CN115718148A - Oxygen interference dynamic compensation method and system for non-methane total hydrocarbon determination - Google Patents
Oxygen interference dynamic compensation method and system for non-methane total hydrocarbon determination Download PDFInfo
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Abstract
本发明属于检测分析技术领域，具体涉及非甲烷总烃测定的氧干扰动态补偿方法及系统。氧干扰动态补偿方法，包括以下步骤：S1、在非甲烷总烃测定过程中，实时检测进样气路中的待测气样的氧气浓度；S2、在FID检测器喷嘴入口前端的气路中设置补偿气路，对待测气样进行氧气补偿，以将待测气样的氧气浓度补偿至目标基准氧气浓度；S3、目标基准氧气浓度的待测气样进入FID检测器进行检测。通过实时监测待测气样中的氧气浓度，对FID检测器氧气浓度进行补偿，使得当待测气样的氧气浓度发生变化时，FID检测器中的氧气浓度始终保持恒定，进而解决氧气浓度变化对测量浓度影响较大的缺陷。
The invention belongs to the technical field of detection and analysis, and in particular relates to an oxygen interference dynamic compensation method and system for the determination of non-methane total hydrocarbons. The oxygen interference dynamic compensation method includes the following steps: S1, during the determination of non-methane total hydrocarbons, real-time detection of the oxygen concentration of the gas sample to be measured in the sample gas path; S2, in the gas path at the front end of the FID detector nozzle inlet Set up a compensation gas circuit to perform oxygen compensation on the gas sample to be tested, so as to compensate the oxygen concentration of the gas sample to be measured to the target reference oxygen concentration; S3. The gas sample to be tested with the target reference oxygen concentration enters the FID detector for detection. By monitoring the oxygen concentration in the gas sample to be tested in real time, the oxygen concentration of the FID detector is compensated, so that when the oxygen concentration of the gas sample to be tested changes, the oxygen concentration in the FID detector remains constant, thereby solving the problem of oxygen concentration changes Defects that have a large impact on the measured concentration.
Description
技术领域technical field
本发明属于检测分析技术领域，具体涉及非甲烷总烃测定的氧干扰动态补偿方法及系统。The invention belongs to the technical field of detection and analysis, and in particular relates to an oxygen interference dynamic compensation method and system for the determination of non-methane total hydrocarbons.
背景技术Background technique
目前，非甲烷总烃的标准测定方法主要采用差减法，即分别测量样品气体中总烃和甲烷的含量，两者之间求差即可获得样品气体中非甲烷总烃的含量。常见的测量技术主要包括气相色谱法与催化氧化法。其中，气相色谱法的原理为采用双柱配合FID检测器技术，通过甲烷柱分离出甲烷后进入FID检测器测量甲烷浓度，总烃柱直接测量总烃浓度。催化氧化法的原理为通过使用加热的催化剂将待测气体中除甲烷以外的烃类反应生成二氧化碳和水后，再将待测气体中剩余的甲烷通入FID检测器得到甲烷的含量，而总烃浓度则通过另一气路进入FID检测器直接测量。At present, the standard determination method of non-methane total hydrocarbons mainly adopts the subtraction method, that is, the content of total hydrocarbons and methane in the sample gas are measured respectively, and the content of non-methane total hydrocarbons in the sample gas can be obtained by calculating the difference between the two. Common measurement techniques mainly include gas chromatography and catalytic oxidation. Among them, the principle of gas chromatography is to use double-column with FID detector technology, separate methane through the methane column and then enter the FID detector to measure the methane concentration, and the total hydrocarbon column directly measures the total hydrocarbon concentration. The principle of the catalytic oxidation method is to use a heated catalyst to react the hydrocarbons in the gas to be tested except methane to generate carbon dioxide and water, and then pass the remaining methane in the gas to be tested into the FID detector to obtain the content of methane, and the total The hydrocarbon concentration enters the FID detector through another gas path for direct measurement.
