CN113092613B - Double-path non-blind area on-line analysis method for aldehyde ketone compounds in atmosphere - Google Patents
Double-path non-blind area on-line analysis method for aldehyde ketone compounds in atmosphere Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2273—Atmospheric sampling
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
- G01N2030/201—Injection using a sampling valve multiport valves, i.e. having more than two ports
Abstract
A method for analyzing aldehyde ketone compounds in double-path non-blind area atmosphere on line comprises the steps of coating a first sampling tube with coating liquid; introducing a quantitative atmospheric sample into a first sampling pipe coated with a coating liquid to collect the sample; introducing a quantitative organic reagent into a first sampling tube for completing sample collection to elute a sample, wherein the obtained eluent is a liquid sample to be detected; detecting and analyzing the liquid sample to be detected to obtain the concentrations of various aldehyde ketone compounds in the atmospheric sample; and coating the second sampling pipe while the first sampling pipe collects the sample, and continuously performing the steps of sample collection, sample elution and detection analysis by using the second sampling pipe to form the method for continuously measuring the atmospheric sample on line. The invention adopts a double-path sampling pipe design, has no sampling blind area and can realize the continuous collection of atmospheric samples; the system is simple and convenient, the equipment and the operation cost are low, and an important technical support is provided for the atmospheric environment chemical detection.
Description
Technical Field
The invention belongs to the technical field of atmospheric environment chemistry and analytical chemistry, and particularly relates to a method for on-line analysis of aldehyde ketone compounds in double-path non-blind area atmosphere.
Background
Aldehyde ketone compounds (carbonyl compounds) are important volatile components in troposphere atmosphere, have strong atmospheric reaction activity, are important precursors of peroxy radicals (ROx) in the atmosphere and organic acids and photo-oxidants (ozone and peroxy acetyl nitrate) in the atmosphere, and have important influence on regional atmospheric environment quality. In addition, aldoketones present potential threats to human health, such as formaldehyde irritation, toxicity and carcinogenicity. Accurate monitoring of the aldehyde ketone compounds in the atmosphere can provide important scientific basis for understanding process mechanisms such as degradation of volatile organic compounds, generation of free radicals and photo-oxidants and assessing environmental health risks.
Based on the important role of aldehyde ketone compounds in the atmosphere, the research of monitoring technology thereof has become one of the important directions of the current environmental monitoring research. The current method for internationally monitoring the aldehyde ketone compounds in the atmosphere mainly comprises the following steps: proton transfer mass spectrometry, preconcentration-gas chromatography/flame ionization or mass spectrometry (GC-FID/MS) online and offline analysis technologies, an offline High Performance Liquid Chromatography (HPLC) ultraviolet visible or Mass Spectrometry (MS) offline detection technology after collection of an adsorption tube, a formaldehyde spectrophotometry and the like, except that the proton transfer mass spectrometry can realize the detection of various aldehyde ketone compounds, other methods can not realize the online detection of the most main multi-component aldehyde ketone compounds in the atmosphere, however, the proton transfer mass spectrometry is difficult in aldehyde ketone calibration and very expensive in equipment price, and therefore, the development of an economic and conveniently used online high-precision analysis method for the aldehyde ketone compounds in the atmosphere is urgently needed.
Disclosure of Invention
In view of the above, one of the main objectives of the present invention is to provide a method for on-line analysis of aldehyde ketone compounds in a two-way non-blind atmosphere, so as to at least partially solve at least one of the above technical problems.
In order to achieve the above object, the present invention provides a method for on-line analysis of aldehyde ketone compounds in a two-way non-blind area atmosphere, comprising:
coating the first sampling pipe with coating liquid;
introducing a quantitative atmospheric sample into a first sampling pipe coated with a coating liquid to collect the sample;
introducing a quantitative organic reagent into a first sampling tube for completing sample collection to elute a sample, wherein the obtained eluent is a liquid sample to be detected;
detecting and analyzing the liquid sample to be detected to obtain the concentrations of various aldehyde ketone compounds in the atmospheric sample;
and coating a second sampling pipe while the first sampling pipe collects the sample, and continuously performing the steps of collecting the sample, eluting the sample, detecting and analyzing by using the second sampling pipe to form the method for continuously measuring the atmospheric sample on line.
