CN108663347B - Multi-parameter interference compensation correction system and method for optical dissolved oxygen sensor - Google Patents
Multi-parameter interference compensation correction system and method for optical dissolved oxygen sensor Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 252
- 239000001301 oxygen Substances 0.000 title claims abstract description 252
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 252
- 238000012937 correction Methods 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 53
- 230000003287 optical effect Effects 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 121
- 230000007613 environmental effect Effects 0.000 claims abstract description 48
- 239000007789 gas Substances 0.000 claims abstract description 37
- 238000005070 sampling Methods 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 230000008859 change Effects 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000000523 sample Substances 0.000 claims description 9
- 238000004364 calculation method Methods 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 238000004445 quantitative analysis Methods 0.000 claims 1
- 238000012625 in-situ measurement Methods 0.000 abstract description 4
- 230000036760 body temperature Effects 0.000 abstract description 3
- 238000012544 monitoring process Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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Abstract
本发明属于溶解氧传感器补偿标定技术领域，公开了光学溶解氧传感器多参数干扰补偿校正系统，包括校正池、与校正池连接的水密插接件、气体通入装置、待校正溶解氧传感器、参比溶解氧传感器、取样装置、盐度调节装置和压力调节装置，盐度调节装置和压力调节装置设置在水密插接件上。本技术方案在不同的水体温度、盐度和环境压力条件下，依次将不同氧含量的混合气体通入校正池，使水体获得多个溶解氧浓度，记录待校正溶解氧传感器的相位值和水体的环境参数，并取水样以碘量法测定溶解氧标准值计算待校正溶解氧传感器的多参数干扰补偿校正系数，自动化程度提高，提高传感器标定精度、校正精度、原位测量准确度，使传感器具有更广泛的适用范围。
The invention belongs to the technical field of compensation and calibration of dissolved oxygen sensors. It discloses a multi-parameter interference compensation and correction system for optical dissolved oxygen sensors, which includes a correction tank, a watertight plug-in connector connected to the correction tank, a gas inlet device, a dissolved oxygen sensor to be corrected, and parameters. The specific dissolved oxygen sensor, sampling device, salinity adjustment device and pressure adjustment device are arranged on the watertight plug connector. This technical solution sequentially passes mixed gases with different oxygen contents into the calibration pool under different water body temperature, salinity and environmental pressure conditions, so that the water body can obtain multiple dissolved oxygen concentrations, and record the phase value of the dissolved oxygen sensor to be calibrated and the water body Environmental parameters, and take water samples to measure the standard value of dissolved oxygen using the iodometric method to calculate the multi-parameter interference compensation correction coefficient of the dissolved oxygen sensor to be calibrated. The degree of automation is improved, and the sensor calibration accuracy, calibration accuracy, and in-situ measurement accuracy are improved, so that Sensors have a wider range of applications.
Description
技术领域Technical field
本发明属于溶解氧传感器补偿标定技术领域，公开了一种光学溶解氧传感器高精度复杂多参数环境因子干扰补偿校正方法及校正系统。The invention belongs to the technical field of compensation and calibration of dissolved oxygen sensors, and discloses a high-precision, complex, multi-parameter environmental factor interference compensation and correction method and correction system for an optical dissolved oxygen sensor.
背景技术Background technique
溶解氧作为海洋生态环境的一个重要组成和控制参数，是衡量海水水质优劣、水体被污染程度的重要指标，也是水体自净能力研究、海洋生态环境评估和海洋科学实验的重要依据。所以，原位、快速、准确、稳定、简捷的检测海水中溶解氧的浓度对于海洋生态环境监测、生态灾害的预警、海洋牧场的良性发展具有重要的价值。目前，溶解氧Winkler分析方法程序繁琐，耗时耗力，更重要的是，这种非实时，断续的检测模式很难对海洋溶解氧进行有效的实时连续检测。而电化学溶解氧传感器需参比电极，且需对被测溶液进行恒速搅拌，以保证水中溶解氧通过电极膜的速率；精度不高，抗干扰能力差，易受电磁场干扰而引起信号漂移，因此电化学溶解氧传感器在海洋溶解氧原位监测方面的应用受到了很大的限制。As an important component and control parameter of the marine ecological environment, dissolved oxygen is an important indicator to measure the quality of seawater and the degree of water pollution. It is also an important basis for research on the self-purification capacity of water bodies, marine ecological environment assessment and marine scientific experiments. Therefore, in-situ, fast, accurate, stable and simple detection of dissolved oxygen concentration in seawater is of great value for marine ecological environment monitoring, ecological disaster early warning, and the healthy development of marine ranches. Currently, the Winkler analysis method for dissolved oxygen is cumbersome, time-consuming and labor-intensive. More importantly, this non-real-time, intermittent detection mode makes it difficult to effectively detect marine dissolved oxygen in real-time and continuously. The electrochemical dissolved oxygen sensor requires a reference electrode, and the measured solution needs to be stirred at a constant speed to ensure the rate at which dissolved oxygen in the water passes through the electrode membrane; the accuracy is not high, the anti-interference ability is poor, and it is susceptible to electromagnetic field interference, causing signal drift. , so the application of electrochemical dissolved oxygen sensors in in-situ monitoring of marine dissolved oxygen has been greatly limited.
