CN110873741A - Three-parameter intelligent compensation correction electrochemical online dissolved oxygen sensor - Google Patents
Three-parameter intelligent compensation correction electrochemical online dissolved oxygen sensor Download PDFInfo
- Publication number
- CN110873741A CN110873741A CN201810991820.XA CN201810991820A CN110873741A CN 110873741 A CN110873741 A CN 110873741A CN 201810991820 A CN201810991820 A CN 201810991820A CN 110873741 A CN110873741 A CN 110873741A
- Authority
- CN
- China
- Prior art keywords
- electrode
- dissolved oxygen
- sensor
- conductivity
- circuit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 101
- 239000001301 oxygen Substances 0.000 title claims abstract description 101
- 238000012937 correction Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000001514 detection method Methods 0.000 claims abstract description 37
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052709 silver Inorganic materials 0.000 claims abstract description 17
- 239000004332 silver Substances 0.000 claims abstract description 17
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052737 gold Inorganic materials 0.000 claims abstract description 15
- 239000010931 gold Substances 0.000 claims abstract description 15
- 239000012528 membrane Substances 0.000 claims abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 238000004891 communication Methods 0.000 claims abstract description 6
- 230000010287 polarization Effects 0.000 claims abstract description 6
- 238000005259 measurement Methods 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 2
- 235000012149 noodles Nutrition 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000003759 clinical diagnosis Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007954 hypoxia Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- GNLCAVBZUNZENF-UHFFFAOYSA-N platinum silver Chemical compound [Ag].[Ag].[Ag].[Pt] GNLCAVBZUNZENF-UHFFFAOYSA-N 0.000 description 1
- 238000012372 quality testing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
Description
技术领域technical field
本发明涉及溶解氧含量检测领域，具体涉及一种三参数智能补偿校正电化学在线溶解氧传感器。The invention relates to the field of dissolved oxygen content detection, in particular to a three-parameter intelligent compensation correction electrochemical on-line dissolved oxygen sensor.
背景技术Background technique
溶解氧是指溶解于液态水中的分子态氧，是作为水体污染及水质优劣评定一个关键指标,是水质检测、污水处理、食品发酵、水产和临床诊断等领域的一个关键指标。一般饮用水溶解氧浓度不低于6mg/L。当生态系统中溶解氧浓度低于4mg/L时，鱼类将缺氧窒息死亡。在食品发酵领域，控制溶解氧浓度是确保微生物生长和重要考虑因素。在临床诊断领域，可以通过掌握细胞中溶解氧浓度来了解细胞和组织的代谢状态，从而诊断疾病。在污水处理领域，对溶解氧进行检测可以提高污水处理的效率，降低运行成本。在火电发电、核动力发电等领域，对高温锅炉供给水的溶解氧浓度检测可以提高工厂运作效率和安全性，有效地预防潜在事故的发生。Dissolved oxygen refers to the molecular oxygen dissolved in liquid water. It is a key indicator in the evaluation of water pollution and water quality. It is also a key indicator in the fields of water quality testing, sewage treatment, food fermentation, aquatic products and clinical diagnosis. In general, the dissolved oxygen concentration in drinking water is not less than 6 mg/L. When the dissolved oxygen concentration in the ecosystem is lower than 4mg/L, fish will suffocate and die due to hypoxia. In the field of food fermentation, controlling dissolved oxygen concentration is an important consideration to ensure microbial growth. In the field of clinical diagnosis, the metabolic state of cells and tissues can be understood by grasping the dissolved oxygen concentration in cells, thereby diagnosing diseases. In the field of sewage treatment, the detection of dissolved oxygen can improve the efficiency of sewage treatment and reduce operating costs. In the fields of thermal power generation, nuclear power generation and other fields, the detection of dissolved oxygen concentration in the supply water of high-temperature boilers can improve the efficiency and safety of plant operation, and effectively prevent the occurrence of potential accidents.