Based on the technical scheme, compared with the prior art, the method for the on-line analysis of the aldehyde ketone compound in the double-path non-blind area atmosphere has at least one or part of the following advantages:
1. the invention adopts an on-line coating method, thereby avoiding artificial pollution in the storage and transportation process of the sampling tube;
2. the high-sensitivity detection of the species to be detected can be realized by adopting the online chromatography analysis;
3. the design of a double-path sampling pipe is adopted, no sampling blind area exists, and the continuous collection of the atmospheric sample can be realized;
4. the system is simple and convenient, the equipment and the operation cost are low, and an important technical support is provided for the atmospheric environment chemical detection.
Drawings
FIG. 1 is a schematic flow chart of a two-way non-blind area method for on-line analysis of aldehyde ketone compounds in the atmosphere according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a two-way non-blind area in-atmosphere aldehyde ketone compound on-line analytical layer system in the embodiment of the present invention.
Description of reference numerals:
101-ambient air; 201-a first derivative sampling tube; 202-a second derivative sampling tube; 211-a first multi-position valve; 212-a second multi-position valve; 213-a third multi-position valve; 214-a fourth multi-position valve; 221-solution storage container; 222-a reagent storage container; 223-a gas container; 224-a waste liquid collection device; 251-a sample injection device; 231-a first liquid pump; 232-a second liquid pump; 233-first gas flow controller; 234-a third liquid pump; 235-a fourth liquid pump; 236-a second gas flow controller; 241-an air inlet pipe; 242-an air pump; 243-electronic gas flow meter; 301-separation detection means.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to the accompanying drawings and examples to assist those skilled in the art in fully understanding the objects, features and effects of the present invention. Exemplary embodiments of the present invention are illustrated in the drawings, but it should be understood that the present invention can be embodied in other various forms and should not be limited to the embodiments set forth herein. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention. In addition, the embodiments of the present invention provided below and the technical features in the embodiments may be combined with each other in an arbitrary manner.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Furthermore, the terms "comprises," "comprising," "includes," "including," "has," "having," and the like, when used herein, specify the presence of stated features, steps, operations, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, or components. The terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," "outer," and the like refer to an orientation or positional relationship that is based on the orientation or positional relationship shown in the drawings for ease of description and simplicity of description only, and do not indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and therefore should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. Unless expressly stated or limited otherwise, the terms "mounted," "connected," and "connected" are intended to be inclusive and mean, for example, that they may be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art. All terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise defined. It is noted that the terms used herein should be interpreted as having a meaning that is consistent with the context of this specification and should not be interpreted in an idealized or overly formal sense.
The aldehyde ketone compounds in the atmosphere are more in types, the physical and chemical properties of the aldehyde ketone compounds are greatly different, the monitoring of the aldehyde ketone compounds is mainly focused on off-line analysis at present, the on-line proton transfer mass spectrometry calibration is difficult, the price of the aldehyde ketone compounds is high, only formaldehyde is used for realizing better on-line monitoring at present, and a better synchronous on-line detection technology for various aldehyde ketone compounds is not available at present. The two-way non-blind area atmosphere aldehyde ketone compound on-line analysis method provided by the invention can synchronously and accurately measure the concentration of various aldehyde ketone compounds in the atmosphere by one-time sample introduction, can realize sensitive on-line detection, and provides an important technical support for further disclosing the research of the aldehyde ketone compounds in the atmosphere.
The invention discloses a method for online analysis of aldehyde ketone compounds in double-path non-blind area atmosphere, which comprises the following steps:
coating the first sampling pipe with coating liquid;
introducing a quantitative atmospheric sample into a first sampling pipe coated with a coating liquid to collect a sample;
introducing a quantitative organic reagent into a first sampling tube for completing sample collection to elute a sample, wherein the obtained eluent is a liquid sample to be detected;
detecting and analyzing the liquid sample to be detected to obtain the concentrations of various aldehyde ketone compounds in the atmospheric sample;
and coating a second sampling pipe while the first sampling pipe collects the sample, and continuously performing the steps of collecting the sample, eluting the sample, detecting and analyzing by using the second sampling pipe to form the method for continuously measuring the atmospheric sample on line.