基于荧光猝灭原理的光学溶解氧传感器克服了传统溶解氧测量上的不足，具有测量精确、快速、高选择性、高稳定性、抗电磁干扰性和可远程监控等优点，可实现溶解氧的原位连续检测，已广泛应用于海洋生态环境监测、水产养殖水质的监测等领域。虽然光学溶解氧传感器相比于电化学溶解氧传感器具有更高的稳定性和测量精度，但是其在长期原位监测的过程中，由于温度、盐度、深度等复杂多参数环境因子的影响，会产生数据漂移的问题，需要对溶解氧传感器的测量数据进行环境因子补偿校正。但是目前使用的补偿校正方法普遍存在校正值不够精确、校正周期长，校正结果不能在较大溶解氧浓度与标准值保持高度一致等缺点，主要的是目前的校正方法只针对温度对溶解氧传感器的数据干扰进行了补偿校正，而忽略了盐度和环境压力对于传感器影响的干扰补偿校正。传统的光学溶解氧传感器温度补偿校正方法为两点校正法，即无氧水和饱和溶氧水校正，该方法通过测量溶解氧传感器在无氧水(加入过量亚硫酸钠和少量二价钴盐溶液)以及饱和溶氧水(空气连续鼓泡法)中溶解氧传感器的相位值，将其与该温度下水中溶解氧理论计算值进行两点线性拟合，从而校正溶解氧传感器，但是该方法具有准确度不高的显著缺陷。而且传统的校正方法往往只考虑到了温度对传感器测量数据的影响，对盐度，尤其是环境压力的干扰没有进行补偿校正，严重影响传感器原位测量环境复杂近岸海域和高盐差、高浊度大型河口海域溶解氧的准确度，对溶解氧的剖面测量也存在较大的误差。为促进光学溶解氧传感器的应用和发展，提升我国溶解氧的业务化监测能力、海洋溶解氧原位监测的数据质量、促进溶解氧传感器的应用和发展，为我国光学溶解氧传感器的计量标定工作提供方法依据。因此，提出一种光学溶解氧传感器复杂多参数环境因子干扰补偿高精度校正系统和校正方法是很有必要的。The optical dissolved oxygen sensor based on the principle of fluorescence quenching overcomes the shortcomings of traditional dissolved oxygen measurement. It has the advantages of accurate measurement, fast, high selectivity, high stability, anti-electromagnetic interference and remote monitoring, and can realize the measurement of dissolved oxygen. In-situ continuous detection has been widely used in fields such as marine ecological environment monitoring and aquaculture water quality monitoring. Although optical dissolved oxygen sensors have higher stability and measurement accuracy than electrochemical dissolved oxygen sensors, during long-term in-situ monitoring, they are affected by complex multi-parameter environmental factors such as temperature, salinity, and depth. The problem of data drift will occur, and the measured data of the dissolved oxygen sensor needs to be compensated and corrected for environmental factors. However, the currently used compensation calibration methods generally have shortcomings such as inaccurate calibration values, long calibration cycles, and the calibration results cannot be highly consistent with the standard value at a large dissolved oxygen concentration. The main thing is that the current calibration method only targets the temperature of the dissolved oxygen sensor. The data interference was compensated and corrected, while the interference compensation correction that affected the sensor by salinity and environmental pressure was ignored. The traditional optical dissolved oxygen sensor temperature compensation calibration method is a two-point calibration method, namely anaerobic water and saturated dissolved oxygen water calibration. This method measures the dissolved oxygen sensor in anaerobic water (adding excess sodium sulfite and a small amount of divalent cobalt salt solution) As well as the phase value of the dissolved oxygen sensor in saturated dissolved oxygen water (continuous air bubbling method), perform a two-point linear fit with the theoretical calculated value of dissolved oxygen in water at this temperature to calibrate the dissolved oxygen sensor. However, this method has accurate Significant defects of low degree. Moreover, traditional calibration methods often only take into account the impact of temperature on sensor measurement data, and do not compensate for the interference of salinity, especially environmental pressure, which seriously affects the in-situ measurement of the sensor in complex offshore sea areas, high salinity differences, and high turbidity. Although the accuracy of dissolved oxygen in large estuaries is limited, there are also large errors in the profile measurements of dissolved oxygen. In order to promote the application and development of optical dissolved oxygen sensors, improve my country's operational monitoring capabilities of dissolved oxygen, improve the data quality of in-situ monitoring of marine dissolved oxygen, and promote the application and development of dissolved oxygen sensors, this paper provides the measurement and calibration work for my country's optical dissolved oxygen sensors. Provide methodological basis. Therefore, it is necessary to propose a high-precision correction system and correction method for complex multi-parameter environmental factor interference compensation for optical dissolved oxygen sensors.
发明内容Contents of the invention
本发明的目的在于针对上述技术问题，克服现有溶解氧传感器环境因子补偿校正方法标定周期长、标准值不够精确、环境因子校正单一、校正算法模型不够精确、校正结果只适用于温度变化海域、无法适用于多参数环境因子变化的复杂海域等显著问题，提供一种基于温度、盐度、深度和溶解氧浓度控制装置的补偿校正系统和相匹配的多参数环境因子补偿校正方法，利用该方法和装置能使校正标定后的溶解氧传感器显著提高原位监测的准确度，特别是能适用于多参数环境因子剧烈变化复杂海域溶解氧的原位监测。The purpose of the present invention is to address the above technical problems and overcome the existing dissolved oxygen sensor environmental factor compensation and correction method with long calibration cycle, insufficient standard value, single environmental factor correction, insufficient correction algorithm model, and correction results only applicable to sea areas with temperature changes. It cannot be applied to significant problems such as complex sea areas where multi-parameter environmental factors change. A compensation and correction system based on temperature, salinity, depth and dissolved oxygen concentration control devices and a matching multi-parameter environmental factor compensation and correction method are provided. Using this method And the device can significantly improve the accuracy of in-situ monitoring of the calibrated dissolved oxygen sensor, and is especially suitable for in-situ monitoring of dissolved oxygen in complex sea areas where multi-parameter environmental factors change drastically.
为解决上述技术问题所采用以下技术方案实现。In order to solve the above technical problems, the following technical solutions are adopted.
提供一种新型溶解氧传感器复杂多参数环境因子补偿校正系统，包括带水温控制装置低温恒温槽、带搅拌功能的标定装置、氧气瓶、氮气瓶、两个减压阀、三个质量流量控制器、带高精度温度和盐度探头的盐度调节装置、带高精度压力表的压力调节装置、安全阀、待校正溶解氧传感器和参比溶解氧传感器；带搅拌功能的校正池内置鼓气气泡石，内部盛满超纯水，且校正池整体置于带水温控制装置低温恒温槽中；校正池上设有气体入口、气体出口和取样口，气体出口连接安全阀；氮气瓶和氧气瓶分别通过管路依次经过减压阀、质量流量控制器、气体出入连接至鼓气气泡石；校正池上设有盐度调节装置和压力调节装置通过顶部开口连接水体；待校正溶解氧传感器和参比溶解氧传感器通过校正池顶部开口浸入标准装置中的水体里。Provide a new type of complex multi-parameter environmental factor compensation and correction system for dissolved oxygen sensors, including a low-temperature thermostat with a water temperature control device, a calibration device with a stirring function, an oxygen cylinder, a nitrogen cylinder, two pressure reducing valves, and three mass flow controllers , salinity regulating device with high-precision temperature and salinity probes, pressure regulating device with high-precision pressure gauge, safety valve, dissolved oxygen sensor to be calibrated and reference dissolved oxygen sensor; calibration tank with stirring function built-in air bubbles stone, the interior is filled with ultrapure water, and the entire calibration tank is placed in a low-temperature constant temperature bath with a water temperature control device; the calibration tank is equipped with a gas inlet, a gas outlet and a sampling port, and the gas outlet is connected to a safety valve; nitrogen bottles and oxygen bottles are passed through pipelines respectively It is connected to the air bubble stone through the pressure reducing valve, mass flow controller, and gas inlet and outlet in sequence; the calibration tank is equipped with a salinity adjustment device and a pressure adjustment device connected to the water body through the top opening; the dissolved oxygen sensor to be calibrated and the reference dissolved oxygen sensor pass through The top opening of the calibration tank is immersed in the water body in the standard device.