上述两种测量技术通过不同方法测量得到甲烷浓度，而总烃浓度皆通过将样品气体直接送入FID检测器测量获得，最后使用差减法计算得出非甲烷总烃浓度。然而，而采用氢火焰离子化检测器(即FID检测器)对总烃浓度进行测量时，由于氧气对FID检测器存在协同效应，氧气含量会影响检测器火焰燃烧状态，进而影响FID检测器响应灵敏度，对测量结果造成干扰，且实际测量应用中，不同工况下氧气含量变化范围大，氧气对检测器测量准确性带来的干扰程度会伴随待测气体中氧气含量变化发生动态改变。The above two measurement techniques measure the methane concentration by different methods, and the total hydrocarbon concentration is obtained by sending the sample gas directly into the FID detector for measurement, and finally calculate the non-methane total hydrocarbon concentration by using the subtraction method. However, when using a hydrogen flame ionization detector (FID detector) to measure the concentration of total hydrocarbons, due to the synergistic effect of oxygen on the FID detector, the oxygen content will affect the flame combustion state of the detector, thereby affecting the response of the FID detector. Sensitivity will cause interference to the measurement results, and in actual measurement applications, the oxygen content varies widely under different working conditions, and the degree of interference caused by oxygen to the measurement accuracy of the detector will change dynamically with the change of the oxygen content in the gas to be measured.
针对氧干扰对FID检测器测量结果准确性造成的影响，现有主要采用以下两种方式对氧干扰进行修正：In view of the impact of oxygen interference on the accuracy of FID detector measurement results, the following two methods are currently used to correct oxygen interference:
第一种方式通过色谱柱分离出待测气体中氧气后进入FID检测器测量得到氧峰面积，在总烃浓度计算时在总烃峰面积中扣除氧峰面积后进行浓度计算，该方法仅考虑了氧气单独在FID检测器上的固定影响，忽略了氧气对其他气体组分的协同效应。The first way is to separate the oxygen in the gas to be tested through the chromatographic column and then enter the FID detector to measure the oxygen peak area. When calculating the total hydrocarbon concentration, subtract the oxygen peak area from the total hydrocarbon peak area to calculate the concentration. This method only considers The fixed effect of oxygen alone on the FID detector is ignored, and the synergistic effect of oxygen on other gas components is ignored.
第二种方式是通过测量单一氧气含量背景下不同浓度的标准气体的总烃浓度，通过该氧气背景条件下氧气对不同浓度标准气体氧干扰程度的差异对包含所有量程范围内的标准气体总烃测量浓度进行修正，该方法仅考虑了氧气对不同浓度标准气体的影响差异及样气对其他气体组分的协同效应，忽略了氧气含量在不同工况中变化范围大，造成不同的氧气含量背景条件下，氧气对测量浓度影响存在差异的问题，且使用该方法对应的修正算法进行修正时，因在线监测仪器长期运行时需进行日常维护或故障停机检修等运维工作，会导致分析系统状态如供气气源纯度等发生改变影响分析仪长期稳定性。因此，需要对修正算法进行定期质控校准更新，应用难度、运维难度大，且当分析系统状态发证改变后难以保证修正效果长期稳定。The second way is to measure the total hydrocarbon concentration of standard gases with different concentrations under the background of a single oxygen content, and the difference in the degree of interference of oxygen to standard gases with different concentrations of oxygen under this oxygen background condition will affect the total hydrocarbons of standard gases in all ranges. The measured concentration is corrected. This method only considers the difference in the influence of oxygen on different concentrations of standard gases and the synergistic effect of sample gas on other gas components, ignoring the large range of changes in oxygen content in different working conditions, resulting in different oxygen content backgrounds Under certain conditions, there is a problem that the influence of oxygen on the measured concentration is different, and when the correction algorithm corresponding to this method is used for correction, due to the long-term operation of the online monitoring instrument, it is necessary to carry out daily maintenance or maintenance work such as downtime and maintenance, which will lead to the analysis of system status. For example, changes in the purity of the gas supply will affect the long-term stability of the analyzer. Therefore, regular quality control calibration updates are required for the correction algorithm, which is difficult to apply and operate, and it is difficult to ensure long-term stability of the correction effect after the status of the analysis system changes.
发明内容Contents of the invention
基于现有技术中存在的上述缺点和不足，本发明的目的之一是至少解决现有技术中存在的上述问题之一或多个，换言之，本发明的目的之一是提供满足前述需求之一或多个的非甲烷总烃测定的氧干扰动态补偿方法及系统。Based on the above-mentioned shortcomings and deficiencies in the prior art, one of the purposes of the present invention is to at least solve one or more of the above-mentioned problems in the prior art. In other words, one of the purposes of the present invention is to provide a A method and system for dynamic compensation of oxygen interference in the determination of one or more non-methane total hydrocarbons.