In some embodiments of the present invention, the method is performed using a two-way non-blind atmospheric aldehyde ketone compound on-line analysis system, comprising:
the sampling pipe device comprises a first sampling pipe and a second sampling pipe;
a multi-position valve arrangement comprising a first multi-position valve, a second multi-position valve, a third multi-position valve and a fourth multi-position valve; the input end of the first sampling pipe is connected with the output end of the first multi-position valve; the output end of the first sampling pipe is connected with the input end of the second multi-position valve; the input end of the second sampling pipe is connected with the output end of the third multi-position valve; the output end of the second sampling pipe is connected with the input end of a fourth multi-position valve;
an in-line coating apparatus including a solution storage container and a gas container; the solution storage container is internally stored with coating solution, and a liquid outlet of the solution storage container is respectively connected with the input end of the first multi-position valve and the input end of the third multi-position valve; the gas outlet of the gas container is respectively connected with the input end of the first multi-position valve and the input end of the third multi-position valve;
the online sampling device comprises an air inlet unit and an air pump unit, wherein an air inlet of the air inlet unit is communicated with the ambient atmosphere; the air outlet of the air inlet unit is respectively connected with the input end of the first multi-position valve and the input end of the third multi-position valve; an air inlet of the air pump unit is respectively connected with the output end of the second multi-position valve and the output end of the fourth multi-position valve;
an on-line elution device comprising a reagent storage container; a liquid outlet of the reagent storage container is respectively connected with the input end of the first multi-position valve and the input end of the third multi-position valve;
the input end of the waste liquid storage device is respectively connected with the output end of the second multi-position valve and the output end of the fourth multi-position valve;
the input end of the sample feeding device is respectively connected with the output end of the second multi-position valve and the output end of the fourth multi-position valve; and
and the input end of the separation detection device is connected with the output end of the sample feeding device.
In some embodiments of the present invention, the in-line coating apparatus further comprises a first gas flow controller, a gas inlet of the first gas flow controller being connected to a gas outlet of the gas container; the gas outlet of the first gas flow controller is connected with the input end of the first multi-position valve.
In some embodiments of the invention, the in-line coating apparatus further comprises a second gas flow controller; the gas inlet of the second flow controller is connected with the gas outlet of the gas container; and the air outlet of the second flow controller is connected with the input end of the third multi-position valve.
In some embodiments of the present invention, the online sampling device further comprises a gas flow meter unit, and the gas outlet of the gas pump unit is connected with the gas inlet of the gas flow meter unit.
In some embodiments of the invention, the system further comprises a first liquid pump having an inlet connected to the outlet of the solution storage vessel; and the liquid inlet of the first liquid pump is connected with the input end of the first multi-position valve.
In some embodiments of the invention, the system comprises a third liquid pump having an inlet connected to the outlet of the solution storage vessel; and a liquid inlet of the third liquid pump is connected with an input end of a third multi-position valve.
In some embodiments of the invention, the system further comprises a second liquid pump having an inlet connected to the outlet of the reagent storage container; and the liquid inlet of the second liquid pump is connected with the input end of the first multi-position valve.
In some embodiments of the invention, the system further comprises a fourth liquid pump having an inlet connected to the outlet of the reagent storage container; and a liquid inlet of the fourth liquid pump is connected with an input end of the third multi-position valve.
In some embodiments of the present invention, the separation detection device comprises a high performance liquid chromatography separation part and a detection part which are connected;
in some embodiments of the invention, the high performance liquid chromatography detection portion is an ultraviolet detector or a mass spectrometry detector.
The invention discloses a system for on-line analysis of aldehyde-ketone compounds in double-path non-blind area atmosphere, which is used for executing the method for on-line analysis of aldehyde-ketone compounds in double-path non-blind area atmosphere, and comprises the following steps:
the sampling pipe device comprises a first sampling pipe and a second sampling pipe;
a multi-position valve arrangement comprising a first multi-position valve, a second multi-position valve, a third multi-position valve and a fourth multi-position valve; the input end of the first sampling pipe is connected with the output end of the first multi-position valve; the output end of the first sampling pipe is connected with the input end of the second multi-position valve; the input end of the second sampling pipe is connected with the output end of the third multi-position valve; the output end of the second sampling pipe is connected with the input end of a fourth multi-position valve;
an in-line coating apparatus including a solution storage container and a gas container; the solution storage container is internally stored with coating solution, and a liquid outlet of the solution storage container is respectively connected with the input end of the first multi-position valve and the input end of the third multi-position valve; the gas outlet of the gas container is respectively connected with the input end of the first multi-position valve and the input end of the third multi-position valve;
the online sampling device comprises an air inlet unit and an air pump unit, wherein an air inlet of the air inlet unit is communicated with the ambient atmosphere; the air outlet of the air inlet unit is respectively connected with the input end of the first multi-position valve and the input end of the third multi-position valve; an air inlet of the air pump unit is respectively connected with the output end of the second multi-position valve and the output end of the fourth multi-position valve;
an on-line elution device comprising a reagent storage container; a liquid outlet of the reagent storage container is respectively connected with the input end of the first multi-position valve and the input end of the third multi-position valve;
the input end of the waste liquid storage device is respectively connected with the output end of the second multi-position valve and the output end of the fourth multi-position valve;
the input end of the sample injection device is respectively connected with the output end of the second multi-position valve and the output end of the fourth multi-position valve; and
and the input end of the separation detection device is connected with the output end of the sample feeding device.