校正池为由耐压耐腐导热良好材料制成的圆柱形桶状罐体，在桶盖上预留有气体入口、气体出口和取样口，气体入口作为混合气的入口，气体出口作为鼓气时的气体出口，连接安全阀，鼓气结束后自动关闭，取样口作为碘量法取样时的取水样口；带水温控制装置的低温恒温槽同时具备加热和制冷功能，能对校正池内的水体温度进行精确控制，校正池内的参比溶解氧传感器用于鼓气时监测水体溶解氧传感器的变化，使校正池内部水体中溶解氧传感器的浓度稳定在设定值附近，不需要精确监测溶解氧浓度；校正池顶部的盐度调节装置和压力调节装置，能精确控制水体的盐度和环境压力值。校正池顶部的气体安全阀能封闭校正池，控制内部水体与外部空气的气液交换。安全阀避免鼓气状态下校正池内部压力过大，同时可以在停止通气的状态下，阻止校正池内部水体与外部空气进行气液交换，影响水体溶解氧浓度稳定。The calibration tank is a cylindrical barrel-shaped tank made of pressure-resistant, corrosion-resistant and heat-conducting materials. There is a gas inlet, gas outlet and sampling port reserved on the barrel cover. The gas inlet serves as the inlet for the mixed gas, and the gas outlet serves as the air blast. The gas outlet is connected to the safety valve, which automatically closes after the gas blowing is completed. The sampling port is used as the water sampling port during iodometric sampling; the low-temperature thermostat with a water temperature control device has both heating and cooling functions, which can correct the temperature in the calibration tank. The temperature of the water body is accurately controlled, and the reference dissolved oxygen sensor in the calibration pool is used to monitor the changes of the dissolved oxygen sensor in the water body when inflating, so that the concentration of the dissolved oxygen sensor in the water body inside the calibration pool is stabilized near the set value, without the need for precise monitoring of dissolved oxygen. Oxygen concentration; the salinity adjustment device and pressure adjustment device at the top of the calibration pool can accurately control the salinity and environmental pressure values of the water body. The gas safety valve on the top of the calibration pool can close the calibration pool and control the gas-liquid exchange between the internal water body and the external air. The safety valve prevents the internal pressure of the calibration pool from being too high when the air is inflated. At the same time, it can prevent the gas-liquid exchange between the water inside the calibration pool and the outside air when ventilation is stopped, affecting the stability of the dissolved oxygen concentration in the water.
光学溶解氧传感器复杂多参数环境因子补偿校正方法，包括如下步骤：The complex multi-parameter environmental factor compensation and correction method for optical dissolved oxygen sensors includes the following steps:
(1)将校正池注满超纯水，并将校正池整体置于低温恒温槽中，设置温度为0～35℃的某一个数值；(1) Fill the calibration pool with ultrapure water, place the entire calibration pool in a low-temperature thermostat, and set the temperature to a value between 0 and 35°C;
(2)等待校正池内温度稳定，通过质量流量控制器调节氧气瓶和高纯氮气瓶的气体流量比例，依次将配比不同的组合气体通入校正池中，获得多个溶解氧浓度的水体；水体溶解氧的饱和度控制在溶解氧传感器实际使用环境的溶解氧浓度范围之间，需涵盖浓度范围的上限和下限这两个浓度；(2) Wait for the temperature in the calibration pool to stabilize, adjust the gas flow ratio of the oxygen bottle and the high-purity nitrogen bottle through the mass flow controller, and sequentially pass the combined gases with different ratios into the calibration pool to obtain water with multiple dissolved oxygen concentrations; The saturation of dissolved oxygen in the water body is controlled within the dissolved oxygen concentration range of the actual environment in which the dissolved oxygen sensor is used, and it needs to cover the upper and lower limits of the concentration range;
(3)等待校正池内每个溶解氧浓度，参比溶解氧传感器示值及待校正溶解氧传感器信号值稳定后，记录待校正溶解氧传感器相位值和水体温度值。并同时从取样口采集水样以碘量分析方法测定溶解氧作为标准值；(3) Wait for each dissolved oxygen concentration in the calibration pool to be calibrated. After the reference value of the dissolved oxygen sensor and the signal value of the dissolved oxygen sensor to be corrected are stable, record the phase value of the dissolved oxygen sensor to be corrected and the water temperature value. At the same time, water samples were collected from the sampling port to measure dissolved oxygen as a standard value using iodine analysis method;
(4)依次将低温恒温槽的恒定温度设定值改为其他3个温度，重复步骤(2)(3)，恒定温度的选择范围一般为溶解氧传感器实际使用的环境温度范围，需要涵盖温度范围上限和下限这两个温度梯度；(4) Change the constant temperature setting value of the low-temperature thermostatic bath to the other three temperatures in sequence, and repeat steps (2) (3). The selection range of the constant temperature is generally the ambient temperature range actually used by the dissolved oxygen sensor, which needs to cover the temperature range. two temperature gradients, the upper and lower limits of the range;
(5)根据校正过程记录的待校正溶解氧传感器的相位值、校正池内部水体的温度值和由碘量法获得的溶解氧浓度标准值，计算待校正溶解氧传感器的温度补偿校正系数。具体方法是：(5) Calculate the temperature compensation correction coefficient of the dissolved oxygen sensor to be corrected based on the phase value of the dissolved oxygen sensor to be corrected recorded during the calibration process, the temperature value of the water body inside the calibration pool, and the standard value of the dissolved oxygen concentration obtained by the iodometry method. The specific method is:
根据每个温度设定点下，待校正溶解氧传感器的相位值、校正池内部水体的温度值和由碘量法获得的溶解氧浓度标准值，获得拟合公式：According to the phase value of the dissolved oxygen sensor to be corrected at each temperature set point, the temperature value of the water body inside the calibration pool and the standard value of dissolved oxygen concentration obtained by the iodometric method, the fitting formula is obtained:
[O2]T＝[(a0+a1t+a2t2)/(a3+a4φraw)–1]/(a5+a6t+a7t2+a8t3)(公式1)[O 2 ] T = [(a 0 +a 1 t+a 2 t 2 )/(a 3 +a 4 φ raw )–1]/(a 5 +a 6 t+a 7 t 2 +a 8 t 3 )(Formula 1)
其中，[O2]T为温度补偿校正后的溶解氧标准值，由碘量法获得，单位为mgL-1，φraw为待校正溶解氧传感器的相位值，t为校正池内部水体的温度值，单位为℃，由该拟合公式获得温度补偿系数a0 a1 a2 a3......a8。Among them, [O 2 ] T is the standard value of dissolved oxygen after temperature compensation correction, obtained by iodometric method, in mgL -1 , φ raw is the phase value of the dissolved oxygen sensor to be corrected, and t is the temperature of the water inside the calibration pool value, the unit is ℃, and the temperature compensation coefficient a 0 a 1 a 2 a 3 ......a 8 is obtained from this fitting formula.
