CN107295809A - 用于气体介质的氢检测器 - Google Patents
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000001257 hydrogen Substances 0.000 title claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 38
- 239000007789 gas Substances 0.000 title claims abstract description 18
- 239000000919 ceramic Substances 0.000 claims abstract description 43
- 238000005259 measurement Methods 0.000 claims abstract description 31
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 15
- 238000007789 sealing Methods 0.000 claims abstract description 15
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 4
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
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- 229910052760 oxygen Inorganic materials 0.000 description 9
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- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
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- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明涉及测量技术并且可用于能源工业、冶金、化学工业中以在宽范围的温度和压力下确定气体介质中的氢浓度。用于检测气体介质中的氢的检测器包括借助于密封剂紧密地固定在所述检测器壳体的上部部分上的操作元件。通过螺母提供另外的密封性。检测器壳体的下部部分通过隔热层界定，所述隔热层确保与加热器的紧密接触，所述加热器提供供给到所述蒸汽氢隔室的氢渗透膜的工作介质的温度条件。测量流程带来的干扰经紧密地固定在陶瓷感测元件的下部部分上的测量用铂电极传递到电势测量单元的中央芯部，所述陶瓷感测元件通过玻璃‑陶瓷与所述感测元件的金属外壳密封地连接。基准电极位于所述陶瓷感测元件的内腔中。所述陶瓷感测元件底部的外部部分覆盖有多孔铂电极层。所述电势测量单元的中央芯部的端部伸出至所述基准电极主体内。本发明实现了如下技术效果：通过提供陶瓷感测元件的内腔的密封性和检测器输入处的工作介质的温度条件的稳定性而在宽范围的工作介质参数下提高了氢检测器的使用寿命和操作可靠性。
Description
技术领域
本发明涉及仪表技术并且可以用于能源生产、冶金和化学工业中，以在宽范围的温度和压力下确定气体介质中的氢浓度。
背景技术
气体和流体介质中的氢浓度的电化学检测器被公开(参照1998年10月20日公布的俄罗斯发明专利No.2120624，IPC G01N27/417，Electrochemical Detector of HydrogenConcentration in Gas and Liquid Media(气体和液体介质中的氢浓度的电化学检测器))。