In some embodiments of the present invention, the in-line coating apparatus further comprises a first gas flow controller, a gas inlet of the first gas flow controller being connected to a gas outlet of the gas container; the gas outlet of the first gas flow controller is connected with the input end of the first multi-position valve.
In some embodiments of the invention, the in-line coating apparatus further comprises a second gas flow controller; the gas inlet of the second flow controller is connected with the gas outlet of the gas container; and the air outlet of the second flow controller is connected with the input end of the third multi-position valve.
In some embodiments of the present invention, the online sampling device further comprises a gas flow meter unit, and the gas outlet of the gas pump unit is connected with the gas inlet of the gas flow meter unit.
In some embodiments of the invention, the system comprises a first liquid pump having an inlet connected to the outlet of the solution storage vessel; and the liquid inlet of the first liquid pump is connected with the input end of the first multi-position valve.
In some embodiments of the invention, the system comprises a third liquid pump having an inlet connected to the outlet of the solution storage vessel; and a liquid inlet of the third liquid pump is connected with an input end of a third multi-position valve.
In some embodiments of the invention, the system comprises a second liquid pump having an inlet connected to the outlet of the reagent storage container; and the liquid inlet of the second liquid pump is connected with the input end of the first multi-position valve.
In some embodiments of the invention, the system comprises a fourth liquid pump having an inlet connected to the outlet of the reagent storage container; and a liquid inlet of the fourth liquid pump is connected with an input end of the third multi-position valve.
In some embodiments of the present invention, the separation detection device comprises a high performance liquid chromatography separation part and a detection part which are connected.
In some embodiments of the invention, the high performance liquid chromatography detection portion is an ultraviolet detector or a mass spectrometry detector.
In an exemplary embodiment, the method for on-line analysis of aldehyde ketone compounds in atmosphere with two paths of non-blind areas provided by the invention comprises the following steps: coating on line to prepare a sampling tube; collecting aldehyde ketone compounds in the atmosphere; quantitatively eluting the sampling tube to obtain a collected sample; and (5) carrying out chromatographic separation detection to obtain the concentration of the aldehyde ketone compound in the atmosphere.
The system adopted in the implementation process of the double-path non-blind area atmosphere aldehyde ketone compound on-line analysis method comprises a sampling tube device, an on-line coating device, an on-line sampling device, an on-line elution device, a sample injection device, a separation detection device, a waste liquid storage device and a multi-position valve device; the input end of the sampling pipe is communicated with the output end of the on-line coating device, the air inlet end of the on-line sampling device and the output end of the on-line elution device through the multi-position valve device, the output end of the sampling pipe is communicated with the input end of the sample introduction device and the input end of the waste liquid storage device through the multi-position valve device, and the output end of the sample introduction device is communicated with the input end of the separation detection device;
the sampling pipe device comprises a first sampling pipe and a second sampling pipe, wherein the first sampling pipe and the second sampling pipe are used for collecting aldehyde ketone compounds in the ambient atmosphere, and the number of the sampling pipes is two, and the sampling pipes are used for continuously and alternately collecting atmospheric environment samples;
wherein the online coating device is used for online coating 2,4 Dinitrophenylhydrazine (DNPH) required by aldehyde ketone collection to the interior of the sampling tube.
The online sampling device is used for trapping aldehyde ketone compounds in the ambient atmosphere to react with DNPH to obtain a collected sample.
The online elution device is used for eluting the sample collected by the sampling tube and purifying the sampling tube, and conveying the sample eluent to the sample injection device to obtain the sample to be detected.
The sample introduction device is used for storing a sample to be detected and inputting the sample to be detected into the separation detection device;
the separation detection device is used for separating and detecting the sample to be detected;
the multi-position valve device is used for communicating a multi-way pipeline with the sampling pipe to realize switching of different functions;
wherein the sampling tube comprises an inert tube, a filling material, a fixing piece and a joint; the inert pipe can be selected from PEEK (polyether ether ketone), PP (polypropylene), polytetrafluoroethylene and other pipes; the filling material can be selected from fine granular silica gel or C18 microspheres and other filling materials; the fixing piece is used for fixing the filling materials in the pipe, and a sieve plate or a stainless steel net and the like can be selected; the joint is used for connecting the sampling pipe with the front end device and the rear end device.
