[go: up one dir, main page]

CN118688338A - A direct measurement device and analysis method for methane and non-methane total hydrocarbons in ambient air - Google Patents

A direct measurement device and analysis method for methane and non-methane total hydrocarbons in ambient air Download PDF

Info

Publication number
CN118688338A
CN118688338A CN202410797208.4A CN202410797208A CN118688338A CN 118688338 A CN118688338 A CN 118688338A CN 202410797208 A CN202410797208 A CN 202410797208A CN 118688338 A CN118688338 A CN 118688338A
Authority
CN
China
Prior art keywords
methane
inlet
way valve
enrichment
outlet
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.)
Granted
Application number
CN202410797208.4A
Other languages
Chinese (zh)
Other versions
CN118688338B (en
Inventor
胡超
李书波
周洁
陈强
李启杰
丁晓晓
李虹杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan Tianhong Environmental Protection Technology Co ltd
Original Assignee
Wuhan Tianhong Environmental Protection Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wuhan Tianhong Environmental Protection Technology Co ltd filed Critical Wuhan Tianhong Environmental Protection Technology Co ltd
Priority to CN202410797208.4A priority Critical patent/CN118688338B/en
Publication of CN118688338A publication Critical patent/CN118688338A/en
Application granted granted Critical
Publication of CN118688338B publication Critical patent/CN118688338B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • G01N30/08Preparation using an enricher
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • G01N30/12Preparation by evaporation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/16Injection
    • G01N30/20Injection using a sampling valve
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/26Conditioning of the fluid carrier; Flow patterns
    • G01N30/38Flow patterns
    • G01N30/46Flow patterns using more than one column
    • G01N30/461Flow patterns using more than one column with serial coupling of separation columns
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/62Detectors specially adapted therefor
    • G01N30/64Electrical detectors
    • G01N30/68Flame ionisation detectors
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/86Signal analysis
    • G01N30/8675Evaluation, i.e. decoding of the signal into analytical information
    • G01N30/8679Target compound analysis, i.e. whereby a limited number of peaks is analysed
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • G01N30/12Preparation by evaporation
    • G01N2030/121Preparation by evaporation cooling; cold traps
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • G01N30/12Preparation by evaporation
    • G01N2030/126Preparation by evaporation evaporating sample
    • G01N2030/128Thermal desorption analysis
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/16Injection
    • G01N30/20Injection using a sampling valve
    • G01N2030/201Injection using a sampling valve multiport valves, i.e. having more than two ports
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/16Injection
    • G01N30/20Injection using a sampling valve
    • G01N2030/207Injection using a sampling valve with metering cavity, e.g. sample loop
    • G01N2030/208Injection using a sampling valve with metering cavity, e.g. sample loop with more than one cavity

Landscapes

  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Library & Information Science (AREA)
  • Engineering & Computer Science (AREA)
  • Sampling And Sample Adjustment (AREA)

Abstract

The invention provides a direct measurement device and an analysis method for methane and non-methane total hydrocarbons in the environment air, wherein the measurement device comprises a ten-way valve, a six-way valve, a non-methane total hydrocarbon enrichment trap, a first quantitative ring, a first EPC and an empty column which are connected with the ten-way valve, a second quantitative ring, a second EPC and a sampling pump which are connected with the six-way valve, an outlet of the empty column is connected with an FID detector, and a PQ column is arranged between the ten-way valve and the six-way valve. The non-methane total hydrocarbon enrichment trap comprises refrigeration equipment, a cold trap cavity, an enrichment pipe, heating equipment and a thermocouple; the refrigerating equipment is connected with the cold trap cavity, the enrichment pipe is arranged in the cold trap cavity, the heating equipment is directly connected with the enrichment pipe, and the thermocouple is arranged at the joint of the cold trap cavity and the refrigerating equipment. The device can realize direct enrichment and direct analysis of non-methane total hydrocarbons in the ambient air sample, avoids the adsorption of methane possibly caused by the adoption of the adsorbent, and has high detection accuracy.

Description

一种环境空气甲烷、非甲烷总烃直接测量装置和分析方法A direct measurement device and analysis method for methane and non-methane total hydrocarbons in ambient air

技术领域Technical Field

本发明属于环境空气在线监测领域,具体涉及一种环境空气甲烷、非甲烷总烃直接测量装置和分析方法。The invention belongs to the field of online monitoring of ambient air, and in particular relates to a direct measurement device and analysis method for methane and non-methane total hydrocarbons in ambient air.

背景技术Background Art

非甲烷总烃(Nonmethane Hydrocarbons,NMHC)通常是指除甲烷以外的所有可挥发的碳氢化合物及其衍生物(其中主要是C2~C8)。HJ 38和HJ 1012中规定非甲烷总烃是在标准规定的测定条件下,从总烃中扣除甲烷以后其他气态有机化合物的总和(除非另有说明,结果以碳计),而在环境监测实践中可发现非甲烷总烃除了含有碳氢化合物外,还包括醇、醛、酸、酯、酮等碳氢化合物衍生物,以及C8以上挥发性有机物质。非甲烷总经有较大的光化学活性,是形成光化学烟雾的前体物。Nonmethane Hydrocarbons (NMHC) usually refers to all volatile hydrocarbons and their derivatives (mainly C2 to C8) except methane. HJ 38 and HJ 1012 stipulate that nonmethane hydrocarbons are the sum of other gaseous organic compounds after methane is deducted from total hydrocarbons under the measurement conditions specified in the standard (unless otherwise specified, the result is calculated in carbon). In environmental monitoring practice, it can be found that nonmethane hydrocarbons, in addition to hydrocarbons, also include hydrocarbon derivatives such as alcohols, aldehydes, acids, esters, ketones, and volatile organic substances above C8. Nonmethane hydrocarbons have greater photochemical activity and are precursors to the formation of photochemical smog.

目前甲烷、非甲烷总烃的测量方法有两种:一种是参照《固定污染源废气 总烃、甲烷和非甲烷总烃的测定气相色谱法》(HJ 38-2017)、《环境空气 总烃、甲烷和非甲烷总烃的测定直接进样-气相色谱法》(HJ 604-2017),其所用的方法为差减法,即分别用两根色谱柱测定总烃和甲烷的含量(以碳计),两者之差即为非甲烷总烃的含量;另一种是参照《环境空气非甲烷总烃连续自动监测技术规定(试行)》规定,其所用的方法为直接法,即通过色谱柱分离、阀切换、反吹等手段分离出总烃中的甲烷,使非甲烷总烃单独出峰,直接测定其浓度。经过大量的实验和研究表明,直接法更适用于环境空气非甲烷总烃连续在线监测领域。At present, there are two methods for measuring methane and non-methane total hydrocarbons: one is to refer to "Gas Chromatography for Determination of Total Hydrocarbons, Methane and Non-methane Total Hydrocarbons in Waste Gas from Stationary Pollution Sources" (HJ 38-2017) and "Direct Injection-Gas Chromatography for Determination of Total Hydrocarbons, Methane and Non-methane Total Hydrocarbons in Ambient Air" (HJ 604-2017). The method used is the difference method, that is, two chromatographic columns are used to determine the content of total hydrocarbons and methane (in terms of carbon), and the difference between the two is the content of non-methane total hydrocarbons; the other is to refer to the "Technical Regulations for Continuous Automatic Monitoring of Non-methane Total Hydrocarbons in Ambient Air (Trial)", and the method used is the direct method, that is, by separating the methane from the total hydrocarbons through chromatographic column separation, valve switching, backflushing and other means, so that the non-methane total hydrocarbons have a separate peak and directly measure their concentration. After a large number of experiments and studies, it has been shown that the direct method is more suitable for the field of continuous online monitoring of non-methane total hydrocarbons in ambient air.