为了达到上述发明目的，本发明采用以下技术方案：In order to achieve the above object of the invention, the present invention adopts the following technical solutions:
非甲烷总烃测定的氧干扰动态补偿方法，包括以下步骤：The method for dynamic compensation of oxygen interference in the determination of non-methane total hydrocarbons comprises the following steps:
S1、在非甲烷总烃测定过程中，实时检测进样气路中的待测气样的氧气浓度；S1. During the determination of non-methane total hydrocarbons, real-time detection of the oxygen concentration of the gas sample to be tested in the sampling gas path;
S2、在FID检测器喷嘴入口前端的气路中设置补偿气路，对待测气样进行氧气补偿，以将待测气样的氧气浓度补偿至目标基准氧气浓度；S2. Set a compensation gas path in the gas path at the front end of the nozzle inlet of the FID detector, and perform oxygen compensation for the gas sample to be tested, so as to compensate the oxygen concentration of the gas sample to be measured to the target reference oxygen concentration;
S3、目标基准氧气浓度的待测气样进入FID检测器进行检测。S3. The gas sample to be tested with the target reference oxygen concentration enters the FID detector for detection.
作为优选方案，所述步骤S2中，氧气补偿的补偿气流量Q为：As a preferred solution, in the step S2, the compensation gas flow Q for oxygen compensation is:
其中，QH为FID检测器的燃烧气流量，QN为FID检测器的载气流量，V为待测气样的进样体积，T为总烃峰的峰宽，C*为待测气样、燃气及载气进入FID检测器喷嘴处的氧气基准浓度，C0为目标基准氧气浓度，C为待测样气的氧气浓度。Among them, Q H is the combustion gas flow rate of the FID detector, Q N is the carrier gas flow rate of the FID detector, V is the injection volume of the gas sample to be tested, T is the peak width of the total hydrocarbon peak, and C * is the gas to be tested The sample, gas and carrier gas enter the oxygen reference concentration at the nozzle of the FID detector, C 0 is the target reference oxygen concentration, and C is the oxygen concentration of the sample gas to be tested.
作为优选方案，所述燃烧气为氢气。As a preferred solution, the combustion gas is hydrogen.
作为优选方案，所述载气为氮气或氦气。As a preferred solution, the carrier gas is nitrogen or helium.
作为优选方案，所述补偿气路设有流量控制器，用于控制补偿气流量。As a preferred solution, the compensation gas path is provided with a flow controller for controlling the compensation gas flow.
作为优选方案，所述目标基准氧气浓度不小于待测工况下的待测气样的最高氧气浓度。As a preferred solution, the target reference oxygen concentration is not less than the highest oxygen concentration of the gas sample to be tested under the working condition to be tested.
本发明还提供非甲烷总烃测定的氧干扰动态补偿系统，应用如上方案所述的氧干扰动态补偿方法，所述氧干扰动态补偿系统包括：The present invention also provides an oxygen interference dynamic compensation system for the determination of non-methane total hydrocarbons. The oxygen interference dynamic compensation method described in the above scheme is applied, and the oxygen interference dynamic compensation system includes:
氧气浓度检测模块，用于实时检测进样气路中的待测气样的氧气浓度；The oxygen concentration detection module is used to detect the oxygen concentration of the gas sample to be tested in the sample gas path in real time;
补偿气路，设于FID检测器喷嘴入口前端的气路，且沿待测气样的流向补偿气路与FID检测器喷嘴入口前端的气路的连接点位于氧气浓度检测模块的下游；补偿气路用于对待测气样进行氧气补偿，以将待测气样的氧气浓度补偿至目标基准氧气浓度；The compensation gas path is set at the front end of the nozzle inlet of the FID detector, and the connection point between the compensation gas path and the gas path at the front end of the nozzle inlet of the FID detector along the flow direction of the gas sample to be tested is located downstream of the oxygen concentration detection module; the compensation gas The circuit is used for oxygen compensation of the gas sample to be tested, so as to compensate the oxygen concentration of the gas sample to be measured to the target reference oxygen concentration;
FID检测器，用于对输入的目标基准氧气浓度的待测气样进行检测。The FID detector is used to detect the gas sample to be tested with the input target reference oxygen concentration.
作为优选方案，所述氧气补偿的补偿气流量Q为：As a preferred solution, the compensation gas flow Q for the oxygen compensation is:
其中，QH为FID检测器的燃烧气流量，QN为FID检测器的载气流量，V为待测气样的进样体积，T为总烃峰的峰宽，C*为待测气样、燃气及载气进入FID检测器喷嘴处的氧气基准浓度，C0为目标基准氧气浓度，C为待测样气的氧气浓度。Among them, Q H is the combustion gas flow rate of the FID detector, Q N is the carrier gas flow rate of the FID detector, V is the injection volume of the gas sample to be tested, T is the peak width of the total hydrocarbon peak, and C * is the gas to be tested The sample, gas and carrier gas enter the oxygen reference concentration at the nozzle of the FID detector, C 0 is the target reference oxygen concentration, and C is the oxygen concentration of the sample gas to be tested.