现有的电化学溶解氧电极大都存在以下技术问题：（1）检测前对传感器的标定需要人手动操作，无法自行标定。（2）检测过程中受环境参数的影响巨大，无法对环境参数的变化进行实时补偿校准。（3）抗干扰能力差，检测数据不准确。（4）工作电极结构设计不合理导致传感器响应速度、精度、稳定性差。Most of the existing electrochemical dissolved oxygen electrodes have the following technical problems: (1) The calibration of the sensor before detection requires manual operation, and cannot be calibrated by itself. (2) The detection process is greatly affected by environmental parameters, and real-time compensation and calibration cannot be performed for changes in environmental parameters. (3) The anti-interference ability is poor, and the detection data is inaccurate. (4) The unreasonable structural design of the working electrode leads to poor response speed, accuracy and stability of the sensor.
发明内容SUMMARY OF THE INVENTION
针对目前电化学溶氧传感检测技术中所存在的问题，本发明的目的是提供一种三参数智能补偿校正电化学在线溶解氧传感器，此电化学溶解氧传感器检测前能够自动检测影响溶解氧检测的三个主要环境参数的数值，并在检测前对传感器进行温度参数、电导率参数、大气压力参数以及溶解氧电极测量曲线的标定，使得电化学溶解氧传感器能够快速准确的测出溶解氧的浓度值，此外，电化学溶解氧传感器检测过程中能够对影响溶解氧检测的三个主要环境参数进行实时补偿，大大的提高了溶解氧传感器的抗干扰能力，使得检测数据更加准确。In view of the problems existing in the current electrochemical dissolved oxygen sensing and detection technology, the purpose of the present invention is to provide a three-parameter intelligent compensation and correction electrochemical on-line dissolved oxygen sensor, which can automatically detect the influence of dissolved oxygen before detection. The values of the three main environmental parameters detected, and the temperature parameters, conductivity parameters, atmospheric pressure parameters and dissolved oxygen electrode measurement curves of the sensor are calibrated before the detection, so that the electrochemical dissolved oxygen sensor can quickly and accurately measure dissolved oxygen. In addition, the electrochemical dissolved oxygen sensor can perform real-time compensation for the three main environmental parameters affecting dissolved oxygen detection during the detection process, which greatly improves the anti-interference ability of the dissolved oxygen sensor and makes the detection data more accurate.
为达到以上目的，本发明采用的技术方案是：一种三参数智能补偿校正电化学在线溶解氧传感器，包括溶解氧电极、电导率传感器、大气压力传感器、温度电极、被测水样流通池、传感器支架及检测电路单元，所述溶解氧电极包括传感器的圆柱外壳、透氧膜、膜盖、作为工作电极的金电极、作为辅助电极的银电极、作为银保护电极的铂电极、液态反应电解液、电极基座及绝缘导线；所述电导率传感器包括电导率检测单元和电导率信号导线；所述传感器支架上有溶解氧电极支架孔、电导率传感器支架孔、温度电极支架孔；所述溶解氧电极、电导率传感器、大气压力传感器、温度电极分别通过绝缘导线、电导率信号线、大气压力传感器信号线、温度电极信号线连接在测量电路单元上；所述被测水样流通池上设置有进水口、调节阀、喷嘴、流量计、排水口，其特征在于：所述溶解氧电极、电导率传感器和温度电极通过传感器支架上的支架孔接入到被测水样流通池中，所述大气压力传感器置于与被测水样流通池相同的大气环境中。In order to achieve the above purpose, the technical scheme adopted in the present invention is: a three-parameter intelligent compensation and correction electrochemical on-line dissolved oxygen sensor, comprising a dissolved oxygen electrode, a conductivity sensor, an atmospheric pressure sensor, a temperature electrode, a flow cell for the water sample to be measured, A sensor bracket and a detection circuit unit, the dissolved oxygen electrode includes a cylindrical shell of the sensor, an oxygen-permeable membrane, a membrane cover, a gold electrode as a working electrode, a silver electrode as an auxiliary electrode, a platinum electrode as a silver protection electrode, and a liquid reaction electrolysis liquid, an electrode base and an insulated wire; the conductivity sensor includes a conductivity detection unit and a conductivity signal wire; the sensor support is provided with dissolved oxygen electrode support holes, conductivity sensor support holes, and temperature electrode support holes; the The dissolved oxygen electrode, the conductivity sensor, the atmospheric pressure sensor and the temperature electrode are respectively connected to the measurement circuit unit through the insulated wire, the conductivity signal wire, the atmospheric pressure sensor signal wire and the temperature electrode signal wire; the measured water sample flow cell is provided with There are water inlets, regulating valves, nozzles, flow meters, and water outlets, and it is characterized in that: the dissolved oxygen electrode, conductivity sensor and temperature electrode are connected to the measured water sample flow cell through the bracket hole on the sensor bracket, so The atmospheric pressure sensor is placed in the same atmospheric environment as the water sample flow cell to be tested.