The online coating device comprises a 2, 4-dinitrophenylhydrazine solution, a solution storage container, a high-purity purified gas, a liquid pump and a gas flow controller; the 2, 4-dinitrophenylhydrazine solution is stored in the solution storage container, the liquid outlet of the solution storage container is connected with the liquid inlet of the liquid pump, the liquid outlet of the liquid pump is connected with the input end of the sampling pipe through the multi-position valve device, the gas outlet of the gas container is connected with the gas inlet of the gas flow controller, and the gas outlet of the gas flow controller is connected with the input end of the sampling pipe through the multi-position valve device.
The online sampling device comprises an air inlet pipeline, an air pump and an air flowmeter; the utility model discloses a sampling pipe, including the pipeline of admitting air, sampling pipe input end, sampling pipe output, air pump inlet, air pump gas outlet, the pipeline of admitting air front end and environmental atmosphere intercommunication, the pipeline of admitting air end through many valves with the sampling pipe input is connected, the sampling pipe output that locates passes through many valves are connected with air pump inlet gas, the air pump gas outlet with the gas flowmeter air inlet is connected, the pipeline of admitting air still has the heat tracing device for the heating is admitted air, avoids the comdenstion water influence.
Wherein, the on-line elution device comprises an organic eluent, a liquid storage container and a liquid pump; the organic eluent is stored in the liquid storage container, the liquid outlet of the liquid storage container is connected with the liquid inlet of the liquid pump, and the liquid outlet of the liquid pump is connected with the input end of the sampling pipe through a multi-position valve.
The input end of the sample injection device is connected with the output end of the sampling pipe through the multi-position valve; the output end of the sample feeding device is connected with the separation detection device; and conveying the collected liquid sample to be detected to the separation detection device for separation detection.
The separation detection device comprises a high performance liquid chromatography separation part, a detection part and a standard sample part which are connected, wherein the input end of the separation part is connected with the output end of the sample injection device, and the output end of the separation part is connected with the input end of the detection part; the separation part adopts a liquid chromatographic column; the detection part is an ultraviolet detector, a two-dimensional array or a mass spectrum detector.
Wherein, the separation detection device is specifically a high performance liquid chromatograph or an ultra high performance liquid chromatograph (HPLC or UPLC).
Wherein the waste liquid collecting device comprises a waste liquid storage container and an exhaust gas purifying device; the input port of the waste liquid storage container is connected with the output end of the sampling pipe through a multi-position valve, and waste liquid generated by the online coating device is collected; and the air outlet of the waste liquid storage container is connected with the exhaust purification device.
As shown in FIG. 1, the flow of the two-way non-blind area on-line analysis method for aldehyde ketone compounds in the atmosphere comprises the following steps:
s1 coating a sampling tube: coating a sampling tube by using a 2,4 dinitrohydrazine solution coating liquid and a high-purity gas;
s2 sample collection: collecting an environmental atmosphere sample by using a sampling pipe coated with 2,4 dinitrophenylhydrazine;
s3 elution sample: quantitatively eluting the sampled sampling tube by using an organic solvent to obtain a sample to be detected;
s4 separation detection: performing aldehyde ketone compound separation detection on the sample by using a high performance liquid chromatography;
s5 quantitative calculation: and calculating according to the gas collection volume and the elution liquid volume to obtain the concentrations of various aldehyde ketone compounds in the ambient atmosphere.
As shown in FIG. 2, the system for the two-way non-blind area on-line analysis of aldehyde ketone compounds in the atmosphere comprises: sampling tube device, online coating device, online sampling device, online elution device, sampling device, separation detection device, waste liquid storage device and multiposition valve device. The input of sampling pipe passes through many valve device with online coating device output, online sampling device inlet end, online elution device output are linked together, the output of sampling pipe passes through many valve device with sampling device's input, waste liquid storage device's input are linked together, sampling device's output with separation detection device's input is linked together.