上述氧气补偿的补偿气流量Q即为动态氧气补偿模型。The compensation gas flow Q for the above oxygen compensation is the dynamic oxygen compensation model.
作为优选方案，所述补偿气路设有流量控制器，用于控制补偿气流量。As a preferred solution, the compensation gas path is provided with a flow controller for controlling the compensation gas flow.
作为优选方案，所述目标基准氧气浓度不小于待测工况下的待测气样的最高氧气浓度。As a preferred solution, the target reference oxygen concentration is not less than the highest oxygen concentration of the gas sample to be tested under the working condition to be tested.
本发明与现有技术相比，有益效果是：The present invention compares with prior art, beneficial effect is:
本发明的非甲烷总烃测定的氧干扰动态补偿方法及系统，通过实时监测待测气样中的氧气浓度，对FID检测器氧气浓度进行补偿，使得当待测气样的氧气浓度发生变化时，FID检测器中的氧气浓度始终保持恒定，进而解决氧气浓度变化对测量浓度影响较大的缺陷。相较于其他现有通过算法对测量结果进行修正的方式，本发明适用性高，不同仪器间可使用统一修正方法，且无需对不同仪器单独建立修正算法并定期校准更新，在满足复杂工况应用需求的同时更便捷地解决了氧干扰问题。The oxygen interference dynamic compensation method and system for the determination of non-methane total hydrocarbons of the present invention compensate the oxygen concentration of the FID detector by monitoring the oxygen concentration in the gas sample to be tested in real time, so that when the oxygen concentration of the gas sample to be tested changes , the oxygen concentration in the FID detector is always kept constant, thereby solving the defect that the change of oxygen concentration has a great influence on the measured concentration. Compared with other existing methods of correcting measurement results through algorithms, the present invention has high applicability, a unified correction method can be used among different instruments, and there is no need to separately establish correction algorithms for different instruments and regularly calibrate and update them. It is more convenient to solve the problem of oxygen interference while meeting the application requirements.
附图说明Description of drawings
图1是本发明实施例1的非甲烷总烃测定的氧干扰动态补偿方法的流程图；Fig. 1 is the flowchart of the oxygen interference dynamic compensation method of the non-methane total hydrocarbon determination of the embodiment of the present invention 1;
图2是本发明实施例1的非甲烷总烃测定的氧干扰动态补偿系统的构架图。Fig. 2 is a schematic diagram of a dynamic compensation system for oxygen interference in the determination of non-methane total hydrocarbons in Example 1 of the present invention.
具体实施方式Detailed ways
为了更清楚地说明本发明实施例，下面将对照附图说明本发明的具体实施方式。显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图，并获得其他的实施方式。In order to illustrate the embodiments of the present invention more clearly, the specific implementation manners of the present invention will be described below with reference to the accompanying drawings. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention, and those skilled in the art can obtain other accompanying drawings based on these drawings and obtain other implementations.
实施例1：Example 1:
本实施例针对不同浓度氧气背景条件下，通过对FID检测器增加氧气气体动态补偿的方式，将FIF检测器内氧气含量补偿至与目标基准点相同，使FID检测器内氧气含量不随待测气样中氧气浓度变化发生改变，始终保持恒定。In this embodiment, under the background conditions of different concentrations of oxygen, the oxygen content in the FID detector is compensated to be the same as the target reference point by adding oxygen gas dynamic compensation to the FID detector, so that the oxygen content in the FID detector does not change with the gas to be tested. The oxygen concentration in the sample changes and remains constant.
因FID检测器氧气浓度保持恒定，氧气对待测因子的影响程度始终保持与目标基准点一致，无需定期单独质控更新修正模型，从根本上解决了待测气样中氧气含量变化导致的测量结果不准确的缺陷。Because the oxygen concentration of the FID detector remains constant, the degree of influence of oxygen on the measured factors is always consistent with the target reference point, and there is no need to update and correct the model for regular separate quality control, which fundamentally solves the measurement results caused by changes in the oxygen content in the gas sample to be tested inaccurate defect.