进一步，所述检测电路单元包括溶解氧电极极化电路、电流转电压电路、电压放大电路、滤波电路、温度补偿电路、电导率补偿电路、大气压力补偿电路、AD转换电路、STM32F103ZET6微控制器、串口通讯电路、液晶显示电路、存储单元、继电器控制电路。Further, the detection circuit unit includes a dissolved oxygen electrode polarization circuit, a current-to-voltage circuit, a voltage amplifier circuit, a filter circuit, a temperature compensation circuit, a conductivity compensation circuit, an atmospheric pressure compensation circuit, an AD conversion circuit, an STM32F103ZET6 microcontroller, Serial communication circuit, liquid crystal display circuit, storage unit, relay control circuit.
进一步，所述的温度电极不仅通过温度补偿电路对溶解氧电极的测定值进行补偿标定，同时也对电导率传感器的测定值进行补偿标定。Further, the temperature electrode not only compensates and calibrates the measured value of the dissolved oxygen electrode through the temperature compensation circuit, but also compensates and calibrates the measured value of the conductivity sensor.
进一步，所述喷嘴正对溶解氧电极下端，且能将被测水样直喷向透氧膜。Further, the nozzle is facing the lower end of the dissolved oxygen electrode, and can directly spray the water sample to be measured towards the oxygen permeable membrane.
更进一步，所述金电极为帽状金质圆柱体，且下端为纳米多孔结构的凸起弧面。Further, the gold electrode is a cap-shaped gold cylinder, and the lower end is a convex arc surface of a nanoporous structure.
由于上述技术方案运用，本发明与现有技术相比具有下列优点和效果：Due to the application of the above-mentioned technical solutions, the present invention has the following advantages and effects compared with the prior art:
1、本发明三参数智能补偿校正电化学在线溶解氧传感器，基于作为工作电极的金电极、作为辅助电极的银电极、作为银保护电极的铂电极组合成三电极检测系统，透氧膜将被测水样与电解液隔离开，当在金电极和银电极之间提供一个0.6V-0.8V之间的恒定电压时，金电极和银电极之间将会产生一个扩散电流，扩散电流的大小与被测水样中的溶解氧浓度成正比，通过测量扩散电流大小便可知溶解氧浓度大小。由于本发明采用三参数（温度、电导率、大气压力）补偿标定方法，能够在检测前提高溶解氧传感器的标定效率及准确度，能够在检测过程中对影响溶解氧浓度检测的主要参数进行实时补偿，大大的提高了溶解氧传感器的抗干扰能力，使得检测数据更加准确。1. The three-parameter intelligent compensation and correction electrochemical on-line dissolved oxygen sensor of the present invention is based on the combination of the gold electrode as the working electrode, the silver electrode as the auxiliary electrode, and the platinum electrode as the silver protection electrode to form a three-electrode detection system. The water sample is isolated from the electrolyte. When a constant voltage between 0.6V-0.8V is provided between the gold electrode and the silver electrode, a diffusion current will be generated between the gold electrode and the silver electrode. The size of the diffusion current It is proportional to the dissolved oxygen concentration in the measured water sample, and the dissolved oxygen concentration can be known by measuring the diffusion current. Because the invention adopts the three-parameter (temperature, conductivity, atmospheric pressure) compensation calibration method, the calibration efficiency and accuracy of the dissolved oxygen sensor can be improved before detection, and the main parameters affecting the detection of dissolved oxygen concentration can be measured in real time during the detection process. Compensation greatly improves the anti-interference ability of the dissolved oxygen sensor, making the detection data more accurate.