该检测器包括借助于金属与固体电解质氢检测器紧密连接的壳体。固体电解质氧检测器包括由固体电解质制成的在下部部分用插塞封闭的陶瓷绝缘体、施加在插塞的外侧面上的多孔铂电极、安置在插塞内部的液体金属氧化物标准电极、附接在覆盖陶瓷绝缘体的顶部的盖子上的电流引线热电偶。成形为卷曲杯状件的选择性隔膜被焊接在壳体的下部部分上。在选择性隔膜与固体电解质插塞之间安装有多孔绝缘氧化物的片块。
所述装置的缺点是由于通过电势测量单元与中央芯部之间的间隙的氧渗入而引发的陶瓷感测元件的内腔的较低的密封性，这种较低的密封性引起基准电极的氧化以及装置的使用寿命及其操作的可靠性的下降。
流体和气体的氢浓度的电化学检测器被公开(I.G.Dmitriev,V.L.Orlov,B.A.Shmatko.Electrochemical Hydrogen Detector in Fluids and Gases//Thecollection of abstracts of Teplofizika-91(Thermophysics-91)IntersectoralConference,Obninsk,1993.p.134-136)。
该检测器包括基于由稳定的二氧化锆形成的固体电解质的电化学氧电池、Bi+Bi2O3混合物的液体-金属基准电极、安置在填充有水蒸气的密封腔室中的测量用铂电极。
公知技术方案的缺点是：
-由于检测器的构造复杂性而引起的装置的较低可靠性和短使用寿命；
-固体电解质氧检测器对水蒸气的较低热稳定性和耐腐蚀性；
-由于测量腔室中的水蒸气的局部压力的稳定复杂性而引起的较长响应时间和灵敏度不足；
-由于维持温度和管的稳定性而导致的氢浓度测量的较低精度。
一种用于气体和流体介质的氢检测器在技术上最接近要求保护的装置(参照2008年1月20日公布的俄罗斯发明专利2379672，IPC G01N27/417，Hydrogen Detector for Gasand Liquid Media(用于气体和液体介质的氢检测器))。
该氢检测器包括选择性隔膜、多孔电绝缘陶瓷和内部具有电势测量单元的壳体、内腔中具有标准电极的由固体电解质制成的陶瓷感测元件、施加至陶瓷感测元件的外层的多孔铂电极、硅石织物、结合材料、覆盖陶瓷感测元件的腔的截面的带孔的堵头、在陶瓷感测元件的上方紧密地安装在壳体内部的密封引入端、穿过密封引入端的中心孔的双包层电缆电势测量装置、筒形套管。壳体在密封引入端与陶瓷感测元件之间的腔是密封的。陶瓷感测元件被设计为筒形件，该筒形件与位于筒形件的下部部分中的球形部的一部分连接。陶瓷感测元件的筒形外表面的上部部分借助于结合材料与外壳的内侧面紧密连接。基准电极位于陶瓷感测元件的内表面与堵头的表面之间的腔中并且占据所述腔的至少一部分。陶瓷感测元件的外球形部分覆盖有多孔铂电极。电势测量单元的中央芯部的指向陶瓷感测元件的端部经堵头中的孔伸至基准电极。它实现了基准电极与电势测量单元的中央芯部的下部部分之间的电接触。陶瓷感测元件的一部分突伸超出壳体。成形为管状件的套管自陶瓷感测元件的突出部与壳体的下部部分连接。套管的下端具有带中心孔的底部，由至少一个管构成的选择性隔膜附接在该底部上。选择性隔膜的下部自由端利用插塞紧密地(密封地，tightly)封闭。由套管的内表面、结合材料、陶瓷感测元件的突伸超出壳体的外部部分和选择性隔膜的内表面限定的腔是密封的。陶瓷感测元件的突出部与套管底部之间的套管的内腔填充有硅石织物。被设计为筒形件的多孔电绝缘陶瓷定位成与选择性隔膜的内表面之间具有环形间隙。
该公知装置的缺点是陶瓷感测元件的内腔的较低的密封性，该较低的密封性可引起氧经电势测量单元的中央芯部与外壳之间的间隙渗入至内腔并且导致基准电极的氧化以及装置的使用寿命及其操作的可靠性的下降。由于电势测量单元的上部部分的可靠密封的缺乏，水分可渗入双包层电缆的绝缘材料中，这可引起中央芯部和电缆壳套的电阻的下降并因此引起有效信号的损失和检测器读数的恶化。
发明内容
本发明的目的在于在宽范围的气体介质参数下提高氢检测器的稳定性和可靠性以及它的使用寿命及其操作的可靠性。
技术效果
技术效果包括通过提供陶瓷感测元件的内腔的密封性以及通过恒定的可靠加热和防止检测器基准电极的热泄漏和氧化的隔热来确保的操作元件的感测部上的稳定工作温度的可持续性而提高了氢检测器的测量精度。