市面上直接法测量环境空气甲烷、非甲烷总烃的方法主要有两类,一类是色谱柱反吹模式,即通过色谱柱分离甲烷和非甲烷总烃,再将非甲烷总烃反吹,计算非甲烷总烃含量,该方法在色谱柱选择上有特殊需求,必须保证甲烷与其他烃类分离,而其他烃类物质在色谱柱上保留也不能太强,当组分越多,组分含碳量越高,峰型拖尾越严重,影响定量,另外由于未对非甲烷总烃进行富集,当其含量较低时容易出现无法检出的现象;另一类是吸附剂冷阱富集模式,即采集大量环境空气通过冷阱,在吸附剂作用下,吸附非甲烷总烃,再通过加热解析,将非甲烷总烃释放,计算非甲烷总烃含量,该方法对吸附剂要求较高,当组分含量越高,吸附效率越低,组分含碳量越高,解析越困难,使用时间越长,吸附剂越容易变性,另外空气湿度较高时,低温条件下,大体积进样,吸附剂容易出现冰堵。There are two main methods for directly measuring methane and non-methane hydrocarbons in ambient air on the market. One is the chromatographic column backflush mode, which separates methane and non-methane hydrocarbons through a chromatographic column, then backflushes the non-methane hydrocarbons to calculate the non-methane hydrocarbon content. This method has special requirements for chromatographic column selection. Methane must be separated from other hydrocarbons, and other hydrocarbons cannot be retained too strongly on the chromatographic column. The more components there are and the higher the carbon content of the components, the more severe the peak tailing will be, affecting quantification. In addition, since non-methane hydrocarbons are not enriched, when their content When the concentration is low, it is easy to fail to detect. The other is the adsorbent cold trap enrichment mode, that is, a large amount of ambient air is collected through the cold trap, and non-methane total hydrocarbons are adsorbed under the action of the adsorbent, and then the non-methane total hydrocarbons are released by heating and analysis, and the non-methane total hydrocarbon content is calculated. This method has high requirements on the adsorbent. The higher the component content, the lower the adsorption efficiency, the higher the carbon content of the component, the more difficult the analysis, the longer the use time, the easier the adsorbent is to denature. In addition, when the air humidity is high, large volume injection under low temperature conditions is prone to ice blockage of the adsorbent.

发明内容Summary of the invention

针对现有技术存在的问题,本发明提供一种非甲烷总烃富集阱,既能够除去环境空气中水分,而且能够只富集环境空气中的非甲烷总烃成分而直接放空环境空气中的甲烷成分,同时,通过深冷方式富集非甲烷总烃,从而提高了对非甲烷总烃的富集效率;并基于该非甲烷总烃富集阱提供一种环境空气甲烷、非甲烷总烃直接测量装置和分析方法。In view of the problems existing in the prior art, the present invention provides a non-methane total hydrocarbon enrichment trap, which can not only remove moisture from ambient air, but also enrich only the non-methane total hydrocarbon components in the ambient air and directly discharge the methane components in the ambient air. At the same time, the non-methane total hydrocarbons are enriched by deep cooling, thereby improving the enrichment efficiency of the non-methane total hydrocarbons; and based on the non-methane total hydrocarbon enrichment trap, a direct measurement device and analysis method for methane and non-methane total hydrocarbons in ambient air are provided.

本发明为解决现有技术中存在的问题采用的技术方案如下:The technical solution adopted by the present invention to solve the problems existing in the prior art is as follows:

一种环境空气甲烷、非甲烷总烃直接测量装置,包括一个十通阀和一个六通阀,以及与十通阀连接的非甲烷总烃富集阱、第一定量环、第一EPC(电子压力控制器)和空柱(空色谱柱),与六通阀连接的第二定量环、第二EPC(电子压力控制器)和采样泵,所述空柱的出口与所述FID检测器(氢火焰离子化检测器)相连,所述十通阀与六通阀之间还设有PQ柱(PQ色谱柱);所述环境空气中的甲烷测定过程为:通过采样泵抽取样气在第二定量环收集后,再利用PQ柱分离样气中的甲烷,经由FID检测器检测甲烷含量;所述环境空气中非甲烷总烃的测定过程为:通过采样泵抽取样气在第一定量环收集后,将样气在非甲烷总烃富集阱中进行低温富集,再加热解析出非甲烷总烃进入FID检测器检测环境空气样品中非甲烷总烃含量。A direct measurement device for methane and non-methane total hydrocarbons in ambient air comprises a ten-way valve and a six-way valve, a non-methane total hydrocarbon enrichment trap connected to the ten-way valve, a first quantitative loop, a first EPC (electronic pressure controller) and an empty column (empty chromatographic column), a second quantitative loop, a second EPC (electronic pressure controller) and a sampling pump connected to the six-way valve, the outlet of the empty column is connected to the FID detector (hydrogen flame ionization detector), and a PQ column (PQ chromatographic column) is further arranged between the ten-way valve and the six-way valve; the methane determination process in ambient air comprises: after the sample gas is extracted by the sampling pump and collected in the second quantitative loop, the methane in the sample gas is separated by the PQ column, and the methane content is detected by the FID detector; the non-methane total hydrocarbon determination process in ambient air comprises: after the sample gas is extracted by the sampling pump and collected in the first quantitative loop, the sample gas is low-temperature enriched in the non-methane total hydrocarbon enrichment trap, and then the non-methane total hydrocarbons are heated and resolved to enter the FID detector to detect the non-methane total hydrocarbon content in the ambient air sample.

所述非甲烷总烃富集阱包括制冷设备、冷阱腔、富集管、加热设备、热电偶;制冷设备与冷阱腔相连,为冷阱腔提供低温环境,富集管放置于冷阱腔之中,加热设备与富集管直接相连,用于快速加热富集管,热电偶置于冷阱腔和制冷设备的连接处,用于测定冷阱腔体内温度。The non-methane total hydrocarbon enrichment trap comprises a refrigeration device, a cold trap cavity, an enrichment tube, a heating device, and a thermocouple; the refrigeration device is connected to the cold trap cavity to provide a low-temperature environment for the cold trap cavity, the enrichment tube is placed in the cold trap cavity, the heating device is directly connected to the enrichment tube to quickly heat the enrichment tube, and the thermocouple is placed at the connection between the cold trap cavity and the refrigeration device to measure the temperature inside the cold trap cavity.

所述富集管包括三段管子,三段管子依次串联,第一段管子为空管,处于所述冷阱腔中的a位,用于除去环境空气的水分,第二段管子为空管,处于所述冷阱腔中的b位,用于富集非甲烷总烃中的高碳组分,第三段管子为AL2O3涂层管子, 处于所述冷阱腔中的c位,用于富集非甲烷总烃中的低碳组分;其中所述冷阱腔中的a位离所述制冷设备最远、b位次之,c位最近,三段管子的温度依次为:第三段<第二段<第一段。The enrichment tube comprises three sections of tubes, which are connected in series in sequence. The first section of the tube is an empty tube, located at position a in the cold trap chamber, and is used to remove moisture from the ambient air. The second section of the tube is an empty tube, located at position b in the cold trap chamber, and is used to enrich high-carbon components in non-methane total hydrocarbons . The third section of the tube is an AL2O3 coated tube, located at position c in the cold trap chamber, and is used to enrich low-carbon components in non-methane total hydrocarbons. Position a in the cold trap chamber is farthest from the refrigeration equipment, position b is the second, and position c is the closest. The temperatures of the three sections of the tube are: third section < second section < first section.

所述制冷设备为斯特林制冷机,最低制冷温度能达到-210℃,所述加热设备为低压高电流变压器,最大加热功率能达到300w,所述热电偶为K型热电偶,温度测量范围为-300℃~1000℃;所述制冷设备与所述冷阱腔之间、所述冷阱腔与所述富集管之间用导热绝缘涂层处理。The refrigeration equipment is a Stirling refrigerator, and the lowest refrigeration temperature can reach -210°C. The heating equipment is a low-voltage high-current transformer, and the maximum heating power can reach 300w. The thermocouple is a K-type thermocouple, and the temperature measurement range is -300°C to 1000°C. The refrigeration equipment and the cold trap cavity, and the cold trap cavity and the enrichment tube are treated with a thermally conductive insulating coating.

所述的十通阀包括十个接口分别为:十通阀样气入口10j、第一定量环入口10a、第一定量环出口10h、十通阀样气出口10i、第一EPC入口10g、非甲烷富集阱入口10b、非甲烷富集阱出口10f、PQ柱出口10d、空柱入口10c、排空口10e。The ten-way valve includes ten interfaces, namely: a ten-way valve sample gas inlet 10j, a first quantitative loop inlet 10a, a first quantitative loop outlet 10h, a ten-way valve sample gas outlet 10i, a first EPC inlet 10g, a non-methane enrichment trap inlet 10b, a non-methane enrichment trap outlet 10f, a PQ column outlet 10d, an empty column inlet 10c, and an exhaust port 10e.