(6)将低温恒温槽的恒定温度设定值改为15℃，通过连续鼓泡法获得饱和溶氧水；(6) Change the constant temperature setting value of the low-temperature thermostat to 15°C, and obtain saturated dissolved oxygen water through continuous bubbling;
(7)通过校正池顶部的盐度控制调节装置，改变水体的盐度值，等待校正池内参比溶解氧传感器示值及待校正溶解氧传感器信号值稳定达到稳定后，记录不同水体盐度条件下的校正池内部水体盐度值、温度值以及待校正溶解氧传感器溶解氧示值，并同时从取样口采集水样以碘量法测定溶解氧作为标准值；可通过如下盐度补偿校正公式计算盐度补偿校正系数：(7) Change the salinity value of the water body through the salinity control and adjustment device on the top of the calibration pool, wait for the reference dissolved oxygen sensor indication value in the calibration pool and the signal value of the dissolved oxygen sensor to be corrected to stabilize, and record the salinity conditions of different water bodies. The salinity value, temperature value of the water body inside the calibration pool and the dissolved oxygen indication value of the dissolved oxygen sensor to be calibrated are collected at the same time. At the same time, water samples are collected from the sampling port and the dissolved oxygen is measured by the iodometry method as the standard value; the following salinity compensation correction formula can be used Calculate the salinity compensation correction coefficient:
[O2]s＝[O2]T exp[(S-S0)(b0+b1ts+b2ts 2+b3ts 3)+b4(S2-S0 2)](公式2)[O 2 ] s = [O 2 ] T exp[(SS 0 )(b 0 +b 1 t s +b 2 t s 2 +b 3 t s 3 )+b 4 (S 2 -S 0 2 )] (Formula 2)
其中，[O2]s为温度盐度补偿校正后的溶解氧标准值，由碘量法获得，[O2]T为同等温度和溶解氧传感器信号值条件下通过公式1计算获得的溶解氧浓度理论值，b0、b1、b2、b3、b4为盐度补偿校正系数，S为水体现在的盐度，S0为水体之前的盐度，本校正方法中，记为0，公式2简化为如下公式：Among them, [O 2 ] s is the standard value of dissolved oxygen after temperature and salinity compensation correction, which is obtained by the iodometric method. [O 2 ] T is the dissolved oxygen calculated by formula 1 under the same temperature and dissolved oxygen sensor signal value conditions. Theoretical value of concentration, b 0 , b 1 , b 2 , b 3 , b 4 are salinity compensation correction coefficients, S is the current salinity of the water body, S 0 is the previous salinity of the water body, in this correction method, it is recorded as 0 , Formula 2 is simplified to the following formula:
[O2]s＝[O2]T exp[S(b0+b1ts+b2ts 2+b3ts 3)+b4S2](公式3)[O 2 ] s = [O 2 ] T exp[S(b 0 +b 1 t s +b 2 t s 2 +b 3 t s 3 )+b 4 S 2 ](Formula 3)
其中，ts是与校正池内部水体的温度值t有关的函数，可由下式计算得到：Among them, t s is a function related to the temperature value t of the water body inside the correction tank, which can be calculated by the following formula:
Ts＝ln[(298.15-t)/(273.15+t)](公式4)T s =ln[(298.15-t)/(273.15+t)](Formula 4)
式中，t为校正池内部水体的温度值，单位为℃。In the formula, t is the temperature value of the water body inside the calibration tank, and the unit is °C.
(8)将低温恒温槽的恒定温度设定值固定为15℃，通过连续鼓泡法获得饱和溶氧水，通过校正池上面的环境压力控制装置，改变水体的压力值，记录不同水体压力条件下的标定装置内部水体压力值和待校正溶解氧传感器溶解氧示值，可得环境压力补偿修正公式，计算压力补偿校正系数：(8) Fix the constant temperature setting value of the low-temperature constant temperature bath at 15°C, obtain saturated dissolved oxygen water through continuous bubbling, change the pressure value of the water body through the environmental pressure control device on the correction tank, and record different water body pressure conditions Based on the internal water pressure value of the calibration device and the dissolved oxygen indication value of the dissolved oxygen sensor to be corrected, the environmental pressure compensation correction formula can be obtained and the pressure compensation correction coefficient can be calculated:
[O2]d＝[O2]s+[O2]s pcp(公式5)[O 2 ] d = [O 2 ] s + [O 2 ] s pcp (Formula 5)
式中，[O2]d为深度补偿校正后的溶解氧标准值，[O2]s为同等温度、盐度和溶解氧传感器相位值条件下通过公式(2)计算获得的溶解氧浓度理论值，p为环境压力，单位为dbar，cp为环境压力补偿系数；In the formula, [O 2 ] d is the standard value of dissolved oxygen after depth compensation correction, [O 2 ] s is the theoretical dissolved oxygen concentration calculated by formula (2) under the same temperature, salinity and phase value of the dissolved oxygen sensor. value, p is the ambient pressure in dbar, cp is the ambient pressure compensation coefficient;
(9)通过上述温度、盐度、环境压力校正补偿方法，可获得光学溶解氧传感器复杂多参数环境因子补偿校正计算方法：(9) Through the above temperature, salinity, and environmental pressure correction and compensation methods, the complex multi-parameter environmental factor compensation calculation method of the optical dissolved oxygen sensor can be obtained:
通过记录水体的温度值、盐度值、环境压力值和待校正溶解氧传感器溶解氧相位值，可由下式计算获得光学溶解氧传感器多参数环境因子补偿校正值：By recording the temperature value, salinity value, environmental pressure value of the water body and the dissolved oxygen phase value of the dissolved oxygen sensor to be corrected, the multi-parameter environmental factor compensation correction value of the optical dissolved oxygen sensor can be calculated by the following formula:
[O2]＝{[(a0+a1t+a2t2)/(a3+a4φraw)–1]/(a5+a6t+a7t2+a8t3)}(1+pcp)exp[S(b0+b1ts+b2ts 2+b3ts 3)+b4S2](公式6)[O 2 ]＝{[(a 0 +a 1 t+a 2 t 2 )/(a 3 +a 4 φ raw )–1]/(a 5 +a 6 t+a 7 t 2 +a 8 t 3 )}(1+pcp)exp[S(b 0 +b 1 t s +b 2 t s 2 +b 3 t s 3 )+b 4 S 2 ](Formula 6)
式中，[O2]为温度、盐度和环境压力补偿校正后的溶解氧传感器示值。In the formula, [O 2 ] is the dissolved oxygen sensor indication value after temperature, salinity and environmental pressure compensation correction.
步骤(2)中多个溶解氧浓度的水体是指根据溶解氧传感器实际使用环境的溶解氧浓度范围，至少等分为6个溶解氧浓度，并且需要溶解氧浓度范围的上限和下限两个溶解氧浓度，一般将水体中的溶解氧饱和度控制在0％至120％，平均等分为0％、20％、40％、60％、80％、100％、120％这7个溶解氧浓度，不需要非常精确。The water body with multiple dissolved oxygen concentrations in step (2) refers to the dissolved oxygen concentration range according to the actual use environment of the dissolved oxygen sensor, which is at least equally divided into 6 dissolved oxygen concentrations, and requires two dissolved oxygen concentrations, the upper and lower limits of the dissolved oxygen concentration range. Oxygen concentration, generally the dissolved oxygen saturation in the water body is controlled between 0% and 120%, which is equally divided into seven dissolved oxygen concentrations of 0%, 20%, 40%, 60%, 80%, 100%, and 120%. , does not need to be very precise.