2、由于本发明采用的检测电路单元包括溶解氧电极极化电路、电流转电压电路、电压放大电路、滤波电路、温度补偿电路、电导率补偿电路、大气压力补偿电路、AD转换电路、STM32F103ZET6微控制器、串口通讯电路、液晶显示电路、存储单元、继电器控制电路，使得检测信号更加准确，且能实时显示在液晶显示屏上，所有数据都存储在一个非易失存储器中，在断电后数据也不会丢失，串口通讯电路能够使得传感器能够下载数据到计算机中。2. Because the detection circuit unit used in the present invention includes dissolved oxygen electrode polarization circuit, current-to-voltage circuit, voltage amplifier circuit, filter circuit, temperature compensation circuit, conductivity compensation circuit, atmospheric pressure compensation circuit, AD conversion circuit, STM32F103ZET6 micro The controller, serial communication circuit, liquid crystal display circuit, storage unit, and relay control circuit make the detection signal more accurate, and can be displayed on the liquid crystal display in real time. All data are stored in a non-volatile memory. The data will not be lost, and the serial communication circuit enables the sensor to download the data to the computer.
3、由于本发明采用的温度电极不仅通过温度补偿电路对溶解氧电极的测定值进行补偿标定，同时也对电导率传感器的测定值进行补偿标定，提高了电导率的检测精度，同时也提高了溶解氧电导率补偿的准确性。3. Because the temperature electrode used in the present invention not only compensates and calibrates the measured value of the dissolved oxygen electrode through the temperature compensation circuit, but also compensates and calibrates the measured value of the conductivity sensor, which improves the detection accuracy of the conductivity and also improves the Accuracy of dissolved oxygen conductivity compensation.
4、由于本发明采用的被测水样流通池的底部有喷嘴设计，被测水样通过喷嘴来实现对溶解氧电极的氧透膜上的高流率，高流率可以极大的减少传感器的响应时间。4. Due to the nozzle design at the bottom of the flow cell of the tested water sample adopted in the present invention, the tested water sample passes through the nozzle to achieve a high flow rate on the oxygen permeable membrane of the dissolved oxygen electrode, and the high flow rate can greatly reduce the sensor response time.
5、由于本发明采用的金电极是帽状金质圆柱体，且下端为纳米多孔结构的凸起弧面，增大了150倍工作电极与电解液的接触面积，提高了溶解氧传感器的响应速度和稳定性。5. Since the gold electrode used in the present invention is a cap-shaped gold cylinder, and the lower end is a convex arc surface of a nano-porous structure, the contact area between the working electrode and the electrolyte is increased by 150 times, and the response of the dissolved oxygen sensor is improved. speed and stability.
附图说明Description of drawings
图1是本发明溶解氧电极的拆分结构示意图。FIG. 1 is a schematic diagram of the disassembled structure of the dissolved oxygen electrode of the present invention.
图2是本发明测量电路单元结构示意图。FIG. 2 is a schematic diagram of the structure of the measuring circuit unit of the present invention.
图3是本发明大气压力传感器结构示意图。FIG. 3 is a schematic structural diagram of the atmospheric pressure sensor of the present invention.
图4是本发明传感器支架结构结构示意图。FIG. 4 is a schematic structural diagram of the sensor support structure of the present invention.
图5是本发明被测水样流通池工作结构示意图。FIG. 5 is a schematic diagram of the working structure of the flow cell of the tested water sample of the present invention.