所述十通阀为两位十通阀,即有两种连通工作状态,分别为A位和B位,当十通阀处于A位时:第一定量环入口10a与十通阀样气入口10j相通、非甲烷富集阱入口10b与空柱入口10c相通、PQ柱出口10d与排空口10e相通、非甲烷富集阱出口10f与第一EPC入口10g相通、第一定量环出口10h与十通阀样气出口10i通;当十通阀处于B位时:第一定量环入口10a与非甲烷富集阱入口10b相通、空柱入口10c与PQ柱出口10d相通、排空口10e与非甲烷富集阱出口10f相通、第一EPC入口10g与第一定量环出口10h相通、十通阀样气出口10i与十通阀样气入口10j相通。The ten-way valve is a two-position ten-way valve, that is, it has two connected working states, namely position A and position B. When the ten-way valve is in position A, the first quantitative loop inlet 10a is connected to the ten-way valve sample gas inlet 10j, the non-methane enrichment trap inlet 10b is connected to the empty column inlet 10c, the PQ column outlet 10d is connected to the exhaust port 10e, the non-methane enrichment trap outlet 10f is connected to the first EPC inlet 10g, and the first quantitative loop outlet 10h is connected to the ten-way valve sample gas outlet 10i; when the ten-way valve is in position B, the first quantitative loop inlet 10a is connected to the non-methane enrichment trap inlet 10b, the empty column inlet 10c is connected to the PQ column outlet 10d, the exhaust port 10e is connected to the non-methane enrichment trap outlet 10f, the first EPC inlet 10g is connected to the first quantitative loop outlet 10h, and the ten-way valve sample gas outlet 10i is connected to the ten-way valve sample gas inlet 10j.

所述的六通阀包括六个接口分别为:六通阀样气入口6b、第二定量环入口6c、第二定量环出口6f、采样泵入口6a、第二EPC入口6e、PQ柱入口6d;其中所述的十通阀样气出口10i与所述的六通阀样气入口6b相连。The six-way valve includes six interfaces: six-way valve sample gas inlet 6b, second quantitative loop inlet 6c, second quantitative loop outlet 6f, sampling pump inlet 6a, second EPC inlet 6e, and PQ column inlet 6d; wherein the ten-way valve sample gas outlet 10i is connected to the six-way valve sample gas inlet 6b.

所述六通阀为两位六通阀,即有两种连通工作状态,分别为A位和B位,当六通阀处于A位时:采样泵入口6a与第二定量环出口6f相通、第二EPC入口6e与PQ柱入口6d相通、第二定量环入口6c与六通阀样气入口6b相通,当六通阀处于B位时:采样泵入口6a与六通阀样气入口6b相通、第二定量环入口6c与PQ柱入口6d相通、第二EPC入口6e与第二定量环出口6f相通。The six-way valve is a two-position six-way valve, that is, it has two connecting working states, namely position A and position B. When the six-way valve is in position A: the sampling pump inlet 6a is connected to the second quantitative loop outlet 6f, the second EPC inlet 6e is connected to the PQ column inlet 6d, and the second quantitative loop inlet 6c is connected to the six-way valve sample gas inlet 6b. When the six-way valve is in position B: the sampling pump inlet 6a is connected to the six-way valve sample gas inlet 6b, the second quantitative loop inlet 6c is connected to the PQ column inlet 6d, and the second EPC inlet 6e is connected to the second quantitative loop outlet 6f.

本发明还提供一种环境空气甲烷、非甲烷总烃直接测量装置的分析方法,包括以下步骤:The present invention also provides an analysis method of a direct measurement device for methane and non-methane total hydrocarbons in ambient air, comprising the following steps:

步骤1、采样,所述的十通阀和六通阀切换到A号位,样气通过采样泵抽取进入第一定量环和第二定量环;Step 1, sampling, the ten-way valve and the six-way valve are switched to position A, and the sample gas is drawn into the first quantitative ring and the second quantitative ring by the sampling pump;

具体地,在采样阶段时:样气(即待测环境空气)依次通过样气入口10j、第一定量环入口10a、第一定量环、第一定量环出口10h、十通阀样气出口10i、六通阀样气入口6b、第二定量环入口6c、第二定量环出口6f、采样泵入口6a连通至采样泵。Specifically, during the sampling stage: the sample gas (i.e., the ambient air to be tested) is connected to the sampling pump in sequence through the sample gas inlet 10j, the first quantitative ring inlet 10a, the first quantitative ring, the first quantitative ring outlet 10h, the ten-way valve sample gas outlet 10i, the six-way valve sample gas inlet 6b, the second quantitative ring inlet 6c, the second quantitative ring outlet 6f, and the sampling pump inlet 6a.

步骤2、甲烷分析与非甲烷总烃富集,所述的十通阀和六通阀切换到B号位,一路载气(载气为高纯氦气,纯度为99.999%)通过第一EPC将第一定量环样品带入非甲烷总烃富集阱中进行富集,富集温度为-185℃~-165℃,另一路载气通过第二EPC将第二定量环样品带入PQ柱中分离出甲烷,由FID检测器检测甲烷含量;Step 2, methane analysis and non-methane total hydrocarbon enrichment, the ten-way valve and the six-way valve are switched to position B, one carrier gas (the carrier gas is high-purity helium with a purity of 99.999%) is used to carry the first quantitative loop sample into the non-methane total hydrocarbon enrichment trap for enrichment through the first EPC, and the enrichment temperature is -185°C to -165°C, and the other carrier gas is used to carry the second quantitative loop sample into the PQ column through the second EPC to separate methane, and the methane content is detected by the FID detector;

具体地,在甲烷分析与非甲烷总烃富集阶段时:一路载气依次通过第一EPC、第一EPC入口10g、第一定量环出口10h、第一定量环、第一定量环入口10a、非甲烷富集阱入口10b、非甲烷总烃富集阱、非甲烷富集阱出口10f、排空口10e;另一路载气依次通过第二EPC、第二EPC入口6e、第二定量环出口6f 、第二定量环、第二定量环入口6c、PQ柱入口6d、PQ柱、PQ柱出口10d、空柱入口10c、空柱、到达FID检测器。Specifically, during the methane analysis and non-methane total hydrocarbon enrichment stage: one carrier gas passes through the first EPC, the first EPC inlet 10g, the first quantitative loop outlet 10h, the first quantitative loop, the first quantitative loop inlet 10a, the non-methane enrichment trap inlet 10b, the non-methane total hydrocarbon enrichment trap, the non-methane enrichment trap outlet 10f, and the exhaust port 10e in sequence; the other carrier gas passes through the second EPC, the second EPC inlet 6e, the second quantitative loop outlet 6f, the second quantitative loop, the second quantitative loop inlet 6c, the PQ column inlet 6d, the PQ column, the PQ column outlet 10d, the empty column inlet 10c, the empty column, and reaches the FID detector in sequence.

步骤3、非甲烷总烃分析与PQ柱吹扫,所述的十通阀和六通阀切换到A号位,快速加热非甲烷总烃富集阱到120℃,一路载气通过第一EPC将加热解析的非甲烷总烃样品带入FID检测器检测,得到非甲烷总烃的含量,另一路载气通过第二EPC反吹分离出甲烷以后的PQ柱残留组分,经十通阀的排空口放空。Step 3, non-methane total hydrocarbon analysis and PQ column purging, the ten-way valve and the six-way valve are switched to position A, the non-methane total hydrocarbon enrichment trap is quickly heated to 120°C, one carrier gas passes through the first EPC to bring the heated and analyzed non-methane total hydrocarbon sample into the FID detector for detection to obtain the content of non-methane total hydrocarbons, and the other carrier gas passes through the second EPC to back-blow the PQ column residual components after separating methane, and is discharged through the exhaust port of the ten-way valve.

具体地,在非甲烷总烃分析与PQ柱吹扫阶段时,一路载气依次通过第一EPC、第一EPC入口10g、非甲烷富集阱出口10f、非甲烷富集阱、非甲烷富集阱入口10b、空柱入口10c、空柱、到达FID检测器;另一路载气依次通过第二EPC、第二EPC入口6e、PQ柱入口6d、PQ柱、PQ柱出口10d、排空口10e进行排空。Specifically, during the non-methane total hydrocarbon analysis and PQ column purge stage, one carrier gas passes through the first EPC, the first EPC inlet 10g, the non-methane enrichment trap outlet 10f, the non-methane enrichment trap, the non-methane enrichment trap inlet 10b, the empty column inlet 10c, the empty column, and reaches the FID detector; the other carrier gas passes through the second EPC, the second EPC inlet 6e, the PQ column inlet 6d, the PQ column, the PQ column outlet 10d, and the exhaust port 10e for exhaust.