具体地，如图1所示，本实施例的非甲烷总烃测定的氧干扰动态补偿方法，包括以下步骤：Specifically, as shown in Figure 1, the oxygen interference dynamic compensation method for the determination of non-methane total hydrocarbons in this embodiment includes the following steps:
S1、在非甲烷总烃测定过程中，实时检测进样气路中的待测气样的氧气浓度；S1. During the determination of non-methane total hydrocarbons, real-time detection of the oxygen concentration of the gas sample to be tested in the sampling gas path;
S2、在FID检测器喷嘴入口前端的气路中设置补偿气路，对待测气样进行氧气补偿，以将待测气样的氧气浓度补偿至目标基准氧气浓度；S2. Set a compensation gas path in the gas path at the front end of the nozzle inlet of the FID detector, and perform oxygen compensation for the gas sample to be tested, so as to compensate the oxygen concentration of the gas sample to be measured to the target reference oxygen concentration;
其中，根据分析检测系统应用的实际工况，选择氧气补偿基准点，即目标基准氧气浓度。基准点为待测气样中氧气浓度的最大典型值，即当待测气样中氧气含量变化时，通过补偿气将待测气样中的氧气浓度补偿至实际可能出现的最高氧浓度值；因此，目标基准氧气浓度不小于待测工况下的待测气样的最高氧气浓度。Among them, according to the actual working conditions of the application of the analysis and detection system, the oxygen compensation reference point, that is, the target reference oxygen concentration, is selected. The reference point is the maximum typical value of the oxygen concentration in the gas sample to be tested, that is, when the oxygen content in the gas sample to be tested changes, the oxygen concentration in the gas sample to be tested is compensated to the actual highest possible oxygen concentration value through the compensation gas; Therefore, the target reference oxygen concentration is not less than the highest oxygen concentration of the gas sample to be tested under the working condition to be tested.
具体地，动态氧气补偿模型，即氧气补偿的补偿气流量Q为：Specifically, the dynamic oxygen compensation model, that is, the compensation gas flow Q for oxygen compensation is:
其中，QH为FID检测器的燃烧气流量，QN为FID检测器的载气流量，V为待测气样的进样体积，T为总烃峰的峰宽(单位min)，C*为待测气样、燃气及载气进入FID检测器喷嘴处的氧气基准浓度(即待测气样、燃气及载气混合后的氧气的占比)，C0为目标基准氧气浓度，C为待测样气的氧气浓度。Among them, Q H is the combustion gas flow rate of the FID detector, Q N is the carrier gas flow rate of the FID detector, V is the injection volume of the gas sample to be tested, T is the peak width of the total hydrocarbon peak (unit min), C * is the oxygen reference concentration at the nozzle of the FID detector where the gas sample to be tested, gas and carrier gas enter (that is, the proportion of oxygen after the gas sample to be tested, gas and carrier gas are mixed), C 0 is the target reference oxygen concentration, and C is The oxygen concentration of the sample gas to be tested.
本实施例的燃烧气为氢气，载气为氮气或氦气。The combustion gas in this embodiment is hydrogen, and the carrier gas is nitrogen or helium.
S3、目标基准氧气浓度的待测气样进入FID检测器进行检测。S3. The gas sample to be tested with the target reference oxygen concentration enters the FID detector for detection.
另外，本实施例的补偿气路设有流量控制器，用于动态控制补偿气流量，适应不同的工况条件。In addition, the compensation air path of this embodiment is provided with a flow controller for dynamically controlling the compensation air flow to adapt to different working conditions.
基于本实施例的上述氧干扰动态补偿方法，如图2所示，本实施例还提供非甲烷总烃测定的氧干扰动态补偿系统，基于现有的非甲烷总烃测定分析系统，包括氧气浓度检测模块、补偿气路和FID检测器。Based on the above-mentioned oxygen interference dynamic compensation method of this embodiment, as shown in Figure 2, this embodiment also provides an oxygen interference dynamic compensation system for the determination of non-methane total hydrocarbons, based on the existing non-methane total hydrocarbons measurement and analysis system, including oxygen concentration Detection module, compensation gas path and FID detector.
具体地，在分析系统的进样气路中增加氧气浓度检测模块，实时测量进入分析系统的待测气样的氧气浓度。另外，在分析系统的FID检测器喷嘴入口前端的气路增加一路补偿气路，进行氧气补偿，使待测气样与补偿气(即氧气)混合后进入FID检测器分析，通过补偿气路的流量控制器控制补偿气气体流量。Specifically, an oxygen concentration detection module is added to the sample gas path of the analysis system to measure the oxygen concentration of the gas sample to be tested entering the analysis system in real time. In addition, a compensation gas path is added to the gas path at the front end of the FID detector nozzle inlet of the analysis system to perform oxygen compensation, so that the gas sample to be tested is mixed with the compensation gas (that is, oxygen) and then enters the FID detector for analysis. The flow controller controls the compensation gas flow.