图中：1、溶解氧电极；2、圆柱外壳；3、透氧膜；4、膜盖；5、金电极；6、银电极；7、铂电极；8、液态反应电解液；9、电极基座；10、溶解氧电极绝缘导线；11、电极极化电路；12、电流转电压电路；13、温度补偿电路；14、电导率补偿电路；15、大气压力补偿电路；16、滤波电路；17、电压放大电路；18、AD转换电路；19、STM32F103ZET6微控制器；20、存储单元；21、继电器控制电路；22、串口通讯电路；23、继电器控制电路；24、大气压力传感器；25、大气压力传感器信号线；26、传感器支架；27、溶解氧电极支架孔；28、电导率传感器支架孔；29、温度电极支架孔；30、电导率传感器；31、电导率检测单元；32、电导率信号线；33、温度电极；34、温度电极信号线；35、被测水样流通池；36、进水口；37、调节阀；38、喷嘴；39、流量计；40、出水口。In the figure: 1. Dissolved oxygen electrode; 2. Cylindrical shell; 3. Oxygen permeable membrane; 4. Membrane cover; 5. Gold electrode; 6. Silver electrode; 7. Platinum electrode; 8. Liquid reaction electrolyte; 9. Electrode Base; 10, dissolved oxygen electrode insulated wire; 11, electrode polarization circuit; 12, current to voltage circuit; 13, temperature compensation circuit; 14, conductivity compensation circuit; 15, atmospheric pressure compensation circuit; 16, filter circuit; 17, voltage amplifier circuit; 18, AD conversion circuit; 19, STM32F103ZET6 microcontroller; 20, storage unit; 21, relay control circuit; 22, serial communication circuit; 23, relay control circuit; 24, atmospheric pressure sensor; 25, Atmospheric pressure sensor signal line; 26, sensor bracket; 27, dissolved oxygen electrode bracket hole; 28, conductivity sensor bracket hole; 29, temperature electrode bracket hole; 30, conductivity sensor; 31, conductivity detection unit; 32, conductivity rate signal line; 33, temperature electrode; 34, temperature electrode signal line; 35, tested water sample flow cell; 36, water inlet; 37, regulating valve; 38, nozzle; 39, flow meter; 40, water outlet.
具体实施方式Detailed ways
下面结合附图和具体实施方式对本发明作进一步描述。The present invention will be further described below with reference to the accompanying drawings and specific embodiments.
实施例：提供一种三参数智能补偿校正电化学在线溶解氧传感器，包括溶解氧电极1、电导率传感器30、大气压力传感器24、温度电极33、被测水样流通池35、传感器支架26及检测电路单元，所述溶解氧电极包括传感器的圆柱外壳2、透氧膜3、膜盖4、作为工作电极的金电极5、作为辅助电极的银电极6、作为银保护电极的铂电极7、液态反应电解液8、电极基座9及绝缘导线10；所述电导率传感器30包括电导率检测单元31和电导率信号导线32；所述传感器支架26上有溶解氧电极支架孔27、电导率传感器支架孔28、温度电极支架孔29；所述溶解氧电极1、电导率传感器30、大气压力传感器24、温度电极33分别通过绝缘导线10、电导率信号线32、大气压力传感器信号线25、温度电极信号线34连接在测量电路单元上；所述被测水样流通池35上设置有进水口36、调节阀37、喷嘴38、流量计39、排水口40，其特征在于：所述溶解氧电极1、电导率传感器30和温度电极33通过传感器支架26上的支架孔接入到被测水样流通池35中，所述大气压力传感器24置于与被测水样流通池35相同的大气环境中。Embodiment: Provide a three-parameter intelligent compensation correction electrochemical on-line dissolved oxygen sensor, including dissolved
本发明的工作原理：The working principle of the present invention:
本发明的电化学溶解氧电极基于Clark电极法，由工作电极（金质阴极）和辅助电极（银质阳极）及银保护电极（铂质保护电极）组成，工作电极、辅助电极和银保护电极完全浸没在液态反应电解液中，当工作电极和辅助电极之间加上0.6-0.8V的极化电压时，被测水样中的氧分子会通过透氧膜，持续的扩散到液态反应电解液中，并在工作电极上被还原，同时工作电极与辅助电极间之间产生一个稳定的扩散电流。扩散电流的大小与工作电极表面反应的氧分子浓度成正比。通过测量扩散电流的大小便可知被测水样中的溶解浓度。此外，铂质银保护电极与辅助电极之间加上-0.6V的保护电压，这样在测量过程中银保护电极能保证银电极不被消耗，电解液中的电解质不被消耗，被测水样中的氧气不被消耗，提高了传感器的使用寿命，减小了传感器的测量误差、节省了经常更换电解液的人力成本。本发明提供的三参数智能补偿校正电化学在线溶解氧传感器测量过程中，液态反应电解液总反应过程的化学方程式如下：The electrochemical dissolved oxygen electrode of the present invention is based on the Clark electrode method, and is composed of a working electrode (gold cathode), an auxiliary electrode (silver anode) and a silver protection electrode (platinum protection electrode). Fully immersed in the liquid reaction electrolyte, when a polarization voltage of 0.6-0.8V is applied between the working electrode and the auxiliary electrode, the oxygen molecules in the measured water sample will pass through the oxygen permeable membrane and continue to diffuse into the liquid reaction electrolyte. It is reduced on the working electrode, and a stable diffusion current is generated between the working electrode and the auxiliary electrode. The magnitude of the diffusion current is