Further, the sampling tube device comprises a first sampling tube 201 and a second sampling tube 202; the multi-position valve arrangement includes a first multi-position valve 211, a second multi-position valve 212, a third multi-position valve 213, and a fourth multi-position valve 214; the input end of the first sampling pipe 201 is connected with the output end of the first multi-position valve 211; the output end of the first sampling pipe 201 is connected with the input end of a second multi-position valve 212; the input end of the second sampling pipe 202 is connected with the output end of a third multi-position valve 213; the output of the second sampling tube 202 is connected to the input of a fourth multi-position valve 214;
further, the in-line coating apparatus includes a solution storage container 221, a gas container 223 (containing a high purity gas therein), and a first liquid pump 231, a third liquid pump 234, a first gas flow controller 233, and a second gas flow controller 236;
the solution storage container 221 contains a 2,4 dinitrophenylhydrazine solution (i.e., a coating solution); two liquid outlets at two ends of the solution storage container 221 are respectively connected with a liquid inlet of the first liquid pump 231 and a liquid inlet of the third liquid pump 234; the liquid outlets of the first liquid pump 231 and the third liquid pump 234 are respectively connected with the input ends of the first multi-position valve 211 and the third multi-position valve 213; two air outlets at two ends of the gas container 223 are respectively connected with an air inlet of the first gas flow controller 233 and an air inlet of the second flow controller 236; the air outlet of the first gas flow controller 233 and the air outlet of the second flow controller 236 are respectively connected with the input end of the first multi-position valve 211 and the input end of the third multi-position valve 213;
further, the online sampling device includes an air inlet pipe 241 (i.e., an air inlet unit), an air pump 242 (i.e., an air pump unit), and an electronic gas flow meter 243 (i.e., a gas flow meter unit); an air inlet at the front end of the air inlet pipe 241 is communicated with the ambient atmosphere 101; two air outlets at two ends of the air inlet pipe 241 are respectively connected with the input end of the first multi-position valve 211 and the input end of the third multi-position valve 213; two air inlets at two ends of the air pump 242 are respectively connected with the output end of the second multi-position valve 211 and the output end of the fourth multi-position valve 213; the air outlet of the air pump 242 is connected with the air inlet of the gas electronic flowmeter 243;
further, the on-line elution apparatus includes a reagent storage container 222, a second liquid pump 232, and a fourth liquid pump 235; two liquid outlets at two ends of the reagent storage container 222 are respectively connected with a liquid inlet of the second liquid pump 232 and a liquid inlet of the fourth liquid pump 235; the liquid outlet of the second liquid pump 232 and the liquid outlet of the fourth liquid pump 235 are connected to the input of the first multi-position valve 211 and the input of the third multi-position valve 213, respectively;
further, two input ends of two ends of the waste liquid storage device 224 are respectively connected with an output end of the second multi-position valve 212 and an output end of the fourth multi-position valve 214;
further, two input ends at two ends of the sample injection device 251 are respectively connected with an output end of the second multi-position valve 212 and an output end of the fourth multi-position valve 214; the output end of the sample introduction device 251 is connected with the input end of the separation detection device 301;
furthermore, the separation detection device comprises a high performance liquid chromatography separation part and a detection part which are connected, wherein the high performance liquid chromatography detection part device adopts an ultraviolet detector or a mass spectrum detector and is used for detecting the separated target compound;
the method for the on-line analysis of the aldehyde ketone compounds in the double-path non-blind area atmosphere by combining the system shown in the attached figure 2 specifically comprises the following steps:
the first step is as follows: and (4) preparing the system. The system comprises a sampling pipe, an online coating device, an online sampling device, an online elution device, a sample introduction device, a separation detection device, a waste liquid storage device, a multi-position valve device and the like, wherein the sampling pipe, the online coating device, the online sampling device, the online elution device, the sample introduction device, the separation detection device, the waste liquid storage device, the multi-position valve device and the like are used for carrying out system self-checking and preparation states;
the second step is that: coating a sampling tube. The first multi-position valve 211 is switched to the input connected to the first liquid pump 231, and the second multi-position valve 212 is switched to the output connected to the waste liquid storage device 224; starting the first liquid pump 231, and conveying the 2,4 dinitrohydrazine solution in the solution storage container 221 to the first sampling pipe 201 through the first multi-position valve 211; excess 2,4 dinitrohydrazine solution passes through a second multiposition valve 212 to a waste reservoir 224; then stopping the operation of the first liquid pump 231, switching the first multi-position valve 211 to an input end connected with a first gas flow controller 233, starting the first gas flow controller 233, enabling the gas container 223 to pass through the first sampling pipe 201 through the first multi-position valve 211, purging the 2,4 dinitrohydrazine solution in the first sampling pipe to the waste liquid storage device 224 through the second multi-position valve 212 by the high-purity gas in the gas container, and closing the first gas flow controller 233 after the solution in the first sampling pipe is purged completely, thereby completing the coating of the sampling pipe;
the third step: and collecting a sample. The first multi-position valve 211 is switched to an input end connected to the air inlet pipe 241, and the second multi-position valve is switched to an output end connected to the air pump 242; starting an air pump 242 and an electronic gas flowmeter 243, and setting a gas production flow U; selecting a sampling time length T according to actual needs, and closing a sampling air pump; reacting 2,4 dinitro basic hydrazine with an aldehyde ketone compound in the ambient atmosphere in the sampling tube to generate a phenylhydrazone compound, and capturing the phenylhydrazone compound in the sampling tube to finish the collection of a sample;