本实施例的氧气浓度检测模块，用于实时检测进样气路中的待测气样的氧气浓度；The oxygen concentration detection module of this embodiment is used for real-time detection of the oxygen concentration of the gas sample to be tested in the sample gas path;
本实施例的补偿气路，设于FID检测器喷嘴入口前端的气路，且沿待测气样的流向补偿气路与FID检测器喷嘴入口前端的气路的连接点位于氧气浓度检测模块的下游；补偿气路用于对待测气样进行氧气补偿，以将待测气样的氧气浓度补偿至目标基准氧气浓度；The compensation gas path of this embodiment is set at the gas path at the front end of the nozzle inlet of the FID detector, and the connection point between the compensation gas path and the gas path at the front end of the nozzle inlet of the FID detector along the flow direction of the gas sample to be tested is located at the oxygen concentration detection module Downstream; the compensation gas path is used for oxygen compensation of the gas sample to be measured, so as to compensate the oxygen concentration of the gas sample to be measured to the target reference oxygen concentration;
FID检测器，用于对输入的目标基准氧气浓度的待测气样进行检测。The FID detector is used to detect the gas sample to be tested with the input target reference oxygen concentration.
作为优选方案，所述氧气补偿的补偿气流量Q为：As a preferred solution, the compensation gas flow Q for the oxygen compensation is:
其中，QH为FID检测器的燃烧气流量，QN为FID检测器的载气流量，V为待测气样的进样体积，T为总烃峰的峰宽，C*为待测气样、燃气及载气进入FID检测器喷嘴处的氧气基准浓度，C0为目标基准氧气浓度，C为待测样气的氧气浓度。Among them, Q H is the combustion gas flow rate of the FID detector, Q N is the carrier gas flow rate of the FID detector, V is the injection volume of the gas sample to be tested, T is the peak width of the total hydrocarbon peak, and C * is the gas to be tested The sample, gas and carrier gas enter the oxygen reference concentration at the nozzle of the FID detector, C 0 is the target reference oxygen concentration, and C is the oxygen concentration of the sample gas to be tested.
本实施例根据分析检测系统应用的实际工况，选择氧气补偿基准点，即目标基准氧气浓度。基准点为待测气样中氧气浓度的最大典型值，即当待测气样中氧气含量变化时，通过补偿气将待测气样中的氧气浓度补偿至实际可能出现的最高氧浓度值；因此，目标基准氧气浓度不小于待测工况下的待测气样的最高氧气浓度。In this embodiment, the oxygen compensation reference point, ie, the target reference oxygen concentration, is selected according to the actual working conditions of the application of the analysis and detection system. The reference point is the maximum typical value of the oxygen concentration in the gas sample to be tested, that is, when the oxygen content in the gas sample to be tested changes, the oxygen concentration in the gas sample to be tested is compensated to the actual highest possible oxygen concentration value through the compensation gas; Therefore, the target reference oxygen concentration is not less than the highest oxygen concentration of the gas sample to be tested under the working condition to be tested.
具体地，动态氧气补偿模型(即氧干扰动态补偿模型)，即氧气补偿的补偿气流量Q为：Specifically, the dynamic oxygen compensation model (that is, the oxygen interference dynamic compensation model), that is, the compensation gas flow Q for oxygen compensation is:
其中，QH为FID检测器的燃烧气流量，QN为FID检测器的载气流量，V为待测气样的进样体积，T为总烃峰的峰宽(单位min)，C*为待测气样、燃气及载气进入FID检测器喷嘴处的氧气基准浓度(即待测气样、燃气及载气混合后的氧气的占比)，C0为目标基准氧气浓度，C为待测样气的氧气浓度。Among them, Q H is the combustion gas flow rate of the FID detector, Q N is the carrier gas flow rate of the FID detector, V is the injection volume of the gas sample to be tested, T is the peak width of the total hydrocarbon peak (unit min), C * is the oxygen reference concentration at the nozzle of the FID detector where the gas sample to be tested, gas and carrier gas enter (that is, the proportion of oxygen after the gas sample to be tested, gas and carrier gas are mixed), C 0 is the target reference oxygen concentration, and C is The oxygen concentration of the sample gas to be tested.
本实施例的燃烧气为氢气，载气为氮气或氦气。The combustion gas in this embodiment is hydrogen, and the carrier gas is nitrogen or helium.