proportional to the concentration of oxygen molecules reacted on the surface of the working electrode. The dissolved concentration in the measured water sample can be known by measuring the size of the diffusion current. In addition, a protective voltage of -0.6V is added between the platinum silver protective electrode and the auxiliary electrode, so that the silver protective electrode can ensure that the silver electrode is not consumed during the measurement process, and the electrolyte in the electrolyte is not consumed. The oxygen is not consumed, the service life of the sensor is improved, the measurement error of the sensor is reduced, and the labor cost of frequently replacing the electrolyte is saved. In the measurement process of the three-parameter intelligent compensation correction electrochemical on-line dissolved oxygen sensor provided by the present invention, the chemical equation of the total reaction process of the liquid reaction electrolyte is as follows:
工作电极-辅助电极：O2+2H2O+4eˉ→4OHˉWorking electrode-auxiliary electrode: O 2 +2H 2 O+4eˉ→4OHˉ
4Ag+4Clˉ→4AgCl+4eˉ4Ag+4Clˉ→4AgCl+4eˉ
银保护电极-辅助电极：4OHˉ+4eˉ→O2+2H2OSilver protective electrode - auxiliary electrode: 4OHˉ+4eˉ→O 2 +2H 2 O
4AgCl+4eˉ→4Ag+4Clˉ4AgCl+4eˉ→4Ag+4Clˉ
工作电极和辅助电极之间由于电荷的移动，产生了nA级的电流，电化学溶解氧传感器通过检测电流的大小从而检测溶解氧浓度。Due to the movement of charges between the working electrode and the auxiliary electrode, a current of nA level is generated, and the electrochemical dissolved oxygen sensor detects the dissolved oxygen concentration by detecting the magnitude of the current.
本发明的补偿原理：The compensation principle of the present invention:
1、对溶解氧电极的温度补偿方法1. Temperature compensation method for dissolved oxygen electrode
温度对溶解氧浓度的检测的影响主要表现在：（1）温度对溶解氧电极输出电流的影响；（2）温度对饱和溶解氧含量的影响。The influence of temperature on the detection of dissolved oxygen concentration is mainly manifested in: (1) the effect of temperature on the output current of the dissolved oxygen electrode; (2) the effect of temperature on the saturated dissolved oxygen content.
根据阿伦尼乌斯定律(Arrhenius law),溶解氧电极的输出扩散电流I与电极工作温度T的关系为：According to the Arrhenius law, the relationship between the output diffusion current I of the dissolved oxygen electrode and the electrode operating temperature T is:
式中，A和β是两个常数，它们与电极的材料和结构有关；I0是被测水样氧分压为零的时候的电极响应电流；PO2是被测水样中的氧分压。In the formula, A and β are two constants, which are related to the material and structure of the electrode; I 0 is the electrode response current when the oxygen partial pressure of the measured water sample is zero; P O2 is the oxygen content in the measured water sample. pressure.
2、对溶解氧电极的大气压力补偿方法2. Atmospheric pressure compensation method for dissolved oxygen electrode
由于溶解氧电极测量的是液态中氧分压的含量，所以当大气压力变化时，溶液中溶解氧的含量也会发生变化，最终影响到检测的准确性，所以需要对溶解氧电极进行大气压力的补偿修正。补偿公式为：Since the dissolved oxygen electrode measures the content of oxygen partial pressure in the liquid state, when the atmospheric pressure changes, the dissolved oxygen content in the solution will also change, which will ultimately affect the detection accuracy. compensation correction. The compensation formula is:
式中：CS1为实测大气压力下饱和溶解氧的值，单位为mg/L；CS为标准大气压下饱和溶解氧的值，单位为mg/L；P为实测大气压力值，单位为kPa；PW为实测条件下与空气接触时水蒸气的压力值，单位为kPa。In the formula: C S1 is the value of saturated dissolved oxygen under the measured atmospheric pressure, the unit is mg/L; C S is the value of the saturated dissolved oxygen under the standard atmospheric pressure, the unit is mg/L; P is the measured atmospheric pressure value, the unit is kPa ; P W is the pressure value of water vapor when it is in contact with air under the measured conditions, and the unit is kPa.