本发明具有如下优点:The present invention has the following advantages:

1、本发明通过多次优化实验设置发现非甲烷总烃富集阱温度为-185℃~-165℃时,甲烷可以全部穿透非甲烷总烃富集阱,而非甲烷总烃中可以被非甲烷总烃富集阱100%捕集;因此本发明装置可以实现非甲烷总烃的直接富集,直接分析,避免了吸附剂可能带来的对甲烷的吸附,准确度高。1. The present invention has found through multiple optimization experimental settings that when the temperature of the non-methane total hydrocarbon enrichment trap is -185°C to -165°C, methane can completely penetrate the non-methane total hydrocarbon enrichment trap, and non-methane total hydrocarbons can be 100% captured by the non-methane total hydrocarbon enrichment trap; therefore, the device of the present invention can achieve direct enrichment and direct analysis of non-methane total hydrocarbons, avoiding the adsorption of methane that may be caused by the adsorbent, and has high accuracy.

2、本发明非甲烷总烃富集阱由三段串联管子组成,三段管子依次串联,第一段管子为空管,处于所述冷阱腔中的a位,用于除去环境空气的水分,第二段为管子为空管,处于所述冷阱腔中的b位,用于富集非甲烷总烃中的高碳组分,第三段管子为AL2O3涂层管子, 处于所述冷阱腔中的c位,用于富集非甲烷总烃中的低碳组分;其中所述冷阱腔中的a位离所述制冷设备最远、b位次之,c位最近,当热电偶监测到非甲烷总烃富集阱温度为-185℃~-165℃时,三个位置的温度依次为:c位(-185℃~-165℃)<b位(-140℃~-120℃)<a位(-50℃~-30℃);通过这一结构设计,本发明巧妙的解决了现有技术中基于吸附剂吸附带来的冰堵、吸附效率低、低碳组分易穿透,高碳组分易残留等缺点,具有富集效率高、灵敏度高、抗干扰能力强,维护成本低的优点。2. The non-methane total hydrocarbon enrichment trap of the present invention is composed of three sections of serially connected pipes. The three sections of pipes are sequentially connected in series. The first section of the pipe is an empty pipe located at position a in the cold trap cavity and is used to remove moisture from the ambient air. The second section of the pipe is an empty pipe located at position b in the cold trap cavity and is used to enrich the high-carbon components in the non-methane total hydrocarbons. The third section of the pipe is an AL2O3 coated pipe. The c position in the cold trap cavity is used to enrich the low-carbon components in the non-methane total hydrocarbons; wherein the a position in the cold trap cavity is farthest from the refrigeration equipment, the b position is the second, and the c position is the closest. When the thermocouple monitors that the temperature of the non-methane total hydrocarbon enrichment trap is -185°C to -165°C, the temperatures of the three positions are: c position (-185°C to -165°C) < b position (-140°C to -120°C) < a position (-50°C to -30°C); through this structural design, the present invention cleverly solves the shortcomings of ice blockage, low adsorption efficiency, easy penetration of low-carbon components, and easy residue of high-carbon components caused by adsorbent adsorption in the prior art, and has the advantages of high enrichment efficiency, high sensitivity, strong anti-interference ability, and low maintenance cost.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1是本发明具体实施方式中环境空气甲烷、非甲烷总烃直接测量装置的结构原理图;1 is a schematic diagram of the structure of a device for directly measuring methane and non-methane total hydrocarbons in ambient air in a specific embodiment of the present invention;

图2是本发明具体实施方式中非甲烷总烃富集阱的结构示意图;FIG2 is a schematic diagram of the structure of a non-methane total hydrocarbon enrichment trap in a specific embodiment of the present invention;

图3是本发明实施例中环境空气甲烷、非甲烷总烃直接分析方法的气路流程图A;3 is a gas flow chart A of a method for direct analysis of methane and non-methane total hydrocarbons in ambient air according to an embodiment of the present invention;

图4是本发明实施例中环境空气甲烷、非甲烷总烃直接分析方法的气路流程图B;4 is a gas flow chart B of a method for direct analysis of methane and non-methane total hydrocarbons in ambient air according to an embodiment of the present invention;

图5是本发明实施例中环境空气甲烷、非甲烷总烃直接分析方法的气路流程图C;5 is a gas flow chart C of a method for direct analysis of methane and non-methane total hydrocarbons in ambient air according to an embodiment of the present invention;

图2中,1-制冷设备、2-冷阱腔、3-富集管A,4-富集管B、5-富集管C、6-热电偶、7-加热设备。In Figure 2, 1-refrigeration equipment, 2-cold trap chamber, 3-enrichment tube A, 4-enrichment tube B, 5-enrichment tube C, 6-thermocouple, 7-heating equipment.

具体实施方式DETAILED DESCRIPTION

下面通过实施例,并结合附图,对本发明的技术方案作进一步具体的说明。The technical solution of the present invention is further specifically described below through embodiments and in conjunction with the accompanying drawings.

如图1所示,一种环境空气甲烷、非甲烷总烃直接测量装置,包括一个十通阀和一个六通阀,以及与十通阀连接的非甲烷总烃富集阱、第一定量环、第一EPC(电子压力控制器)和空柱(空色谱柱),与六通阀连接的第二定量环、第二EPC(电子压力控制器)和采样泵,空柱的出口与FID检测器相连,十通阀与六通阀之间还设有PQ柱(PQ色谱柱)。其中,两个定量环均采用美国vici公司生产的定量环,第一定量环体积为5ml,第二定量环体积为2ml;EPC和FID检测器分别采用上海孚合自动化仪表有限公司生产的型号为301-10051的EPC和型号为FID-M401的FID检测器;采样泵采用德国KNF公司生产的型号为N86的采样泵。As shown in Figure 1, a direct measurement device for methane and non-methane total hydrocarbons in ambient air includes a ten-way valve and a six-way valve, as well as a non-methane total hydrocarbon enrichment trap connected to the ten-way valve, a first quantitative ring, a first EPC (electronic pressure controller) and an empty column (empty chromatographic column), a second quantitative ring connected to the six-way valve, a second EPC (electronic pressure controller) and a sampling pump, the outlet of the empty column is connected to the FID detector, and a PQ column (PQ chromatographic column) is also provided between the ten-way valve and the six-way valve. Among them, both quantitative rings are quantitative rings produced by Vici Company of the United States, the volume of the first quantitative ring is 5ml, and the volume of the second quantitative ring is 2ml; the EPC and FID detectors are respectively EPC model 301-10051 and FID model FID-M401 produced by Shanghai Fuhe Automation Instrument Co., Ltd.; the sampling pump is a sampling pump model N86 produced by KNF Company of Germany.

十通阀包括:十通阀样气入口10j、第一定量环入口10a、第一定量环出口10h、十通阀样气出口10i、第一EPC入口10g、非甲烷总烃富集阱入口10b、非甲烷总烃富集阱出口10f、PQ柱出口10d、空柱入口10c、排空口10e;The ten-way valve includes: a ten-way valve sample gas inlet 10j, a first quantitative loop inlet 10a, a first quantitative loop outlet 10h, a ten-way valve sample gas outlet 10i, a first EPC inlet 10g, a non-methane total hydrocarbon enrichment trap inlet 10b, a non-methane total hydrocarbon enrichment trap outlet 10f, a PQ column outlet 10d, an empty column inlet 10c, and an exhaust port 10e;

六通阀包括:六通阀样气入口6b、第二定量环入口6c、第二定量环出口6f、采样泵入口6a、第二EPC入口6e、PQ柱入口6d;其中十通阀样气出口10i与六通阀样气入口6b相连,空柱出口与FID检测器相连。The six-way valve includes: a six-way valve sample gas inlet 6b, a second quantitative loop inlet 6c, a second quantitative loop outlet 6f, a sampling pump inlet 6a, a second EPC inlet 6e, and a PQ column inlet 6d; wherein the ten-way valve sample gas outlet 10i is connected to the six-way valve sample gas inlet 6b, and the empty column outlet is connected to the FID detector.