步骤(3)是使用参比溶解氧传感器监测水体溶解氧浓度变化，控制通气速率，使溶解氧浓度变化不会过快。保持搅拌装置始终处于工作状态，使标定装置内部水体溶解氧含量保持均匀，搅拌装置速度不宜过快，否则会造成涡旋。溶解氧浓度在达到预设值后，停止通入不同配比的混合气体，关闭搅拌装置，并使水气混合器保持在密封状态。待系统稳定后，确保取样位置与溶解氧传感器探头位置相近并处于同一水层。Step (3) is to use a reference dissolved oxygen sensor to monitor changes in dissolved oxygen concentration in the water body and control the ventilation rate so that the dissolved oxygen concentration does not change too quickly. Keep the stirring device in working condition at all times to keep the dissolved oxygen content in the water inside the calibration device uniform. The speed of the stirring device should not be too fast, otherwise it will cause vortex. After the dissolved oxygen concentration reaches the preset value, stop introducing mixed gases with different ratios, close the stirring device, and keep the water-gas mixer in a sealed state. After the system is stable, ensure that the sampling position is close to the dissolved oxygen sensor probe and in the same water layer.
步骤(4)低温恒温槽恒定温度设定值的选择范围应根据溶解氧传感器实际使用的环境温度范围进行调整，温度设定值需要涵盖环境温度范围的上限和下限两个温度梯度；一般取0～35℃，需要涵盖0℃和35℃这两个温度梯度；Step (4) The selection range of the constant temperature set value of the cryogenic thermostat should be adjusted according to the actual ambient temperature range of the dissolved oxygen sensor. The temperature set value needs to cover the upper and lower temperature gradients of the ambient temperature range; generally 0 ~35℃, needs to cover the two temperature gradients of 0℃ and 35℃;
带水温控制装置低温恒温槽可以在-50℃至80℃很宽的温度范围内进行精确温度控制，测量精度±0.05℃，能够提供更好的温度适用性；盐度调节装置可以在0-40很宽的盐度范围内进行精确的盐度控制，深度调节装置可以在很宽的压力范围内进行精确的压力控制，整套校正系统可以涵盖溶解氧传感器实际使用环境的整个温度、盐度和压力范围，相比于现有装置，能够提供更多的温度、盐度和深度修正算法的校正基准点，可根据溶解氧传感器实际使用环境的多参数环境因子变化情况，灵活设置溶解氧浓度、温度点、盐度点、环境压力点的数量和间隔，能够控制单一环境因子的变化，也可以控制多参数环境因子的共同变化，进行联合补偿校正，有效控制环境条件，避免环境突然变化造成的误差，确保溶解氧传感器示值能够在很大的温度、盐度和环境压力范围内与溶解氧标准值保持高度的一致。The low-temperature thermostat with water temperature control device can perform precise temperature control within a wide temperature range of -50°C to 80°C, with a measurement accuracy of ±0.05°C, which can provide better temperature applicability; the salinity adjustment device can control the temperature within a wide range of -50°C to 80°C. Precise salinity control within a wide salinity range. The depth adjustment device can perform precise pressure control within a wide pressure range. The entire calibration system can cover the entire temperature, salinity and pressure of the actual environment in which the dissolved oxygen sensor is used. Compared with existing devices, it can provide more calibration reference points for temperature, salinity and depth correction algorithms, and can flexibly set dissolved oxygen concentration and temperature according to the changes in multi-parameter environmental factors of the actual environment in which the dissolved oxygen sensor is used. The number and spacing of points, salinity points, and environmental pressure points can control changes in a single environmental factor or the joint changes in multiple parameter environmental factors, perform joint compensation and correction, effectively control environmental conditions, and avoid errors caused by sudden changes in the environment. , ensuring that the dissolved oxygen sensor indication can maintain a high degree of consistency with the dissolved oxygen standard value over a wide range of temperature, salinity and environmental pressure.
本技术方案通过调节氧气和氮气的质量流量比例来调节校正池中溶解氧的浓度，并在同步取样后采用碘量法获得溶解氧浓度标准值，与现有根据氧气在水中的溶解度计算溶解氧标准值的方法和使用组合气体进行气体校正的方法相比，显著提高了校正的精度；使用4个温度条件下的20个溶解氧浓度进行传感器温度补偿校正，并配合该发明提出新的温度补偿校正算法公式进行溶解氧传感器温度补偿计算，相比于现有使用5个以上温度条件，超过60个溶解氧浓度进行溶解氧传感器温度校正的方法，大大减少了校正基准点的要求，显著缩短了校正周期，简化了校正过程，新的算法公式相比于现有多项式计算公式，在校正精度上有了极大的提升，简化计算过程，而且能在较大的温度和溶解氧范围内与溶解氧标准值保持一致；通过调节盐度和压力条件，进行光学溶解氧传感器的盐度和环境压力补偿校正，实现对溶解氧传感器全面系统的复杂多参数环境因子补偿校正，自动化程度高，提升传感器标定精度和校正精度，提高溶解氧传感器原位测量的准确度，使传感器具有更广泛的适用范围，适用于盐度变化较大的恶劣海域和大型河口，以及环境压力剧烈变化的海洋剖面溶解氧浓度的监测。This technical solution adjusts the concentration of dissolved oxygen in the calibration pool by adjusting the mass flow ratio of oxygen and nitrogen, and uses the iodometric method to obtain the standard value of dissolved oxygen concentration after synchronous sampling, which is different from the existing method of calculating dissolved oxygen based on the solubility of oxygen in water. Compared with the method of using combined gases for gas calibration, the standard value method significantly improves the accuracy of the calibration; 20 dissolved oxygen concentrations under 4 temperature conditions are used for sensor temperature compensation calibration, and a new temperature compensation is proposed in conjunction with this invention The correction algorithm formula is used to calculate the temperature compensation of the dissolved oxygen sensor. Compared with the existing method of using more than 5 temperature conditions and more than 60 dissolved oxygen concentrations to calibrate the temperature of the dissolved oxygen sensor, it greatly reduces the requirements for calibration reference points and significantly shortens the time. The calibration cycle simplifies the calibration process. Compared with the existing polynomial calculation formula, the new algorithm formula has greatly improved the calibration accuracy, simplifies the calculation process, and can be used with dissolved oxygen in a larger range of temperature and dissolved oxygen. The oxygen standard value remains consistent; by adjusting the salinity and pressure conditions, the salinity and environmental pressure compensation correction of the optical dissolved oxygen sensor is performed, and a comprehensive system of complex multi-parameter environmental factor compensation correction of the dissolved oxygen sensor is realized. The degree of automation is high, and the sensor is improved. Calibration accuracy and correction accuracy improve the accuracy of in-situ measurement of the dissolved oxygen sensor, making the sensor have a wider scope of application. It is suitable for harsh sea areas and large estuaries with large changes in salinity, as well as dissolved oxygen in ocean profiles with drastic changes in environmental pressure. Concentration monitoring.
