CN107636454A - 一种浸水式检测器 - Google Patents
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Abstract
用于检测水中气态分析物存在的设备，包括包围防水感测室(20)的可潜水外壳(10)，所述防水感测室具有由对UV光可透的材料制成的第一壁(22)和可透气膜制成的第二壁(18)用于允许在操作期间所述外壳所浸入的水中溶解的气体进入所述感测室，设置在所述感测室内间隔的第一和第二感测电极(24和26)，以及连接到所述感测电极的电路，所述电路用于测量由于所述感测室中的气体通过UV光电离而产生流经所述感测电极的电流，其特征在于，将第三电极(28)放置于所述感测室(20)中，并且所述电路可被操作以在所述第三电极(28)和所述第一感测电极(24)两端施加电压，所述电压具有足够大小使得可以通过水解与所述第一和第三电极电接触的冷凝液滴来降低感测室(20)内的冷凝。
Description
技术领域
本发明涉及使用检测器对溶解于水中和其他水性液体中的气态挥发性分析物的检测，在所述检测器中以气相检测这些物质。特别关注的分析物是在水中或水溶液中发现的质量浓度从小于十亿分之一(ppb,10-9)到千分之几(ppt,10-3)的不同的挥发性有机化合物(volatile organic compounds，VOC’s)。
背景技术
需要在自然或人为保有的水源或其他水性液体中检测和测量挥发性化合物的存在。许多这样的化合物被归类为挥发性有机化合物(VOC’s)，并包括刺激物、雌激素、致癌物和其他对人类、动物和植物生命有害的化学物质。在海洋环境、水路、港口、工业过程用水和废水中，它们都是一个令人关切的问题。在其它水性液体中它们也可能是具有意义的，例如在由于液体食品的发酵和酿造的乙醇检测中。
在大片水内调查气态物质的存在以及以近似实时的方式探查(trace)其来源和程度是经常被加以关注的，例如由石油化工产品泄漏到海水中而引起。这样的水体也受到潮流和漂流的影响。因此，优选的是，能够检测水中目标分析物的传感器提供对气态种类浓度的快速和定量测量。
应当注意的是，清洁的饮用水中含有的任何VOC’s的浓度是非常低或不可察觉的，而污染水体中则可能含有广泛的一系列VOC’s任何一种。因此，水中VOC检测器可以在快速识别水中存在一系列不同分析物的情况下起到最大的作用，以便有把握地在VOC’s扩散之前识别它们的来源，并且使得可以以较少时限要求和不再较昂贵的详细分析来选取欲追溯的若干水样。以这种方式使用的检测器通常被称为筛选工具。
一类这样的传感器或检测器包含一个通常为疏水性的膜，该膜在水性感测环境和检测器包隔体(enclosure)之间提供了屏障，分析物能够穿过该膜而进行扩散。在通过引用而并入本专利申请的英国专利GB1421306.0中，具有气态包隔体作为一个元件的这样的检测器，位于优选为疏水性多孔膜内的几毫米处，该疏水性多孔膜将该检测器与含有VOC’s的水分隔开。声称该检测器在某个气体平衡浓度下提供对水中VOC’s的响应。
本发明涉及用于检测水中挥发物的光致电离检测器的操作和构造。
诸如GB1421306.0中的水中挥发物传感器的传感器可能面临的一个问题是水中挥发物的冷凝。水中挥发物传感器可能会从相对冷的空气或水中环境中急剧浸入明显更暖的水中。在这种情况下,在传感器膜的液体界面处的气体中的水蒸气是暖的并处以饱和蒸汽浓度。在自由扩散而通过多孔膜进入冷的传感器内部时，富水的空气被冷却到低于其露点的温度，导致了传感器内的水冷凝。在许多温度波动之后，传感器气体腔中的水可能积聚到导致传感器失效的程度。
本发明寻求减轻上述问题的方法，并在此延长水中挥发物传感器可以在水中操作的时间。
发明内容
根据本发明来提供一种如所附权利要求书的权利要求1所述用于检测水中气体分析物的存在的设备。
优选的是，两个感测电极之间的电位差至少为2伏特，并且它们之间的距离为2毫米或更小。在光致电离检测器的情况下，优选的是，初级阴极和阳极之间的电位差在它们之间的间距下为至少100伏特每毫米。
有利的是，分隔初级电极和次级电极的分隔件兼顾(compromise)低介电和防水材料，诸如聚四氟乙烯(polytetrafluoroethylene，PTFE)。
附图说明
现在将参考附图通过示例进一步描述本发明，其中的单图是在水下使用的光致电离检测器(photoionisation detector,PID)的示意图。
具体实施方式
为了方便起见，以下将吸引且中和阴离子并由于水的电解还可能产生氢气的电极称为阴极，将吸引阳离子并由于水的电解还可能产生氧气的电极称为阳极。
现转到图1，示意图表示通过PID光电元件14的一断面。PID光电元件与通过引用而并入本发明的GB2449664的PID光电元件类似，在于该PID光电元件包含毗连气体感测室20而布置并通过UV透明窗22的方式而分隔开的UV光源12。