十通阀为两位十通阀,即有两种连通工作状态,分别为A位和B位,当十通阀处于A位时:第一定量环入口10a与十通阀样气入口10j相通、非甲烷富集阱入口10b与空柱入口10c相通、PQ柱出口10d与排空口10e相通、非甲烷富集阱出口10f与第一EPC入口10g相通、第一定量环出口10h与十通阀样气出口10i通,当十通阀处于B位时:第一定量环入口10a与非甲烷富集阱入口10b相通、空柱入口10c与PQ柱出口10d相通、排空口10e与非甲烷富集阱出口10f相通、第一EPC入口10g与第一定量环出口10h相通、十通阀样气出口10i与十通阀样气入口10j相通。The ten-way valve is a two-position ten-way valve, that is, it has two connected working states, namely position A and position B. When the ten-way valve is in position A: the first quantitative loop inlet 10a is connected to the ten-way valve sample gas inlet 10j, the non-methane enrichment trap inlet 10b is connected to the empty column inlet 10c, the PQ column outlet 10d is connected to the exhaust port 10e, the non-methane enrichment trap outlet 10f is connected to the first EPC inlet 10g, and the first quantitative loop outlet 10h is connected to the ten-way valve sample gas outlet 10i. When the ten-way valve is in position B: the first quantitative loop inlet 10a is connected to the non-methane enrichment trap inlet 10b, the empty column inlet 10c is connected to the PQ column outlet 10d, the exhaust port 10e is connected to the non-methane enrichment trap outlet 10f, the first EPC inlet 10g is connected to the first quantitative loop outlet 10h, and the ten-way valve sample gas outlet 10i is connected to the ten-way valve sample gas inlet 10j.

六通阀为两位六通阀,即有两种连通工作状态,分别为A位和B位,当六通阀处于A位时:采样泵入口6a与第二定量环出口6f相通、第二EPC入口6e与PQ柱入口6d相通、第二定量环入口6c与六通阀样气入口6b相通,当六通阀处于B位时:采样泵入口6a与六通阀样气入口6b相通、第二定量环入口6c与PQ柱入口6d相通、第二EPC入口6e与第二定量环出口6f相通。The six-way valve is a two-position six-way valve, that is, it has two connecting working states, namely position A and position B. When the six-way valve is in position A: the sampling pump inlet 6a is connected to the second quantitative loop outlet 6f, the second EPC inlet 6e is connected to the PQ column inlet 6d, and the second quantitative loop inlet 6c is connected to the six-way valve sample gas inlet 6b. When the six-way valve is in position B: the sampling pump inlet 6a is connected to the six-way valve sample gas inlet 6b, the second quantitative loop inlet 6c is connected to the PQ column inlet 6d, and the second EPC inlet 6e is connected to the second quantitative loop outlet 6f.

如图2所示,非甲烷总烃富集阱包括制冷设备1、冷阱腔2、富集管A3、富集管B4、富集管C5、加热设备7、热电偶6;制冷设备1与冷阱腔2相连,为冷阱腔2提供低温环境,富集管A3、富集管B4、富集管C5放置于冷阱腔2之中,加热设备7与富集管直接相连,用于快速加热富集管,热电偶6置于冷阱腔2和制冷设备1的连接处,用于测定冷阱腔体内温度。As shown in FIG2 , the total non-methane hydrocarbon enrichment trap includes a refrigeration device 1, a cold trap cavity 2, an enrichment tube A3, an enrichment tube B4, an enrichment tube C5, a heating device 7, and a thermocouple 6; the refrigeration device 1 is connected to the cold trap cavity 2 to provide a low-temperature environment for the cold trap cavity 2, the enrichment tubes A3, B4, and C5 are placed in the cold trap cavity 2, the heating device 7 is directly connected to the enrichment tubes to quickly heat the enrichment tubes, and the thermocouple 6 is placed at the connection between the cold trap cavity 2 and the refrigeration device 1 to measure the temperature inside the cold trap cavity.

富集管包括三段管子,分别为富集管A3、富集管B4、富集管C5,三段管子依次串联,富集管A3为空管,处于冷阱腔中的a位,用于除去环境空气的水分,富集管B4为空管,处于冷阱腔中的b位,用于富集非甲烷总烃中的高碳组分,富集管C5为AL2O3涂层管子, 处于冷阱腔中的c位,用于富集非甲烷总烃中的低碳组分;其中冷阱腔中的a位离制冷设备1最远、b位次之,c位最近。The enrichment tube includes three sections of tubes, namely, enrichment tube A3, enrichment tube B4, and enrichment tube C5. The three sections of tubes are connected in series in sequence. Enrichment tube A3 is an empty tube, located at position a in the cold trap cavity, and is used to remove moisture from the ambient air. Enrichment tube B4 is an empty tube, located at position b in the cold trap cavity, and is used to enrich high-carbon components in non-methane total hydrocarbons. Enrichment tube C5 is an AL2O3 coated tube, located at position c in the cold trap cavity, and is used to enrich low-carbon components in non-methane total hydrocarbons. Among them, position a in the cold trap cavity is farthest from the refrigeration equipment 1, position b is the second, and position c is the closest.

制冷设备1为斯特林制冷机,最低制冷温度能达到-210℃,加热设备7为低压高电流变压器,最大加热功率能达到300w,热电偶6为K型热电偶,温度测量范围为-300℃~1000℃;制冷设备1与冷阱腔2之间,冷阱腔2与富集管之间用导热绝缘涂层处理。The refrigeration equipment 1 is a Stirling refrigerator, and the lowest refrigeration temperature can reach -210°C. The heating equipment 7 is a low-voltage high-current transformer, and the maximum heating power can reach 300w. The thermocouple 6 is a K-type thermocouple, and the temperature measurement range is -300°C to 1000°C. The refrigeration equipment 1 and the cold trap chamber 2, and the cold trap chamber 2 and the enrichment tube are treated with a thermal conductive insulating coating.

一种基于环境空气甲烷、非甲烷总烃直接测量装置的分析方法,包括以下步骤:An analysis method based on a direct measurement device for methane and non-methane total hydrocarbons in ambient air comprises the following steps:

步骤1、采样,十通阀和六通阀切换到A号位,样气通过采样泵抽取进入第一定量环和第二定量环。Step 1: Sampling. The ten-way valve and the six-way valve are switched to position A. The sample gas is drawn into the first quantitative loop and the second quantitative loop by the sampling pump.

具体地,在采样阶段时,如图3所示:样气依次通过样气入口10j、第一定量环入口10a、第一定量环、第一定量环出口10h、十通阀样气出口10i、六通阀样气入口6b、第二定量环入口6c、第二定量环出口6f、采样泵入口6a连通至采样泵。Specifically, during the sampling stage, as shown in Figure 3: the sample gas is connected to the sampling pump through the sample gas inlet 10j, the first quantitative ring inlet 10a, the first quantitative ring, the first quantitative ring outlet 10h, the ten-way valve sample gas outlet 10i, the six-way valve sample gas inlet 6b, the second quantitative ring inlet 6c, the second quantitative ring outlet 6f, and the sampling pump inlet 6a.

步骤2、甲烷分析与非甲烷总烃富集,十通阀和六通阀切换到B号位,一路载气通过第一EPC将第一定量环样品带入非甲烷总烃富集阱中进行富集,富集温度为-185℃,另一路载气通过第二EPC将第二定量环样品带入PQ柱中分离出甲烷,由FID检测器检测甲烷含量。Step 2: Methane analysis and non-methane total hydrocarbon enrichment. The ten-way valve and the six-way valve are switched to position B. One carrier gas passes through the first EPC to bring the first quantitative loop sample into the non-methane total hydrocarbon enrichment trap for enrichment. The enrichment temperature is -185°C. Another carrier gas passes through the second EPC to bring the second quantitative loop sample into the PQ column to separate methane. The methane content is detected by the FID detector.

具体地,在甲烷分析与非甲烷总烃富集阶段时,如图4所示:一路载气依次通过第一EPC、第一EPC入口10g、第一定量环出口10h、第一定量环、第一定量环入口10a、非甲烷富集阱入口10b、非甲烷总烃富集阱、非甲烷富集阱出口10f、排空口10e;另一路载气依次通过第二EPC、第二EPC入口6e、第二定量环出口6f 、第二定量环、第二定量环入口6c、PQ柱入口6d、PQ柱、PQ柱出口10d、空柱入口10c、空柱、到达FID检测器。Specifically, during the methane analysis and non-methane total hydrocarbon enrichment stage, as shown in Figure 4: one carrier gas passes through the first EPC, the first EPC inlet 10g, the first quantitative loop outlet 10h, the first quantitative loop, the first quantitative loop inlet 10a, the non-methane enrichment trap inlet 10b, the non-methane total hydrocarbon enrichment trap, the non-methane enrichment trap outlet 10f, and the exhaust port 10e in sequence; the other carrier gas passes through the second EPC, the second EPC inlet 6e, the second quantitative loop outlet 6f, the second quantitative loop, the second quantitative loop inlet 6c, the PQ column inlet 6d, the PQ column, the PQ column outlet 10d, the empty column inlet 10c, the empty column, and reaches the FID detector in sequence.

