权利要求7的组合物的一种方法，其中首先把所述的粉末状担体按照干浸渍技术用钯盐的水溶液进行浸渍，借助一种碱性溶液把这样浸渍过的粉末进行处理，并把所得到的产物过滤，干燥，转变成粉末，最后与氧化钡粉末混合，然后把得到的混合物压制成小片或颗粒。
9.按照权利要求8的方法，其特征在于，所述的担体为矾土，并且PdO∶BaO重量比为1∶1至1∶200。
10.一种适于做存放液体的热容器，靠权利要求2的套筒进行隔热。
CN94191152A 1993-02-24 1994-02-22 用于存放液体的热容器的隔热真空套筒 Pending CN1118570A (zh)

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JP3370993B2 (ja) 2003-01-27
ITMI930356A0 (it) 1993-02-24
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JPH09500031A (ja) 1997-01-07
US5518138A (en) 1996-05-21
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EP0686010A1 (en) 1995-12-13
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ITMI930356A1 (it) 1994-08-24
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