3、对溶解氧电极盐度补偿方法3. Compensation method for dissolved oxygen electrode salinity
氧气在水中的溶解度会随着含盐量的增加而减少，在实际应用中，当水中含盐量小于35g/L时，可认为氧气在水中的溶解度和水中的含盐量呈线性关系。其补偿公式为：The solubility of oxygen in water will decrease with the increase of salt content. In practical applications, when the salt content in water is less than 35g/L, it can be considered that the solubility of oxygen in water and the salt content in water have a linear relationship. Its compensation formula is:
式中：C为被测水样实际饱和溶解氧的值，单位为mg/L；CS2为去离子水中饱和溶解氧的值，单位为mg/L；n为被测水样的盐度值，单位为g/L，此值的大小与被测水样的电导率有关；△CS为1g/L的含盐量的变化造成的溶解氧含量的变化值，单位为mg/L。In the formula: C is the actual saturated dissolved oxygen value of the tested water sample, the unit is mg/L; C S2 is the saturated dissolved oxygen value of the deionized water, the unit is mg/L; n is the salinity value of the tested water sample , the unit is g/L, the size of this value is related to the conductivity of the water sample to be tested; ΔC S is the change value of dissolved oxygen content caused by the change of 1g/L salt content, the unit is mg/L.
本发明所述的装置并不限于具体实施方式中所述的实施例，本领域技术人员根据本发明的技术方案得出其他的实施方式，同样属于本发明的技术创新范围。The device described in the present invention is not limited to the embodiments described in the specific embodiments, and those skilled in the art can obtain other embodiments according to the technical solutions of the present invention, which also belong to the technical innovation scope of the present invention.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810991820.XA CN110873741A (en) | 2018-08-29 | 2018-08-29 | Three-parameter intelligent compensation correction electrochemical online dissolved oxygen sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810991820.XA CN110873741A (en) | 2018-08-29 | 2018-08-29 | Three-parameter intelligent compensation correction electrochemical online dissolved oxygen sensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110873741A true CN110873741A (en) | 2020-03-10 |
Family
ID=69714203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810991820.XA Pending CN110873741A (en) | 2018-08-29 | 2018-08-29 | Three-parameter intelligent compensation correction electrochemical online dissolved oxygen sensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110873741A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019100939A (en) * | 2017-12-06 | 2019-06-24 | 日本電信電話株式会社 | Hydrogen permeation amount measuring method, hydrogen permeation amount measuring device, and hydrogen permeation amount measuring program |
| CN113030211A (en) * | 2021-03-10 | 2021-06-25 | 广东海洋大学 | Polarographic dissolved oxygen meter and dissolved oxygen measurement compensation method |
| CN113866362A (en) * | 2021-09-28 | 2021-12-31 | 明石创新(烟台)微纳传感技术研究院有限公司 | Intelligent efficient accurate oxygen measuring instrument calibration and compensation method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101398405A (en) * | 2008-11-04 | 2009-04-01 | 中国农业大学 | Water electric conductivity intelligent sensor |
| CN101408526A (en) * | 2008-11-14 | 2009-04-15 | 西安建筑科技大学 | Dissolved oxygen micro electrode and preparing method thereof |
| CN101533031A (en) * | 2009-04-15 | 2009-09-16 | 中国农业大学 | Dissolved oxygen intelligent transducer |
| US20120125790A1 (en) * | 2009-08-04 | 2012-05-24 | Heinz Wohlrab | Electrochemical sensor for measuring the oxygen partial pressure in a process fluid and a method for testing its function |
| CN104807862A (en) * | 2015-04-20 | 2015-07-29 | 中国农业大学 | Method and device for detecting dissolved oxygen in water |
| US20150308975A1 (en) * | 2012-11-29 | 2015-10-29 | Horiba Advanced Techno Co., Ltd. | Measuring device |
| CN106645330A (en) * | 2016-11-29 | 2017-05-10 | 福州微启迪物联科技有限公司 | Portable NB-IoT water quality detecting device and parameter correcting method thereof |
-
2018
- 2018-08-29 CN CN201810991820.XA patent/CN110873741A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101398405A (en) * | 2008-11-04 | 2009-04-01 | 中国农业大学 | Water electric conductivity intelligent sensor |