步骤3、非甲烷总烃分析与PQ柱吹扫,十通阀和六通阀切换到A号位,快速加热非甲烷总烃富集阱到120 ℃,一路载气通过第一EPC将加热解析的非甲烷总烃样品带入FID检测器检测,得到非甲烷总烃的含量,另一路载气通过第二EPC反吹分离出甲烷以后的PQ柱残留组分,经十通阀的排空口放空。Step 3: Analysis of non-methane total hydrocarbons and purging of the PQ column. The ten-way valve and the six-way valve are switched to position A. The non-methane total hydrocarbon enrichment trap is quickly heated to 120°C. One carrier gas passes through the first EPC to bring the heated and resolved non-methane total hydrocarbon sample into the FID detector for detection to obtain the content of non-methane total hydrocarbons. The other carrier gas passes through the second EPC to back-blow the PQ column residual components after separating methane and discharge them through the exhaust port of the ten-way valve.

具体地,在非甲烷总烃分析与PQ柱吹扫阶段时,如图5所示:一路载气依次通过第一EPC、第一EPC入口10g、非甲烷富集阱出口10f、非甲烷富集阱、非甲烷富集阱入口10b、空柱入口10c、空柱、到达FID检测器;另一路载气依次通过第二EPC、第二EPC入口6e、PQ柱入口6d、PQ柱、PQ柱出口10d、排空口10e进行排空。Specifically, during the non-methane total hydrocarbon analysis and PQ column purge stage, as shown in Figure 5: one carrier gas passes through the first EPC, the first EPC inlet 10g, the non-methane enrichment trap outlet 10f, the non-methane enrichment trap, the non-methane enrichment trap inlet 10b, the empty column inlet 10c, the empty column, and reaches the FID detector; the other carrier gas passes through the second EPC, the second EPC inlet 6e, the PQ column inlet 6d, the PQ column, the PQ column outlet 10d, and the exhaust port 10e for exhaust.

本发明的保护范围并不限于上述的实施例,显然,本领域的技术人员可以对本发明进行各种改动和变形而不脱离本发明的范围和精神。倘若这些改动和变形属于本发明权利要求及其等同技术的范围内,则本发明的意图也包含这些改动和变形在内。The protection scope of the present invention is not limited to the above-mentioned embodiments. Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the scope and spirit of the present invention. If these changes and modifications fall within the scope of the claims of the present invention and their equivalents, the intention of the present invention also includes these changes and modifications.

Claims (10)