本技术方案在不同的水体温度、盐度和环境压力条件下，依次将不同氧含量的混合气体通入校正池，使水体获得多个溶解氧浓度，记录待校正溶解氧传感器的相位值和水体的环境参数，并取水样以碘量法测定溶解氧标准值计算待校正溶解氧传感器的复杂多参数环境因子干扰补偿校正系数,可以实现多参数复杂环境因子的同时校正，自动化程度提高，提高传感器标定精度、校正精度、原位测量准确度，使传感器具有更广泛的适用范围。This technical solution sequentially passes mixed gases with different oxygen contents into the calibration pool under different water body temperature, salinity and environmental pressure conditions, so that the water body can obtain multiple dissolved oxygen concentrations, and record the phase value of the dissolved oxygen sensor to be calibrated and the water body Environmental parameters, and take water samples to measure the dissolved oxygen standard value by iodometric method to calculate the complex multi-parameter environmental factor interference compensation correction coefficient of the dissolved oxygen sensor to be calibrated, which can realize the simultaneous correction of multi-parameter complex environmental factors, improve the degree of automation, and improve Sensor calibration accuracy, correction accuracy, and in-situ measurement accuracy make the sensor have a wider scope of application.
附图说明Description of the drawings
图1：本发明光学溶解氧传感器多参数干扰补偿校正系统结构图。Figure 1: Structural diagram of the multi-parameter interference compensation and correction system of the optical dissolved oxygen sensor of the present invention.
其中：1.低温恒温槽；2.校正池；3.氧气瓶；4.氮气瓶；5.减压阀；6.质量流量控制器；7.盐度调节装置；8.压力调节装置；9.安全阀；10.待校正溶解氧传感器；11.参比溶解氧传感器；12.鼓气气泡石；13.液体流量计；14.采样瓶；15.导管；16.取样口；17.气体出口；18.气体入口；19.水密插接件；20.支架。Among them: 1. Low-temperature thermostat; 2. Calibration tank; 3. Oxygen cylinder; 4. Nitrogen cylinder; 5. Pressure reducing valve; 6. Mass flow controller; 7. Salinity adjustment device; 8. Pressure adjustment device; 9 .Safety valve; 10. Dissolved oxygen sensor to be calibrated; 11. Reference dissolved oxygen sensor; 12. Air bubble stone; 13. Liquid flow meter; 14. Sampling bottle; 15. Conduit; 16. Sampling port; 17. Gas Exit; 18. Gas inlet; 19. Watertight connector; 20. Bracket.
具体实施方式Detailed ways
下面将结合说明书附图和具体实施方式对本发明作进一步的详细说明。The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments of the description.
如图1所示，本发明中光学溶解氧传感器校正系统，包括带水温控制装置的低温恒温槽1、带搅拌功能的校正池2、氧气瓶3、氮气瓶4、两个减压阀5、三个质量流量控制器6、带高精度温度和盐度探头的盐度调节装置7、带高精度压力表的压力调节装置8、安全阀9、待校正溶解氧传感器10、参比溶解氧传感器11、鼓气气泡石12、液体流量计13、采样瓶14。As shown in Figure 1, the optical dissolved oxygen sensor calibration system of the present invention includes a low-temperature thermostatic bath 1 with a water temperature control device, a calibration pool 2 with a stirring function, an oxygen cylinder 3, a nitrogen cylinder 4, two pressure reducing valves 5, Three mass flow controllers 6. Salinity regulating device with high-precision temperature and salinity probes 7. Pressure regulating device with high-precision pressure gauge 8. Safety valve 9. Dissolved oxygen sensor to be calibrated 10. Reference dissolved oxygen sensor 11. Air bubble stone 12. Liquid flow meter 13. Sampling bottle 14.
其中，校正池2是由导热性能良好、耐高压、耐腐蚀的316不锈钢材料制成的圆柱形桶状罐体，内部盛满超纯水；在校正池2顶部预留有方便外部内部管线和电线连接的水密接插件，校正池整体置于带水温控制装置的低温恒温槽1中；待校正溶解氧传感器10和参比溶解氧传感器11通过校正池2顶部开口浸入校正池中的水体里，依靠支架固定在水体中央位置，且两者位置相近并处于同一水层，后者用于监测水体中溶解氧的浓度；校正池上2设有带高精度温度和盐度探头的盐度调节装置7和带高精度压力表的压力调节装置8，二者通过校正池顶部开口连接水体，用于调节水体的盐度和环境压力，并记录水体温度、盐度和环境压力值，用于该校正方法的盐度和环境压力补偿校正计算；校正池上设有气体入口、气体出口和取样口，气体出口连接安全阀9，用于保护标定装置避免压力过大，阻止校正池内部水体与外部空气进行气液交换，取样口通过导管连接溶解氧传感器探头邻近位置水体至取样瓶，用于碘量法分析，确定水体溶解氧浓度标准值；校正池2内部放置鼓气气泡石12，氮气瓶4和氧气瓶3分别通过管路依次经过减压阀5、质量流量控制器6、气体入口与其连接，用于增加气泡提高水气混合效率。Among them, the calibration tank 2 is a cylindrical barrel-shaped tank made of 316 stainless steel with good thermal conductivity, high pressure resistance, and corrosion resistance. The inside is filled with ultrapure water; there is reserved space on the top of the calibration tank 2 to facilitate the connection of external and internal pipelines and wires. The watertight connector, the entire calibration pool is placed in a low-temperature constant temperature bath 1 with a water temperature control device; the dissolved oxygen sensor 10 to be calibrated and the reference dissolved oxygen sensor 11 are immersed in the water body in the calibration pool through the top opening of the calibration pool 2, relying on the bracket Fixed in the center of the water body, and the two are close to each other and in the same water layer, the latter is used to monitor the concentration of dissolved oxygen in the water body; the calibration pool 2 is equipped with a salinity adjustment device 7 with a high-precision temperature and salinity probe and a belt The pressure regulating device 8 of the high-precision pressure gauge, which is connected to the water body through the top opening of the calibration pool, is used to adjust the salinity and environmental pressure of the water body, and record the water body temperature, salinity and environmental pressure values. The salt used for this calibration method is temperature and ambient pressure compensation correction calculation; the calibration pool is equipped with a gas inlet, a gas outlet and a sampling port, and the gas outlet is connected to a safety valve 9 to protect the calibration device from excessive pressure and prevent gas-liquid exchange between the water inside the calibration pool and the outside air. , the sampling port is connected to the water body adjacent to the dissolved oxygen sensor probe through a conduit to the sampling bottle, which is used for iodometric analysis to determine the standard value of the dissolved oxygen concentration in the water body; inside the calibration tank 2, place an air bubble stone 12, a nitrogen bottle 4 and an oxygen bottle 3 The pipelines are connected to the pressure reducing valve 5, the mass flow controller 6 and the gas inlet in order to increase bubbles and improve the water-gas mixing efficiency.
下面对本发明中的光学溶解氧传感器的温度、盐度、深度补偿校正方法作进一步说明，具体包括以下步骤：The temperature, salinity and depth compensation and correction method of the optical dissolved oxygen sensor in the present invention will be further described below, which specifically includes the following steps:
步骤(1)，将带水温控制装置的低温恒温槽设定在第一个温度值0℃，等待校正池内水体温度达到设定值并稳定。Step (1): Set the low-temperature thermostat with a water temperature control device at the first temperature value of 0°C, and wait for the water temperature in the correction tank to reach the set value and stabilize.