| CN101408526A (en) * | 2008-11-14 | 2009-04-15 | 西安建筑科技大学 | Dissolved oxygen micro electrode and preparing method thereof |
| CN101533031A (en) * | 2009-04-15 | 2009-09-16 | 中国农业大学 | Dissolved oxygen intelligent transducer |
| US20120125790A1 (en) * | 2009-08-04 | 2012-05-24 | Heinz Wohlrab | Electrochemical sensor for measuring the oxygen partial pressure in a process fluid and a method for testing its function |
| US20150308975A1 (en) * | 2012-11-29 | 2015-10-29 | Horiba Advanced Techno Co., Ltd. | Measuring device |
| CN104807862A (en) * | 2015-04-20 | 2015-07-29 | 中国农业大学 | Method and device for detecting dissolved oxygen in water |
| CN106645330A (en) * | 2016-11-29 | 2017-05-10 | 福州微启迪物联科技有限公司 | Portable NB-IoT water quality detecting device and parameter correcting method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 丁启胜等: "溶解氧智能传感器补偿校正方法研究与应用", 《山东农业大学学报(自然科学版)》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019100939A (en) * | 2017-12-06 | 2019-06-24 | 日本電信電話株式会社 | Hydrogen permeation amount measuring method, hydrogen permeation amount measuring device, and hydrogen permeation amount measuring program |
| CN113030211A (en) * | 2021-03-10 | 2021-06-25 | 广东海洋大学 | Polarographic dissolved oxygen meter and dissolved oxygen measurement compensation method |
| CN113866362A (en) * | 2021-09-28 | 2021-12-31 | 明石创新(烟台)微纳传感技术研究院有限公司 | Intelligent efficient accurate oxygen measuring instrument calibration and compensation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110873741A (en) | Three-parameter intelligent compensation correction electrochemical online dissolved oxygen sensor | |
| CN109142491A (en) | Water quality monitoring method based on continuous flow without film biological-cathode microbiological fuel cell | |
| CN109001275B (en) | A three-electrode electrochemical dissolved oxygen sensor | |
| CN113466423A (en) | Dissolved oxygen meter calibration test system and method | |
| CN108061745A (en) | A kind of method for surveying feed solution system oxidation-reduction potential using current-vs-time and open circuit potential combined techniques | |
| CN105181774B (en) | A kind of dissolved oxygen concentration measurement apparatus and method | |
| JPS638423B2 (en) | ||
| CN110057895B (en) | Method for optimizing polarization parameters of two-electrode Clark type trace dissolved oxygen sensor | |
| CN109406614A (en) | Hand-held oxygen detection instrument and its working method | |
| US2585811A (en) | Electrochemical method of automatically determining available chlorine in an aqueous liquid | |
| US8382974B2 (en) | Sensor to measure a concentration of alkali alcoholate | |
| CN216816536U (en) | Water quality residual chlorine sensor | |
| RU223971U1 (en) | Flow-through potentiometric cell for measuring chloride ion concentrations in high-purity aqueous media | |
| CN202956358U (en) | PH detector | |
| CN103105472B (en) | Method and system for detecting dissolved hydrogen in water | |
| CN205449876U (en) | Oxygen current measurement circuit and dissolved oxygen measuring apparatu | |
| JP4406792B2 (en) | Biosensor calibration method | |
| CN109307704A (en) | Hand-held dissolved oxygen analytic instrument and working method | |
| CN217505724U (en) | Dissolved oxygen test pen with from stirring function | |
| CN211978799U (en) | A titration cell for pH potentiometric titration | |
| CN201477068U (en) | Salt electrolysis cell | |
| Chen et al. | Study on Polarization Parameters of Micro Dissolved Oxygen Sensor | |
| CN104730131B (en) | A kind of pH measuring methods and device | |
| JP2004125668A (en) | Oxidation-reduction potential measuring instrument | |
| CA2772706A1 (en) | Water analysis measurement arrangement |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200310 |
|
| WD01 | Invention patent application deemed withdrawn after publication |