1.一种环境空气甲烷、非甲烷总烃直接测量装置,其特征在于:包括一个十通阀和一个六通阀,以及与十通阀连接的非甲烷总烃富集阱、第一定量环、第一EPC和空柱,与六通阀连接的第二定量环、第二EPC和采样泵,所述空柱的出口与所述FID检测器相连,所述十通阀与六通阀之间还设有PQ柱;1. A direct measurement device for methane and non-methane total hydrocarbons in ambient air, characterized in that it comprises a ten-way valve and a six-way valve, and a non-methane total hydrocarbon enrichment trap, a first quantitative loop, a first EPC and an empty column connected to the ten-way valve, a second quantitative loop, a second EPC and a sampling pump connected to the six-way valve, the outlet of the empty column is connected to the FID detector, and a PQ column is further provided between the ten-way valve and the six-way valve; 所述非甲烷总烃富集阱包括制冷设备、冷阱腔、富集管、加热设备、热电偶;制冷设备与冷阱腔相连,为冷阱腔提供低温环境,富集管放置于冷阱腔之中,加热设备与富集管直接相连,用于快速加热富集管,热电偶置于冷阱腔和制冷设备的连接处,用于测定冷阱腔体内温度。The non-methane total hydrocarbon enrichment trap comprises a refrigeration device, a cold trap cavity, an enrichment tube, a heating device, and a thermocouple; the refrigeration device is connected to the cold trap cavity to provide a low-temperature environment for the cold trap cavity, the enrichment tube is placed in the cold trap cavity, the heating device is directly connected to the enrichment tube to quickly heat the enrichment tube, and the thermocouple is placed at the connection between the cold trap cavity and the refrigeration device to measure the temperature inside the cold trap cavity. 2.如权利要求1所述的一种环境空气甲烷、非甲烷总烃直接测量装置,其特征在于:所述富集管包括三段管子,三段管子依次串联,第一段管子为空管,处于所述冷阱腔中的a位,用于除去环境空气的水分,第二段管子为空管,处于所述冷阱腔中的b位,用于富集非甲烷总烃中的高碳组分,第三段管子为AL2O3涂层管子, 处于所述冷阱腔中的c位,用于富集非甲烷总烃中的低碳组分;其中所述冷阱腔中的a位离所述制冷设备最远、b位次之,c位最近,三段管子的温度依次为:第三段<第二段<第一段。2. A direct measurement device for methane and non-methane total hydrocarbons in ambient air as described in claim 1, characterized in that: the enrichment tube includes three sections of tubes, the three sections of tubes are connected in series in sequence, the first section of the tube is an empty tube, located at position a in the cold trap cavity, and is used to remove moisture from the ambient air, the second section of the tube is an empty tube, located at position b in the cold trap cavity, and is used to enrich high-carbon components in non-methane total hydrocarbons, and the third section of the tube is an AL2O3 coated tube, located at position c in the cold trap cavity, and is used to enrich low-carbon components in non-methane total hydrocarbons; wherein position a in the cold trap cavity is farthest from the refrigeration equipment, position b is second, and position c is closest, and the temperatures of the three sections of the tube are: third section < second section < first section. 3.如权利要求1所述的一种环境空气甲烷、非甲烷总烃直接测量装置,其特征在于:所述制冷设备为斯特林制冷机,所述加热设备为低压高电流变压器,所述热电偶为K型热电偶,温度测量范围为-300℃~1000℃;所述制冷设备与所述冷阱腔之间、所述冷阱腔与所述富集管之间用导热绝缘涂层处理。3. A direct measurement device for methane and non-methane total hydrocarbons in ambient air as described in claim 1, characterized in that: the refrigeration equipment is a Stirling refrigerator, the heating equipment is a low-voltage high-current transformer, the thermocouple is a K-type thermocouple, and the temperature measurement range is -300°C to 1000°C; a thermal conductive insulating coating is used between the refrigeration equipment and the cold trap cavity, and between the cold trap cavity and the enrichment tube. 4.如权利要求1所述的一种环境空气甲烷、非甲烷总烃直接测量装置,其特征在于:所述的十通阀包括十个接口分别为:十通阀样气入口(10j)、第一定量环入口(10a)、第一定量环出口(10h)、十通阀样气出口(10i)、第一EPC入口(10g)、非甲烷富集阱入口(10b)、非甲烷富集阱出口(10f)、PQ柱出口(10d)、空柱入口(10c)、排空口(10e)。4. A direct measurement device for methane and non-methane total hydrocarbons in ambient air as described in claim 1, characterized in that: the ten-way valve includes ten interfaces, namely: a ten-way valve sample gas inlet (10j), a first quantitative loop inlet (10a), a first quantitative loop outlet (10h), a ten-way valve sample gas outlet (10i), a first EPC inlet (10g), a non-methane enrichment trap inlet (10b), a non-methane enrichment trap outlet (10f), a PQ column outlet (10d), an empty column inlet (10c), and an exhaust port (10e). 5.如权利要求4所述的一种环境空气甲烷、非甲烷总烃直接测量装置,其特征在于:所述十通阀为两位十通阀,即有两种连通工作状态,分别为A位和B位,当十通阀处于A位时:第一定量环入口(10a)与十通阀样气入口(10j)相通、非甲烷富集阱入口(10b)与空柱入口(10c)相通、PQ柱出口(10d)与排空口(10e)相通、非甲烷富集阱出口(10f)与第一EPC入口(10g)相通、第一定量环出口(10h)与十通阀样气出口(10i)通;当十通阀处于B位时:第一定量环入口(10a)与非甲烷富集阱入口(10b)相通、空柱入口(10c)与PQ柱出口(10d)相通、排空口(10e)与非甲烷富集阱出口(10f)相通、第一EPC入口(10g)与第一定量环出口(10h)相通、十通阀样气出口(10i)与十通阀样气入口(10j)相通。5. A direct measurement device for methane and non-methane total hydrocarbons in ambient air as claimed in claim 4, characterized in that: the ten-way valve is a two-position ten-way valve, that is, it has two connected working states, namely position A and position B. When the ten-way valve is in position A: the first quantitative loop inlet (10a) is connected to the ten-way valve sample gas inlet (10j), the non-methane enrichment trap inlet (10b) is connected to the empty column inlet (10c), the PQ column outlet (10d) is connected to the emptying port (10e), and the non-methane enrichment trap outlet (10f) is connected to the first EPC inlet (10g), the first quantitative loop outlet (10h) is connected to the ten-way valve sample gas outlet (10i); when the ten-way valve is in position B: the first quantitative loop inlet (10a) is connected to the non-methane enrichment trap inlet (10b), the empty column inlet (10c) is connected to the PQ column outlet (10d), the exhaust port (10e) is connected to the non-methane enrichment trap outlet (10f), the first EPC inlet (10g) is connected to the first quantitative loop outlet (10h), and the ten-way valve sample gas outlet (10i) is connected to the ten-way valve sample gas inlet (10j). 6.如权利要求1所述的一种环境空气甲烷、非甲烷总烃直接测量装置,其特征在于:所述的六通阀包括六个接口分别为:六通阀样气入口(6b)、第二定量环入口(6c)、第二定量环出口(6f)、采样泵入口(6a)、第二EPC入口(6e)、PQ柱入口(6d);其中所述的十通阀样气出口(10i)与所述的六通阀样气入口(6b)相连。6. A direct measurement device for methane and non-methane total hydrocarbons in ambient air as described in claim 1, characterized in that: the six-way valve includes six interfaces: a six-way valve sample gas inlet (6b), a second quantitative loop inlet (6c), a second quantitative loop outlet (6f), a sampling pump inlet (6a), a second EPC inlet (6e), and a PQ column inlet (6d); wherein the ten-way valve sample gas outlet (10i) is connected to the six-way valve sample gas inlet (6b). 7.如权利要求6所述的一种环境空气甲烷、非甲烷总烃直接测量装置,其特征在于:所述六通阀为两位六通阀,即有两种连通工作状态,分别为A位和B位,当六通阀处于A位时:采样泵入口(6a)与第二定量环出口(6f)相通、第二EPC入口(6e)与PQ柱入口(6d)相通、第二定量环入口(6c)与六通阀样气入口(6b)相通,当六通阀处于B位时:采样泵入口(6a)与六通阀样气入口(6b)相通、第二定量环入口(6c)与PQ柱入口(6d)相通、第二EPC入口(6e)与第二定量环出口(6f)相通。7. A direct measurement device for methane and non-methane total hydrocarbons in ambient air as claimed in claim 6, characterized in that: the six-way valve is a two-position six-way valve, that is, it has two connected working states, namely position A and position B. When the six-way valve is in position A: the sampling pump inlet (6a) is connected to the second quantitative loop outlet (6f), the second EPC inlet (6e) is connected to the PQ column inlet (6d), and the second quantitative loop inlet (6c) is connected to the six-way valve sample gas inlet (6b); when the six-way valve is in position B: the sampling pump inlet (6a) is connected to the six-way valve sample gas inlet (6b), the second quantitative loop inlet (6c) is connected to the PQ column inlet (6d), and the second EPC inlet (6e) is connected to the second quantitative loop outlet (6f). 8.如权利要求1-7任一项所述的一种环境空气甲烷、非甲烷总烃直接测量装置的分析方法,其特征在于,包括以下步骤:8. The analysis method of the direct measurement device for methane and non-methane total hydrocarbons in ambient air according to any one of claims 1 to 7, characterized in that it comprises the following steps: 步骤1、采样:将所述十通阀和六通阀切换到A号位,样气通过采样泵抽取进入第一定量环和第二定量环;Step 1, sampling: switch the ten-way valve and the six-way valve to position A, and draw the sample gas into the first quantitative loop and the second quantitative loop through the sampling pump; 步骤2、甲烷分析与非甲烷总烃富集:将所述十通阀和六通阀切换到B号位,一路载气通过第一EPC将第一定量环样品带入非甲烷总烃富集阱中进行富集,富集温度为-185℃~-165℃,另一路载气通过第二EPC将第二定量环样品带入PQ柱中分离出甲烷,由FID检测器检测甲烷含量;Step 2, methane analysis and non-methane total hydrocarbon enrichment: the ten-way valve and the six-way valve are switched to position B, one carrier gas passes through the first EPC to bring the first quantitative loop sample into the non-methane total hydrocarbon enrichment trap for enrichment, the enrichment temperature is -185°C to -165°C, and the other carrier gas passes through the second EPC to bring the second quantitative loop sample into the PQ column to separate methane, and the methane content is detected by the FID detector; 步骤3、非甲烷总烃分析与PQ柱吹扫,将所述十通阀和六通阀切换到A号位,快速加热非甲烷总烃富集阱到120℃,一路载气通过第一EPC将加热解析的非甲烷总烃样品带入FID检测器检测,得到非甲烷总烃的含量,另一路载气通过第二EPC反吹分离出甲烷以后的PQ柱残留组分,经十通阀的排空口放空。Step 3, non-methane total hydrocarbon analysis and PQ column purging, the ten-way valve and the six-way valve are switched to position A, the non-methane total hydrocarbon enrichment trap is quickly heated to 120°C, one carrier gas passes through the first EPC to bring the heated and analyzed non-methane total hydrocarbon sample into the FID detector for detection to obtain the content of non-methane total hydrocarbons, and the other carrier gas passes through the second EPC to back-blow the PQ column residual components after separating methane, and is discharged through the exhaust port of the ten-way valve. 9.如权利要求8所述一种环境空气甲烷、非甲烷总烃直接测量装置的分析方法,其特征在于,具体包括以下步骤:在采样阶段时:样气依次通过样气入口(10j)、第一定量环入口(10a)、第一定量环、第一定量环出口(10h)、十通阀样气出口(10i)、六通阀样气入口(6b)、第二定量环入口(6c)、第二定量环出口(6f)、采样泵入口(6a)连通至采样泵;9. An analysis method for a direct measurement device for methane and non-methane total hydrocarbons in ambient air as claimed in claim 8, characterized in that the method specifically comprises the following steps: in the sampling stage: the sample gas is connected to the sampling pump in sequence through the sample gas inlet (10j), the first quantitative loop inlet (10a), the first quantitative loop, the first quantitative loop outlet (10h), the ten-way valve sample gas outlet (10i), the six-way valve sample gas inlet (6b), the second quantitative loop inlet (6c), the second quantitative loop outlet (6f), and the sampling pump inlet (6a); 在甲烷分析与非甲烷总烃富集阶段时:一路载气依次通过第一EPC、第一EPC入口(10g)、第一定量环出口(10h)、第一定量环、第一定量环入口(10a)、非甲烷富集阱入口(10b)、非甲烷总烃富集阱、非甲烷富集阱出口(10f)、排空口(10e);另一路载气依次通过第二EPC、第二EPC入口(6e)、第二定量环出口(6f)、第二定量环、第二定量环入口(6c)、PQ柱入口(6d)、PQ柱、PQ柱出口(10d)、空柱入口(10c)、空柱、到达FID检测器;During the methane analysis and non-methane total hydrocarbon enrichment stage: one carrier gas passes through the first EPC, the first EPC inlet (10g), the first quantitative loop outlet (10h), the first quantitative loop, the first quantitative loop inlet (10a), the non-methane enrichment trap inlet (10b), the non-methane total hydrocarbon enrichment trap, the non-methane enrichment trap outlet (10f), and the exhaust port (10e) in sequence; the other carrier gas passes through the second EPC, the second EPC inlet (6e), the second quantitative loop outlet (6f), the second quantitative loop, the second quantitative loop inlet (6c), the PQ column inlet (6d), the PQ column, the PQ column outlet (10d), the empty column inlet (10c), the empty column, and reaches the FID detector in sequence; 在非甲烷总烃分析与PQ柱吹扫阶段时,一路载气依次通过第一EPC、第一EPC入口(10g)、非甲烷富集阱出口(10f)、非甲烷富集阱、非甲烷富集阱入口(10b)、空柱入口(10c)、空柱、到达FID检测器;另一路载气依次通过第二EPC、第二EPC入口(6e)、PQ柱入口(6d)、PQ柱、PQ柱出口(10d)、排空口(10e)进行排空。During the non-methane total hydrocarbon analysis and PQ column purging stage, one carrier gas passes through the first EPC, the first EPC inlet (10g), the non-methane enrichment trap outlet (10f), the non-methane enrichment trap, the non-methane enrichment trap inlet (10b), the empty column inlet (10c), the empty column, and reaches the FID detector; the other carrier gas passes through the second EPC, the second EPC inlet (6e), the PQ column inlet (6d), the PQ column, the PQ column outlet (10d), and the exhaust port (10e) for exhaust. 10.如权利要求8所述一种环境空气甲烷、非甲烷总烃直接测量装置的分析方法,其特征在于:所述载气为高纯氦气,纯度为99.999%,所述样气为待测环境空气。10. An analysis method for a direct measurement device for methane and non-methane total hydrocarbons in ambient air as claimed in claim 8, characterized in that: the carrier gas is high-purity helium with a purity of 99.999%, and the sample gas is the ambient air to be measured.
CN202410797208.4A 2024-06-20 2024-06-20 A direct measurement device and analysis method for methane and non-methane total hydrocarbons in ambient air Active CN118688338B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202410797208.4A CN118688338B (en) 2024-06-20 2024-06-20 A direct measurement device and analysis method for methane and non-methane total hydrocarbons in ambient air