步骤(2)，通过连接在氧气瓶和高纯氮气瓶上面的三个质量流量控制器改变通入校正池的氧气和氮气的气体流量比例，使校正池内部水体依次获得0％、20％、40％、60％、80％、100％、120％，共计7个溶解氧浓度；Step (2), change the gas flow ratio of oxygen and nitrogen into the calibration pool through three mass flow controllers connected to the oxygen bottle and the high-purity nitrogen bottle, so that the water inside the calibration pool can obtain 0%, 20%, 40%, 60%, 80%, 100%, 120%, a total of 7 dissolved oxygen concentrations;
步骤(3)，在每个溶解氧浓度下，使用参比溶解氧传感器监测水体中的溶解氧浓度，待其测值达到预设值附近时，停止通入混合气体并关闭安全阀，校正池中参比溶解氧传感器示值和待校正溶解氧传感器信号值达到稳定后，记录此时的温度值，连续记录待校正溶解氧传感器的信号值，次数应不少于6次，以其平均值作为待校正溶解氧传感器的标准相位，同时从取样口通过导管平行采集与待校正溶解氧传感器探头处于同一水层相近位置的水样，使用碘量分析方法进行溶解氧分析，次数应不少于3次，以其平均值作为水样的标准溶解氧值；Step (3), at each dissolved oxygen concentration, use the reference dissolved oxygen sensor to monitor the dissolved oxygen concentration in the water body. When the measured value reaches near the preset value, stop flowing in the mixed gas and close the safety valve to calibrate the pool. After the indication value of the medium reference dissolved oxygen sensor and the signal value of the dissolved oxygen sensor to be corrected reach stability, record the temperature value at this time, and continuously record the signal value of the dissolved oxygen sensor to be corrected. The number of times should be no less than 6 times, and the average value shall be used. As the standard phase of the dissolved oxygen sensor to be calibrated, at the same time, collect water samples in parallel from the sampling port through the catheter in the same water layer and close to the dissolved oxygen sensor probe to be calibrated, and use the iodine analysis method to perform dissolved oxygen analysis. The number of times should be no less than Three times, the average value is used as the standard dissolved oxygen value of the water sample;
步骤(4)，依次将低温恒温槽的恒定温度设置为10℃、25℃和35℃，重复步骤(2)和步骤(3)；Step (4), set the constant temperature of the low-temperature thermostat to 10°C, 25°C and 35°C in sequence, and repeat steps (2) and (3);
步骤(5)，以每个温度设定点下，待校正溶解氧传感器的相位值、校正池内部水体的温度值和由碘量法获得的溶解氧标准值，计算待校正溶解氧传感器的温度补偿校正系数，计算方法如下：Step (5): Calculate the temperature of the dissolved oxygen sensor to be calibrated based on the phase value of the dissolved oxygen sensor to be calibrated at each temperature set point, the temperature value of the water body inside the calibration pool, and the dissolved oxygen standard value obtained by the iodometric method. Compensation correction coefficient, the calculation method is as follows:
根据记录的待校正溶解氧传感器相位平均值、温度值和溶解氧标准值，获得拟合公式：According to the recorded phase average value, temperature value and dissolved oxygen standard value of the dissolved oxygen sensor to be corrected, the fitting formula is obtained:
[O2]T＝[(a0+a1t+a2t2)/(a3+a4φraw)–1]/(a5+a6t+a7t2+a8t3)[O 2 ] T = [(a 0 +a 1 t+a 2 t 2 )/(a 3 +a 4 φ raw )–1]/(a 5 +a 6 t+a 7 t 2 +a 8 t 3 )
其中，[O2]T为温度补偿校正后的溶解氧标准值，由碘量法获得，单位为mgL-1，φraw为待校正溶解氧传感器的相位值，t为标定装置内部水体的温度值，单位为℃，由该拟合公式获得温度补偿系数a0 a1 a2 a3 a4 a5 a6 a7 a8；Among them, [O 2 ] T is the standard value of dissolved oxygen after temperature compensation, obtained by iodometric method, in mgL -1 , φ raw is the phase value of the dissolved oxygen sensor to be corrected, and t is the temperature of the water body inside the calibration device Value, unit is ℃, the temperature compensation coefficient a 0 a 1 a 2 a 3 a 4 a 5 a 6 a 7 a 8 is obtained from this fitting formula;
步骤(6)，将带水温控制装置的低温恒温槽恒定温度设定在15℃，等待校正池内水体温度达到设定值并稳定，以1Lmin-1的流量将混合气体(氮气氧气比例同空气相同)通入校正池内部超纯水曝气2h以上，使其中的溶解氧达到饱和，并静置一段时间使溶解氧达到稳定，获得饱和溶氧水。Step (6), set the constant temperature of the low-temperature thermostatic bath with a water temperature control device at 15°C, wait for the water temperature in the calibration pool to reach the set value and stabilize, and add the mixed gas (nitrogen and oxygen in the same proportion as air) at a flow rate of 1Lmin-1 ) into the calibration tank and aerate the ultrapure water for more than 2 hours to allow the dissolved oxygen to reach saturation, and let it stand for a period of time to stabilize the dissolved oxygen and obtain saturated dissolved oxygen water.
步骤(7)，通过连接在校正池上面的盐度调节装置改变加入校正池水体的试剂量，使校正池内部水体依次获得5、10、15、20、25、30，共计6个盐度；Step (7), change the amount of reagent added to the water body of the calibration pool through the salinity adjustment device connected to the calibration pool, so that the water body inside the calibration pool obtains 5, 10, 15, 20, 25, and 30 in sequence, for a total of 6 salinities;
步骤(8)，在每个盐度下，使用盐度计监测水体中的盐度，待其测值达到预设值时，停止通入试剂，待校正溶解氧传感器信号值达到稳定后，记录此时的温度值和盐度值，连续使用待校正溶解氧传感器测量不少于6次的信号值，以其平均值作为待校正溶解氧传感器的标准相位，同时从取样口平行采集不少于3组的水样，用碘量分析方法进行溶解氧分析，以其平均值作为水样的标准溶解氧值；Step (8), at each salinity, use a salinometer to monitor the salinity in the water body. When the measured value reaches the preset value, stop feeding the reagent. After the signal value of the calibrated dissolved oxygen sensor reaches stability, record For the temperature and salinity values at this time, continuously use the dissolved oxygen sensor to be calibrated to measure the signal value no less than 6 times, and use the average value as the standard phase of the dissolved oxygen sensor to be calibrated. At the same time, collect no less than 6 signals in parallel from the sampling port. For the water samples of the three groups, the dissolved oxygen was analyzed using the iodine analysis method, and the average value was used as the standard dissolved oxygen value of the water sample;
步骤(9)，根据记录的待校正溶解氧传感器相位平均值、温度值、盐度值和溶解氧标准值，可获得盐度补偿校正公式，计算待校正溶解氧传感器的盐度补偿校正系数：Step (9), according to the recorded phase average value, temperature value, salinity value and dissolved oxygen standard value of the dissolved oxygen sensor to be corrected, the salinity compensation correction formula can be obtained to calculate the salinity compensation correction coefficient of the dissolved oxygen sensor to be corrected:
[O2]s＝[O2]Texp[S(b0+b1ts+b2ts 2+b3ts 3)+b4S2][O 2 ] s = [O 2 ] T exp[S(b 0 +b 1 t s +b 2 t s 2 +b 3 t s 3 )+b 4 S 2 ]
式中，[O2]s为温度盐度补偿校正后的溶解氧标准值，由碘量法获得，[O2]T为同等温度和溶解氧传感器信号值条件下通过公式(1)计算获得的溶解氧浓度理论值，S为水体现在的盐度，根据该公式可建立六个线性联立方程，求解六个线性联立方程即可获得传感器的盐度校正系数b0、b1、b2、b3、b4。In the formula, [O 2 ] s is the standard value of dissolved oxygen after temperature and salinity compensation correction, which is obtained by the iodometric method. [O 2 ] T is the calculated value of formula (1) under the same temperature and dissolved oxygen sensor signal value. The theoretical value of dissolved oxygen concentration, S is the current salinity of the water body. According to this formula, six linear simultaneous equations can be established. Solving the six linear simultaneous equations can obtain the sensor's salinity correction coefficients b 0 , b 1 , b 2 , b3 , b4 .