作为上述问题的解决方案，我们要求保护一种检测器设计，该检测器包括：由至少一个管构成的防水隔膜，该防水隔膜在上部部分中设置有测量用铂电极；内部具有电势测量单元的壳体；和由固体电解质制成的陶瓷感测元件。陶瓷感测元件腔包含基准电极。操作元件在感测元件的上方紧密地固定在壳体的内部。电势测量单元穿过操作元件的中心孔和下部部分，其中感测元件被设计为筒形件，该筒形件与位于筒形件的下部部分中的底部连接。电势测量单元的上部部分是密封的并且包含带有紧密固定的螺母的密封剂。感测元件的筒形外表面与壳体的内侧面紧密连接。基准电极位于感测元件的内腔的内部。电势测量单元的中央芯部的端部伸出到基准电极中，其中在基准电极与电势测量单元的中央芯部的下部部分之间提供电接触。成形为管状件的感测元件的金属外壳借助于密封剂与感测元件的上部部分连接。该密封剂是由氧化硅(SiO2)–45÷55重量％、氧化铝(Al2O3)–4÷6重量％、氧化硼(В2О3)–18÷22重量％、氧化钛(TiO2)–9÷12重量％、氧化钠(Na2O)–12÷15重量％、氧化钾(K2O)-1÷2重量％和氧化镁(MgO)–2÷3重量％组成的玻璃-陶瓷。
密封剂填充感测元件和上套管的金属外壳壁的内表面与陶瓷感测元件的外表面之间的环形腔。
该检测器的特征在于，它配备有用于加热和保持操作元件的感测部上的稳定工作温度的另外的隔热加热器；它还包括蒸汽氢隔室，该蒸汽氢隔室包括镍外壳和由薄壁式镍管制成的薄壁式防水隔膜并且焊接到感测元件外壳上，部分所述感测元件外壳由耐腐蚀钢制成。该检测器设计允许在宽范围的工作介质参数下提高氢检测器读数的稳定性和可靠性以及它的使用寿命及其操作的可靠性。
附图说明
利用附图说明本发明。
图1是检测器的纵轴截面的概略图。
图2是检测器操作元件的纵轴截面的概略图。
图3是检测器感测元件的纵轴截面的概略图。
具体实施方式
氢检测器包括位于陶瓷感测元件4的下部部分中的基准电极1，该基准电极1具有电势测量单元3的浸入式中央芯部2，陶瓷感测元件4借助于玻璃-陶瓷5与位于蒸汽-水隔室8的内部的感测元件7的金属外壳6连接。所示的部件被包括在具有带中心孔的底部的操作元件9中，防水隔膜附接在所述底部上。隔膜由在上部部分中设置有测量用铂电极11的至少一个管构成。操作元件位于金属壳体12中，金属壳体12的密封性通过密封剂3和螺母14来提供。具有隔热层16的加热器15用于加热并且保持操作元件的感测部上的稳定工作温度。
隔热层16填充加热器15壁部的内表面与确定气体中的氢浓度的检测器的壳体12的外表面之间的环形腔。
陶瓷感测元件4位于检测器的下部部分中并且成形为与底部连接的筒形部件。
陶瓷感测元件4的筒形外表面与金属壳体12的内侧面紧密连接。
基准电极1位于陶瓷感测元件4的内腔中。
壳体12被设计为与感测元件7的金属外壳连接的管。
密封剂3是由氧化硅(SiO2)–50重量％、氧化铝(Al2O3)–5重量％、氧化硼(В2О3)–20重量％、氧化钛(TiO2)–10重量％、氧化钠(Na2O)–12重量％、氧化钾(K2O)-1重量％和氧化镁(MgO)–2重量％组成的玻璃-陶瓷。
需要该密封剂以防止空气中的氧进入检测器的内腔中并且避免基准电极特性的变化。
该氢检测器采用了允许借助于由固体氧化物电解质制成的氧传感器来确定氧浓度的电化学方法。为了测量气体介质中的氢浓度，氧检测器另外配备有具有恒定水蒸气压力的隔室8和防水隔膜10。介质中包含的氢经氢检测器的隔膜至测量用铂电极11可逆地扩散到蒸汽氢隔室8中，从而改变检测器的电动势。检测器的电动势由于浓差电池的电极中的氧的局部压力差而引发。电池的方案可以采用以下方式呈现：Me-ES(电化学传感器)-固体氧化物电解质-AE(致动元件)-H2O，H2-H-隔膜-受控介质。
浓差电池包括由固体氧化物电解质构成的陶瓷感测元件(CSE)4、基准电极(RE)1和测量用铂电极(MPE)11。
选择基于部分稳定的二氧化锆(PSZD)的材料用作固体氧化物电解质。PSZD具有高热-机械特性。300-400℃的温度范围内的离子电导率可高达0.95并且在400-500℃的范围内不小于0.97。耐热冲击性超过20℃/s。