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202410797208.4A CN118688338B (en) 2024-06-20 2024-06-20 A direct measurement device and analysis method for methane and non-methane total hydrocarbons in ambient air

Publications (2)

Publication Number Publication Date
CN118688338A true CN118688338A (en) 2024-09-24
CN118688338B CN118688338B (en) 2025-04-04

Family

ID=92777048

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202410797208.4A Active CN118688338B (en) 2024-06-20 2024-06-20 A direct measurement device and analysis method for methane and non-methane total hydrocarbons in ambient air

Country Status (1)

Country Link
CN (1) CN118688338B (en)

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103111298A (en) * 2013-02-27 2013-05-22 天津大学 Cobalt-based catalyst for Fischer-Tropsch synthesis by hydrogen plasma method and preparation method thereof
CN107478488A (en) * 2016-06-07 2017-12-15 中国石油化工股份有限公司 Minor Heavy Hydrocarbon gas isotope sample-preparing system and its method for making sample
CN110333127A (en) * 2019-06-24 2019-10-15 北京大学 A gas-phase semi-volatile organic compound online measurement system, method and application
CN110568118A (en) * 2019-09-29 2019-12-13 广东环境保护工程职业学院 c2-C3Method for determining concentration of hydrocarbon substance
CN111007188A (en) * 2019-12-30 2020-04-14 常州磐宇仪器有限公司 Water removal and concentration gas circuit system and method for volatile organic compounds in atmosphere
CN212568651U (en) * 2020-06-19 2021-02-19 青岛众瑞智能仪器有限公司 Non-methane total hydrocarbon detection device
CN213903428U (en) * 2020-09-20 2021-08-06 杭州谱育科技发展有限公司 Non-methane total hydrocarbon analysis device
CN113791133A (en) * 2021-09-15 2021-12-14 上海朋环测控技术股份有限公司 A kind of direct measurement method and detection system of non-methane total hydrocarbons
CN114235941A (en) * 2022-02-28 2022-03-25 华电智控(北京)技术有限公司 Direct detection device and method for non-methane total hydrocarbons in ambient air
CN216350570U (en) * 2021-09-29 2022-04-19 苏州天蓝分析仪器有限公司 Device for directly measuring non-methane total hydrocarbon with low concentration
CN116183735A (en) * 2022-08-18 2023-05-30 天津津普利环保科技股份有限公司 Online detection system and detection method for total non-methane hydrocarbon content in ambient air
CN117907448A (en) * 2022-10-12 2024-04-19 中国石油天然气股份有限公司 Device for measuring intermediate carbon isotope of propane and application thereof

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103111298A (en) * 2013-02-27 2013-05-22 天津大学 Cobalt-based catalyst for Fischer-Tropsch synthesis by hydrogen plasma method and preparation method thereof
CN107478488A (en) * 2016-06-07 2017-12-15 中国石油化工股份有限公司 Minor Heavy Hydrocarbon gas isotope sample-preparing system and its method for making sample
CN110333127A (en) * 2019-06-24 2019-10-15 北京大学 A gas-phase semi-volatile organic compound online measurement system, method and application
US20200400622A1 (en) * 2019-06-24 2020-12-24 Peking University Online measuring system, method and application for semi-volatile organic compound in gas phase
CN110568118A (en) * 2019-09-29 2019-12-13 广东环境保护工程职业学院 c2-C3Method for determining concentration of hydrocarbon substance
CN111007188A (en) * 2019-12-30 2020-04-14 常州磐宇仪器有限公司 Water removal and concentration gas circuit system and method for volatile organic compounds in atmosphere
CN212568651U (en) * 2020-06-19 2021-02-19 青岛众瑞智能仪器有限公司 Non-methane total hydrocarbon detection device
CN213903428U (en) * 2020-09-20 2021-08-06 杭州谱育科技发展有限公司 Non-methane total hydrocarbon analysis device
CN113791133A (en) * 2021-09-15 2021-12-14 上海朋环测控技术股份有限公司 A kind of direct measurement method and detection system of non-methane total hydrocarbons
CN216350570U (en) * 2021-09-29 2022-04-19 苏州天蓝分析仪器有限公司 Device for directly measuring non-methane total hydrocarbon with low concentration
CN114235941A (en) * 2022-02-28 2022-03-25 华电智控(北京)技术有限公司 Direct detection device and method for non-methane total hydrocarbons in ambient air
CN116183735A (en) * 2022-08-18 2023-05-30 天津津普利环保科技股份有限公司 Online detection system and detection method for total non-methane hydrocarbon content in ambient air
CN117907448A (en) * 2022-10-12 2024-04-19 中国石油天然气股份有限公司 Device for measuring intermediate carbon isotope of propane and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
姬红波 等: "环境空气非甲烷总烃连续监测系统研制与应用", 分析仪器, 31 May 2023 (2023-05-31), pages 10 - 19 *

Also Published As

Publication number Publication date
CN118688338B (en) 2025-04-04

Similar Documents

Publication Publication Date Title
US11467135B2 (en) Online measuring system, method and application for semi-volatile organic compound in gas phase
CN101294936B (en) Plant source volatile organic matter test method
CN102288698B (en) Analysis method and system for gas phase combustion product of cigarette
CN104777261B (en) In air, volatile organic matter cryogenic gas-chromatography analyzes system, method and device
CN102937627B (en) Online analysis method for gas components in natural gas hydrogen production process
CN103439153B (en) Atmosphere volatile organic compound condensation and concentration sampling device and method
CN112415119B (en) Cold trap pre-concentration system and method
CN102095827A (en) System and method for measuring carbon dioxide, methane and nitrous oxide in air simultaneously
CN212159710U (en) An automatic analysis system for the total composition of atmospheric volatile organic compounds
WO2019144795A1 (en) Rapid online analyzer for 14c-ams
CN110044663B (en) Laboratory flame intermediate product sampling system and analysis method
CN113791133B (en) A direct measurement method and detection system for non-methane total hydrocarbons
CN111679025A (en) Gas chromatography detection system and method for determination of perfluoroisobutyronitrile gas composition
WO1986005276A1 (en) Method and apparatus for analyzing gases dissolved in a liquid sample
CN113155988A (en) Non-methane total hydrocarbon detection system and method based on single valve
CN104007196A (en) Secondary cold trap enrichment and GC-FID (Gas Chromatography-Flame Ionization Detector) combining device and method for detecting trace hydrogen phosphide
CN205404512U (en) Freezing continuous on line analyzer of VOC that collects of electron refrigeration second grade
CN203758978U (en) Automatic continuous determination device for volume content of greenhouse gases in atmosphere
CN203443820U (en) Condensing, concentrating and sampling device for volatile organic materials in air
CN118688338A (en) A direct measurement device and analysis method for methane and non-methane total hydrocarbons in ambient air
CN209198394U (en) VOCs online monitoring system
CN106525998A (en) Method of measuring content of benzene series ingredients in stationary pollution source waste gas
CN115089993A (en) A kind of gas pre-concentration equipment and control method
CN219552352U (en) Enrichment and desorption device and equipment for organic matters in C8-C40 volatile range in atmospheric particle phase
CN202614732U (en) On-line gathering and analyzing device for polycyclic aromatic hydrocarbon in thermal cracking products

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
GR01 Patent grant