the fourth step: the sample was eluted. The first multi-position valve 211 is switched to the input end connected with the second liquid pump 232, and the second multi-position valve is switched to the output end connected with the sample feeding device 251; turning on the second liquid pump 232 to deliver the organic reagent in the reagent storage container 222 to the first sampling pipe 201 through the first multi-position valve 211; quantitatively (volume is V) passing the organic reagent through a sampling tube, conveying the eluted liquid into a sample injection device 251, and closing a second liquid pump 232 to obtain a liquid sample to be detected;
and fifthly, sample introduction and purification. The output end of the sample introduction device 251 is connected with the input end of the separation detection device 301, a liquid sample to be detected is conveyed to the separation detection device 301, and the sample introduction is switched to an analysis state from the sample introduction state through the switching of the sample introduction device in the separation detection device 301, so that the sample introduction is completed; then, the second liquid pump 232 is started, the organic reagent quantitatively passes through the sampling tube, the eluted liquid is conveyed to the sample injection device 251, and then the sample injection device 251 discharges the clean organic reagent, so that the purification of the first sampling tube 201, the sample injection device 251 and related pipelines is completed;
and a sixth step: and (5) separating and detecting. Separating and detecting 301, namely separating the aldehyde ketone compounds in the elution liquid sample by using methods such as gradient elution and the like, detecting by using a detector, and obtaining the concentration Ci of each aldehyde ketone compound in the elution liquid sample by combining an external standard method;
the seventh step: and (4) carrying out quantitative calculation. From the gas collection volume (U x T), the elution liquid volume (V) and the concentration Ci of each aldone compound in the elution liquid sample, the concentration Mi Ci x V/(U x T) of each aldone compound in the ambient atmosphere can be calculated.
Eighth step: a second sample tube is coated. In the third step, the coating operation of the second sample tube 202 is started. A third multi-position valve 213 is switched to an input connected to a third liquid pump 234, and a fourth multi-position valve 214 is switched to an output connected to a waste liquid storage 224; the third liquid pump 234 is started to deliver the 2,4 dinitro basic hydrazine solution in the solution storage container 221 to the second sampling pipe 202 through the third multi-position valve 213; excess 2,4 dinitro hydrazine solution passes through a fourth multi-position valve 214 to a waste liquid storage device 224; then the third liquid pump 234 is stopped, the third multi-position valve 213 is switched to the input end connected with the second gas flow controller 236, the second gas flow controller 236 is opened, the gas container 223 passes through the second sampling pipe 202 through the third multi-position valve 213, the gas container purges the 2,4 dinitrohydrazine solution in the second sampling pipe to the waste liquid storage device 224 through the fourth multi-position valve 212, and when the solution in the second sampling pipe is purged completely, the second gas flow controller 236 is closed, and the coating of the sampling pipe is completed;
the ninth step: and collecting a second sampling pipe sample. And when the third step is finished, immediately starting the sampling operation of the second sampling pipe 202. The third multi-position valve 213 is switched to an input end connected to the intake pipe 241, and the fourth multi-position valve is switched to an output end connected to the air pump 242; starting an air pump 242 and an electronic gas flowmeter 243, and setting a gas production flow U; selecting a sampling time length T according to actual needs, and closing a sampling air pump; 2,4 dinitro basic hydrazine in the sampling tube reacts with aldehyde ketone compounds in the ambient atmosphere to generate phenylhydrazone compounds which are captured in the sampling tube, so that the collection of a sample is completed;
the tenth step: and eluting the second sampling tube sample. The third multi-position valve 213 is switched to the input end connected with the fourth liquid pump 235, and the fourth multi-position valve is switched to the output end connected with the sample injection device 251; turning on the fourth liquid pump 235 to deliver the organic reagent in the reagent storage container 222 to the second sampling tube 202 through the third multi-position valve 213; quantitatively passing the organic reagent (volume is V) through a sampling tube, conveying the eluted liquid into a sample injection device 251, and closing a fourth liquid pump 235 to obtain a liquid sample to be detected;
and step eleven, sampling and purifying a second sampling pipe sample and a pipeline. The output end of the sample introduction device 251 is connected with the input end of the separation detection device 301, a liquid sample of a second sampling pipe to be detected is conveyed to the separation detection device 301, and the sample introduction is switched from a sample introduction state to an analysis state through the switching of the sample introduction device in the separation detection device 301, so that the sample introduction is completed; then, the fourth liquid pump 235 is started, the organic reagent quantitatively passes through the sampling tube, the eluted liquid is conveyed to the sample injection device 251, and then the sample injection device 251 discharges the clean organic reagent, so that the purification of the second sampling tube 202, the sample injection device 251 and related pipelines is completed;
the twelfth step: and (5) separating and detecting. Separating and detecting 301, namely separating the aldehyde ketone compounds in the elution liquid sample by using methods such as gradient elution and the like, detecting by using a detector, and obtaining the concentration Ci of each aldehyde ketone compound in the elution liquid sample by combining an external standard method;
the thirteenth step: and (4) performing quantitative calculation. From the gas collection volume (U x T), the elution liquid volume (V) and the concentration Ci of each aldone compound in the elution liquid sample, the concentration Mi Ci x V/(U x T) of each aldone compound in the ambient atmosphere can be calculated.