在室20内有至少三个电极的堆叠，该堆叠由一对感测电极24和26，和在此被称为栅栏电极(fence electrode)的第三电极28组成。第一和第二感测电极将栅栏电极夹在中间，第一感测电极(阴极)24在距UV光源的最远处，而第二感测电极(阳极)26与将光源从感测室分隔开的窗22毗连。
与GB1421306.0中类似的所示设备与GB2449664相比的区别是该PID光电元件适用于淹没的情况。通过一优选为疏水的可透气膜18的方式将感测室20与样品液体30密封隔离。如GB1421306.0中所述，该膜允许进入感测室20的分析物与样品液体30毗连液体的液相中的分析物的浓度形成近似平衡。
随后PID测量感测室20内的分析物的浓度，有赖于平衡状态，该PID指示了样品液体30中的分析物的浓度。PID用于测量分析物浓度的机理本质上与在非淹没情况下使用时的机理是相同的，因此不需要在本发明上下文中更详细地描述。
此外，可以用由诸如聚四氟乙烯的低介电性防水材料制成的间隔体将电极(24、26、28)支承和分离。该间隔体形成感测室20的壁的主要部分，并用于减少冷凝的润湿作用。应避免壁的润湿，因为这允许了电流在感测电极之间的传导从而对传感器的精度造成不利的影响。
在以前的非淹没条件下使用栅栏电极的目的在EP1474681中有记载，其通过引用并入本发明。总而言之，它涉及从感测电极感测到的电流中除去由PID光电元件内的除了光致电离之外的机构产生的附加电流。
之前并没有考虑使用第三“栅栏”电极进行溶解的VOC’s的检测，因为直到最近才将PID用于淹没条件下对溶解在水中的VOC’s的浓度的检测。
在应用中，感测电极24和26之间的电位差大约为200伏特。第三“栅栏”电极处于与阳极26大致相同的电位，使得它们之间没有电流流动。
当在水下使用时，如上所述，感测室内部可能遭受冷凝的影响，从而损害传感器的使用寿命。然而在使用PID检测器来检测空气中的VOC’s的应用中，栅栏电极简单地将感测电极遮蔽而免受聚集在感测室壁上的冷凝物的影响,但它在浸水式检测器中的目的是防止这种冷凝物。特别地，有赖于栅栏电极28与第一感测电极(阴极)24之间的电位差，与这两个电极电接触的任何水都会被水解成氢气和氧气，从而除去作为感测室20污染物的水。
当不浸入水中时，PID 14中的冷凝程度所造成的问题较小，并且由于流过栅栏电极的电流通常小于一微安，可以将可能发生的任何水解最小化。相比之下，在优选实施例中，申请人试图提高栅栏电极功率处理能力，从而当在水下条件下使用时能够水解较大量的影响PID14的水。
栅栏电极用于阻断可能流经PID光电元件内受污染壁的电流。这对于多个PID暴露于含盐环境和分析物中的场合是特别有用的，其中所述分析物将盐作为光致电离和光致解离(photo-dissociation)产物而沉积。当在空气中使用PID传感器时，通过容纳直径为6毫米的灯，通常为0.3微安的栅栏电流阈值足以摄取由这种污染形式引起的壁电流，从而确保了在感测电极选择性地感测光致电离腔本身以内产生的电流。
而在将PID浸入水中时，理想的是将该电流阈值提高1000倍(300微安)，以使栅栏电极能够中和来自导电PID腔体壁表面所引起的电流的影响，从而可以精确地确定由光致电离导致的电流。在这样的电流下，可以很快地将水消耗并使PID光电元件随时间变干。当然，对于在空气中使用栅栏电极的PID，超过常规0.3微安的任何电流限制将在传感器内对水的水解方面产生成比例的有益结果。在0.05毫安、0.1毫安和0.2毫安下已经获得了持续增加的成果。
用于电解水所提供并因此参与诸如以下的半电池反应
2H+(液态)+2e＝H2(气态)
的阴极可能有意无意地参与其他反应，这些反应包括但不限于由例如在形成邻接阴极的气体腔的一部分的壁构件上沉淀的盐溶解或潮解而形成的盐液中阳离子的还原反应，或溶解在水性流体中氧的还原反应。
相应地，用于电解水所提供并因此可能参与以下半电池反应
H2O＝1/2O2+2H++2e
的阳极也可能参与其他反应，这些反应包括但不限于由例如在形成邻接阴极的气体腔的一部分的壁构件上沉淀的盐溶解或潮解而形成的盐液中阴离子的氧化反应，在气体所携带电子的去除中，这些反应可能是诸如由从暴露于光子的阴极并由阴极向阳极推进的光子喷射(photon-ejection)所产生的反应。
Claims (7)
1.用于检测水中气态分析物存在的设备，包括包围防水感测室(20)的可潜水外壳(10)，所述防水感测室具有由对UV光可透的材料制成的第一壁(22)和可透气膜制成的第二壁(18)，所述第二壁(18)用于允许在操作期间所述外壳所浸入的水中溶解的气体进入所述感测室，设置在所述感测室内的间隔的第一和第二感测电极(24和26)，以及连接到所述感测电极的电路，所述电路用于测量由于所述感测室中的气体通过UV光电离而产生流经所述感测电极的电流，其特征在于，将第三电极(28)放置于所述感测室(20)中，并且所述电路可被操作以在所述第三电极(28)和所述第一感测电极(24)两端施加电压，所述电压具有足够大小使得可以通过水解与所述第一和第三电极电接触的冷凝液滴来降低感测室(20)内的冷凝。