Bi-Bi2O3由于其热力学特性的稳定性而被用作基准电极1。
基于铂的多孔复合涂层最适合作为测量用(工作)电极11，其用作用于其表面上的快速氢氧化的催化剂。特殊配方和在感测元件的生陶瓷上施加这种材料并接着进行退火的方法允许形成具有对陶瓷的良好粘附性的、厚度为30μm的高多孔工作电极。
蒸汽氢隔室8位于测量用铂电极11与陶瓷感测元件4之间的腔中并且用作将氢热力势转化为铂电极11上的蒸汽氢混合物的氧化电势的转化器。镍由于其氢渗透性和铅-铋共晶体中的耐腐蚀性而成为最适于氢隔膜10的材料。
工业适用性
该检测器可以商业地制造。此外，它的制造不需要特殊设备。
Claims (4)
1.一种用于气体介质的氢检测器，包括防水隔膜、内部具有电势测量单元的壳体、由固体电解质制成的陶瓷感测元件——所述陶瓷感测元件的腔包含基准电极、施加在所述陶瓷感测元件的外层上的多孔铂电极、在所述陶瓷感测元件的上方紧密地固定在所述壳体的内部的密封引入端、穿过所述密封引入端的中央芯部的电势测量单元、和下套管，其中所述陶瓷感测元件被设计为筒形件，该筒形件与位于所述筒形件的下部部分的底部连接；所述陶瓷感测元件的筒形外表面与所述壳体的内侧面紧密连接；所述标准电极位于所述陶瓷感测元件的内腔中；所述陶瓷感测元件的底部的外部部分覆盖有多孔铂电极层；所述电势测量单元的中央芯部的端部伸出至所述标准电极，由此在所述标准电极与所述电势测量单元的中央芯部的下部部分之间提供电接触；被设计为管状件的所述下套管在所述陶瓷感测元件侧与所述壳体的下部部分连接；所述下套管的下端具有带中心孔的底部，所述带中心孔的底部附接有由至少一个管构成的选择性隔膜；所述选择性隔膜的下部自由端利用插塞紧闭；由所述下套管的内表面、所述陶瓷感测元件的底部的外部部分、以及所述选择性隔膜和所述插塞的内表面限定的腔借助于玻璃-陶瓷密封剂而被密封；所述检测器配备有用于加热并且保持操作元件的感测部的稳定工作温度的另外的隔热加热器。
2.根据权利要求1所述的检测器，其中，氧传感器附加地配备有具有恒定的水蒸气压力的隔室和防水隔膜以更有效地测量气体介质中的氢浓度。
3.根据权利要求1所述的检测器，其中，在所述电势测量单元的上部部分中安装有上部螺母，并且在螺母壁的内表面与所述电势测量单元的外表面之间的环形腔内填充有密封剂。
4.根据权利要求1所述的检测器，其中，所述检测器的包括镍外壳和由薄壁式镍管制成的薄壁式防水隔膜的蒸汽氢隔室焊接在由耐腐蚀钢制成的感测元件外壳上。
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| EP3236250A1 (en) | 2017-10-25 |
| JP2018503081A (ja) | 2018-02-01 |
| BR112017013045B1 (pt) | 2021-03-30 |
| KR20170102494A (ko) | 2017-09-11 |
| JP6777633B2 (ja) | 2020-10-28 |
| KR102278286B1 (ko) | 2021-07-20 |
| CA2971160A1 (en) | 2016-06-23 |
| RU2014150467A (ru) | 2016-07-10 |
| WO2016099330A1 (ru) | 2016-06-23 |
| EP3236250A4 (en) | 2018-06-20 |
| BR112017013045A2 (pt) | 2018-01-02 |
| MY195048A (en) | 2023-01-04 |
| EA032157B1 (ru) | 2019-04-30 |
| US20170322175A1 (en) | 2017-11-09 |
| RU2602757C2 (ru) | 2016-11-20 |
| EA201650104A1 (ru) | 2017-07-31 |
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