以下对本实施例的氧干扰动态补偿方法及系统进行性能测试对比，分别将氧含量为0％、5％、10％、15％、20％，总烃浓度为1ppm、2ppm、5ppm、10ppm、20ppm的丙烷标准气体通入FID检测器，计算不同浓度氧气含量背景下的标准气体测量浓度相对于氧气含量为补偿基准点20％时的标准气体测量浓度的相对误差。通过氧干扰动态补偿模型，通过补偿气将不同氧气含量的样品中FID检测器喷嘴处的氧气浓度补偿至基准值，计算不同浓度氧气含量背景下的标准气体经氧干扰补偿模型补偿后的测量浓度相对于氧气含量为补偿基准点20％时的标准气体测量浓度的相对误差，计算结果具体如下：The following is a performance test comparison of the oxygen interference dynamic compensation method and system of this embodiment. The oxygen content is 0%, 5%, 10%, 15%, and 20%, respectively, and the total hydrocarbon concentration is 1ppm, 2ppm, 5ppm, 10ppm, and 20ppm. The propane standard gas is passed into the FID detector, and the relative error of the standard gas measurement concentration under the background of different concentrations of oxygen content relative to the standard gas measurement concentration when the oxygen content is 20% of the compensation reference point is calculated. Through the oxygen interference dynamic compensation model, the oxygen concentration at the nozzle of the FID detector in samples with different oxygen contents is compensated to the reference value by the compensation gas, and the measured concentration of the standard gas under the background of different concentrations of oxygen content after being compensated by the oxygen interference compensation model is calculated. Relative to the relative error of the standard gas measurement concentration when the oxygen content is 20% of the compensation reference point, the calculation results are as follows:
表1样品气体测量浓度经修正前后示值误差差异Table 1 Difference of indication error before and after correction of sample gas measurement concentration
由上表1可知，样品气体测量浓度经修正前与实际浓度偏差大，氧气对测量结果准确性影响较大。经氧干扰补偿模型修正后，测量浓度与理论浓度相对偏差大大降低，减小了样气中氧气含量对测量结果的影响，保证了不同氧气背景条件下测量结果的准确性，修正后测量浓度与理论浓度的示值误差能够满足标准HJ 1013-2018中对氧气影响示值误差小于等于2％F.S的指标要求。It can be seen from the above table 1 that the measured concentration of the sample gas has a large deviation from the actual concentration before correction, and oxygen has a great influence on the accuracy of the measurement results. After the oxygen interference compensation model is corrected, the relative deviation between the measured concentration and the theoretical concentration is greatly reduced, which reduces the influence of the oxygen content in the sample gas on the measurement results, and ensures the accuracy of the measurement results under different oxygen background conditions. The indication error of the theoretical concentration can meet the index requirements of the standard HJ 1013-2018 on the influence of oxygen on the indication error of less than or equal to 2% F.S.
综上，本发明的氧干扰动态补偿方法及系统对待测气样中的氧干扰进行修正，具有以下优点：In summary, the oxygen interference dynamic compensation method and system of the present invention corrects the oxygen interference in the gas sample to be measured, and has the following advantages:
1、本发明基于气相色谱法配合FID检测器测量非甲烷总烃技术，结合该技术中氧气对FID检测器影响特征制定氧干扰动态补偿模型，对不同氧含量背景的待测气样进行独立修正，有效解决了实际测量中不同浓度氧气对测量结果的干扰程度存在差异问题，大大提高了测量浓度准确性。1. The present invention is based on gas chromatography with FID detector to measure non-methane total hydrocarbons, combined with the characteristics of the influence of oxygen on FID detector in this technology to formulate an oxygen interference dynamic compensation model, and independently corrects the gas samples to be tested with different oxygen content backgrounds , which effectively solves the problem of differences in the degree of interference of different concentrations of oxygen on the measurement results in actual measurement, and greatly improves the accuracy of the measurement concentration.
2、本发明建立的氧干扰动态补偿模型可根据不同工况选择补偿基准点，可将不同氧气浓度条件下的样品气体补偿至统一浓度，最大程度降低待测气样中氧气含量变化导致的测量结果准确性差的问题，且修正范围广，可满足不同氧气含量背景中更多工况条件下待测气样测量准确修正。2. The oxygen interference dynamic compensation model established by the present invention can select the compensation reference point according to different working conditions, and can compensate the sample gas under different oxygen concentration conditions to a uniform concentration, minimizing the measurement caused by the change of the oxygen content in the gas sample to be tested The accuracy of the result is poor, and the correction range is wide, which can meet the accurate correction of the measurement of the gas sample to be tested under more working conditions in different oxygen content backgrounds.