2.根据权利要求1的设备，其中所述第一和第二感测电极(24和26)之间的距离为2毫米或更小。
3.根据权利要求1或2的设备，其中所述第一和第二感测电极之间的电位差在它们之间的间距下为至少100伏特每毫米。
4.根据前述任一项权利要求的设备，其中所述第二和第三电极(26和28)之间的电位差基本为零。
5.根据前述任一项权利要求的设备，其中所述第一感测电极(24)为阴极而所述第二感测电极(26)为阳极。
6.根据前述任一项权利要求的设备，其中分隔所述第一和第二感测电极的分隔件由例如聚四氟乙烯的低介电防水材料制成。
7.根据前述任一项权利要求的设备，其中所述第一和第三电极(24和28)的电流流动容量为300微安。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1506150.0 | 2015-04-10 | ||
| GB1506150.0A GB2537361B (en) | 2015-04-10 | 2015-04-10 | A Water Immersible Detector |
| PCT/IB2016/051693 WO2016162773A1 (en) | 2015-04-10 | 2016-03-24 | A water immersible detector |
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| US (1) | US10345265B2 (zh) |
| EP (1) | EP3281002B1 (zh) |
| CN (1) | CN107636454A (zh) |
| GB (1) | GB2537361B (zh) |
| WO (1) | WO2016162773A1 (zh) |
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| CN112179975A (zh) | 2019-07-01 | 2021-01-05 | 霍尼韦尔国际公司 | 用于限制光致电离检测器中的水的方法和系统 |
| CN112834490B (zh) * | 2021-01-07 | 2022-12-20 | 上海雷密传感技术有限公司 | 光离子检测装置 |
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| GB2527867B (en) | 2014-12-01 | 2016-06-29 | Ion Science Ltd | Detection of organics in water |
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- 2016-03-24 CN CN201680024058.7A patent/CN107636454A/zh active Pending
- 2016-03-24 US US15/564,508 patent/US10345265B2/en not_active Expired - Fee Related
- 2016-03-24 WO PCT/IB2016/051693 patent/WO2016162773A1/en active Application Filing
- 2016-03-24 EP EP16716696.6A patent/EP3281002B1/en not_active Not-in-force
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Also Published As
| Publication number | Publication date |
|---|---|
| EP3281002A1 (en) | 2018-02-14 |
| GB201506150D0 (en) | 2015-05-27 |
| US10345265B2 (en) | 2019-07-09 |
| EP3281002B1 (en) | 2019-02-27 |
| GB2537361B (en) | 2017-05-03 |
| US20180080900A1 (en) | 2018-03-22 |
| GB2537361A8 (en) | 2016-10-26 |
| GB2537361A (en) | 2016-10-19 |
| WO2016162773A1 (en) | 2016-10-13 |
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