步骤(10)，将带水温控制装置的低温恒温槽恒定温度设定为15℃，等待校正池内水体温度达到设定值并稳定，采用步骤(6)的方法，获得饱和溶氧水；从取样口平行采集不少于3组的水样，用碘量分析方法进行溶解氧分析，以其平均值作为水体的标准溶解氧值。Step (10), set the constant temperature of the low-temperature thermostat with a water temperature control device to 15°C, wait for the water temperature in the calibration tank to reach the set value and stabilize, and use the method of step (6) to obtain saturated dissolved oxygen water; from the sampling Collect no less than 3 groups of water samples in parallel, conduct dissolved oxygen analysis using iodine analysis method, and use the average value as the standard dissolved oxygen value of the water body.
步骤(11)，通过校正池顶部的环境压力控制调节装置，改变校正池内部水体的压力值，使校正池内部水体依次获得0.1MPa、0.5MPa、1MPa，共计3个压力；在每个压力下，使用压力表监测水体中的压力，待其测值达到预设值时，停止加压，待校正溶解氧传感器示值达到稳定后，记录不同水体压力条件下的校正池内部水体压力值、温度值、盐度值和通过上述温度盐度补偿校正方法标定过的溶解氧传感器溶解氧示值，根据加压前的水体溶解氧浓度标准值、水体压力值和待标定溶解氧传感器示值，可得环境压力补偿校正公式，计算压力补偿校正系数：Step (11), through the environmental pressure control and adjustment device on the top of the calibration pool, change the pressure value of the water body inside the calibration pool, so that the water body inside the calibration pool obtains 0.1MPa, 0.5MPa, and 1MPa in sequence, a total of 3 pressures; under each pressure , use a pressure gauge to monitor the pressure in the water body. When the measured value reaches the preset value, stop pressurizing. After the value of the calibrated dissolved oxygen sensor reaches stability, record the water body pressure value and temperature inside the calibration pool under different water body pressure conditions. value, salinity value and the dissolved oxygen indication value of the dissolved oxygen sensor calibrated by the above temperature and salinity compensation correction method. According to the standard value of the dissolved oxygen concentration of the water before pressurization, the water pressure value and the indication value of the dissolved oxygen sensor to be calibrated, it can be Obtain the environmental pressure compensation correction formula and calculate the pressure compensation correction coefficient:
[O2]d＝[O2]s+[O2]s pcp[O 2 ] d = [O 2 ] s + [O 2 ] s pcp
式中，[O2]d为深度补偿校正后的溶解氧标准值，[O2]s为同等温度、盐度和溶解氧传感器相位值条件下通过公式(2)计算获得的溶解氧浓度理论值，p为环境压力，单位为dbar，cp为环境压力补偿系数。In the formula, [O 2 ] d is the standard value of dissolved oxygen after depth compensation correction, [O 2 ] s is the theoretical dissolved oxygen concentration calculated by formula (2) under the same temperature, salinity and phase value of the dissolved oxygen sensor. value, p is the ambient pressure in dbar, and cp is the ambient pressure compensation coefficient.
通过上述方法计算获得的温度、盐度、环境压力补偿校正系数可获得光学溶解氧传感器温度、盐度、环境压力综合补偿校正计算公式：The temperature, salinity, and environmental pressure compensation correction coefficients calculated by the above method can be used to obtain the optical dissolved oxygen sensor temperature, salinity, and environmental pressure comprehensive compensation correction calculation formula:
[O2]＝{[(a0+a1t+a2t2)/(a3+a4φraw)–1]/(a5+a6t+a7t2+a8t3)}(1+pcp)exp[S(b0+b1ts+[O 2 ]＝{[(a 0 +a 1 t+a 2 t 2 )/(a 3 +a 4 φ raw )–1]/(a 5 +a 6 t+a 7 t 2 +a 8 t 3 )}(1+pcp)exp[S(b 0 +b 1 t s +
b2ts 2+b3ts 3)+b4S2]b 2 t s 2 +b 3 t s 3 )+b 4 S 2 ]
式中，[O2]为温度、盐度和环境压力补偿校正后的溶解氧传感器示值，t为温度，S为水体现在的盐度，p为水体压力；In the formula, [O 2 ] is the dissolved oxygen sensor indication value after temperature, salinity and environmental pressure compensation correction, t is the temperature, S is the current salinity of the water body, and p is the water body pressure;
经过校正后的光学溶解氧传感器在校正范围内任意温度、盐度、环境压力和溶解氧浓度下测定时，只需通过记录水体的温度值、盐度值、环境压力值和待校正溶解氧传感器溶解氧相位值，可由上述计算公式获得光学溶解氧传感器多参数环境因子补偿校正值。When the calibrated optical dissolved oxygen sensor is measured at any temperature, salinity, ambient pressure and dissolved oxygen concentration within the calibration range, it only needs to record the temperature value, salinity value, ambient pressure value of the water body and the dissolved oxygen sensor to be calibrated. The dissolved oxygen phase value can be obtained from the above calculation formula to obtain the multi-parameter environmental factor compensation correction value of the optical dissolved oxygen sensor.
实施例仅说明本发明的技术方案，而非对其进行任何限制；尽管参照前述实施例对本发明进行了详细的说明，对于本领域的普通技术人员来说，依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或替换，并不使相应技术方案的本质脱离本发明所要求保护的技术方案的精神和范围。The embodiments only illustrate the technical solutions of the present invention, but do not limit them in any way. Although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art can still make modifications to the technical solutions described in the foregoing embodiments. The technical solution may be modified, or some of the technical features thereof may be equivalently substituted; however, these modifications or substitutions shall not cause the essence of the corresponding technical solution to deviate from the spirit and scope of the technical solution claimed by the present invention.
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