3、本发明通过氧气浓度检测模块对每一分析周期内的待测气样中氧气浓度进行实时测量及修正，可满足复杂工况条件中氧气浓度存在实时动态变化时对测量结果进行准确修正，工况适应性更强。3. The present invention uses the oxygen concentration detection module to measure and correct the oxygen concentration in the gas sample to be tested in real time in each analysis cycle, which can accurately correct the measurement results when there is a real-time dynamic change in the oxygen concentration in complex working conditions. The working conditions are more adaptable.
4、本发明相较于其他通过算法对测量结果数值进行修正的方式，实际应用更加便捷，无需定期对修正算法进行质控更新，可以保证修正方式的长期稳定有效。4. Compared with other methods of correcting the value of measurement results through algorithms, the present invention is more convenient in practical application, and does not need to regularly update the correction algorithm for quality control, which can ensure the long-term stability and effectiveness of the correction method.
以上所述仅是对本发明的优选实施例及原理进行了详细说明，对本领域的普通技术人员而言，依据本发明提供的思想，在具体实施方式上会有改变之处，而这些改变也应视为本发明的保护范围。The above is only a detailed description of the preferred embodiments and principles of the present invention. For those of ordinary skill in the art, according to the ideas provided by the present invention, there will be changes in the specific implementation, and these changes should also be It is regarded as the protection scope of the present invention.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117147671A (en) * | 2023-10-30 | 2023-12-01 | 杭州盈创环境科技有限公司 | Non-methane total hydrocarbon detection device and method based on dilution technology |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040035183A1 (en) * | 2000-01-25 | 2004-02-26 | The State Of Oregon Acting And Through The State Board Of Higher Education On Behalf Of Portl | Method and apparatus for sample analysis |
| CN109991345A (en) * | 2019-05-07 | 2019-07-09 | 赛默飞世尔（上海）仪器有限公司 | Device for detecting sample gas and method for detecting sample gas by means of flame ionization detector |
| CN112903879A (en) * | 2019-12-04 | 2021-06-04 | 株式会社岛津制作所 | Method and apparatus for flame ionization detection of oxygen-containing samples |
| CN213580285U (en) * | 2020-07-10 | 2021-06-29 | 杭州因诺维新科技有限公司 | Non-methane total hydrocarbon on-line analysis device |
| CN115201071A (en) * | 2022-09-09 | 2022-10-18 | 杭州泽天春来科技有限公司 | Air diffusion tracing method and system based on factory-bound malodor online monitoring system |
-
2022
- 2022-10-31 CN CN202211349920.5A patent/CN115718148A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040035183A1 (en) * | 2000-01-25 | 2004-02-26 | The State Of Oregon Acting And Through The State Board Of Higher Education On Behalf Of Portl | Method and apparatus for sample analysis |
| CN109991345A (en) * | 2019-05-07 | 2019-07-09 | 赛默飞世尔（上海）仪器有限公司 | Device for detecting sample gas and method for detecting sample gas by means of flame ionization detector |
| CN112903879A (en) * | 2019-12-04 | 2021-06-04 | 株式会社岛津制作所 | Method and apparatus for flame ionization detection of oxygen-containing samples |
| JP2021089268A (en) * | 2019-12-04 | 2021-06-10 | 株式会社島津製作所 | Method and device for detecting ionization of hydrogen flames for oxygen-containing sample |
| CN213580285U (en) * | 2020-07-10 | 2021-06-29 | 杭州因诺维新科技有限公司 | Non-methane total hydrocarbon on-line analysis device |
| CN115201071A (en) * | 2022-09-09 | 2022-10-18 | 杭州泽天春来科技有限公司 | Air diffusion tracing method and system based on factory-bound malodor online monitoring system |
Non-Patent Citations (1)
| Title |
|---|
| 王兴华等: "改进气相色谱法测定总烃与非甲烷总烃", 《化工环保》, vol. 35, no. 6, 31 December 2015 (2015-12-31), pages 662 - 666 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117147671A (en) * | 2023-10-30 | 2023-12-01 | 杭州盈创环境科技有限公司 | Non-methane total hydrocarbon detection device and method based on dilution technology |
| CN117147671B (en) * | 2023-10-30 | 2024-02-06 | 杭州盈创环境科技有限公司 | Non-methane total hydrocarbon detection device and method based on dilution technology |
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