The alternating circulation is carried out, so that the real-time on-line analysis of various aldehyde ketone compounds in the ambient atmosphere can be realized.
It should be noted that, although the invention has been shown and described with reference to the specific exemplary embodiments thereof, it should be understood by those skilled in the art that the present invention is not limited to the above-mentioned embodiments, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, and it is intended that the invention encompass such changes and modifications as fall within the scope of the claims and the equivalent technical scope of the invention.
In particular, various combinations and/or combinations of features recited in the various embodiments and/or claims of the present invention can be made without departing from the spirit and teachings of the invention, even if such combinations or combinations are not explicitly recited in the present invention. All such combinations and/or associations are within the scope of the present invention. The scope of the invention should, therefore, be determined not with reference to the appended claims, but should instead be determined with reference to the following claims.
Claims (9)
1. A method for analyzing aldehyde ketone compounds in atmosphere on line in a double-path non-blind area mode comprises the following steps:
coating the first sampling pipe with coating liquid;
introducing a quantitative atmospheric sample into a first sampling pipe coated with a coating liquid to collect the sample;
introducing a quantitative organic reagent into a first sampling tube for completing sample collection to elute a sample, wherein the obtained eluent is a liquid sample to be detected;
detecting and analyzing the liquid sample to be detected to obtain the concentrations of various aldehyde ketone compounds in the atmospheric sample;
coating a second sampling pipe while the first sampling pipe collects a sample, and continuously performing the steps of collecting the sample, eluting the sample, detecting and analyzing by using the second sampling pipe to form a method for continuously measuring the atmospheric sample on line;
the method for the two-way non-blind area atmosphere aldehyde ketone compound on-line analysis is implemented by a two-way non-blind area atmosphere aldehyde ketone compound on-line analysis system, and the two-way non-blind area atmosphere aldehyde ketone compound on-line analysis system comprises the following steps:
the sampling pipe device comprises a first sampling pipe and a second sampling pipe, is used for collecting aldehyde ketone compounds in the ambient atmosphere, and is used for continuously and alternately collecting atmospheric environment samples;
a multi-position valve arrangement comprising a first multi-position valve, a second multi-position valve, a third multi-position valve and a fourth multi-position valve; the input end of the first sampling pipe is connected with the output end of the first multi-position valve; the output end of the first sampling pipe is connected with the input end of the second multi-position valve; the input end of the second sampling pipe is connected with the output end of the third multi-position valve; the output end of the second sampling pipe is connected with the input end of a fourth multi-position valve;
an in-line coating apparatus including a solution storage container and a gas container; the solution storage container is used for storing coating solution, and a liquid outlet of the solution storage container is respectively connected with an input end of the first multi-position valve and an input end of the third multi-position valve; the gas outlet of the gas container is respectively connected with the input end of the first multi-position valve and the input end of the third multi-position valve, and the online coating device is used for coating the coating liquid required by collecting the aldehyde ketone compound into the collecting pipe on line;
the online sampling device comprises an air inlet unit and an air pump unit, wherein an air inlet of the air inlet unit is communicated with the ambient atmosphere; the air outlet of the air inlet unit is respectively connected with the input end of the first multi-position valve and the input end of the third multi-position valve; an air inlet of the air pump unit is respectively connected with the output end of the second multi-position valve and the output end of the fourth multi-position valve, and the online acquisition device is used for capturing aldehyde ketone compounds in the ambient atmosphere to react with the coating liquid to obtain an acquired sample;
an on-line elution device comprising a reagent storage container; the online elution device is used for eluting the sample collected by the collection tube and purifying the collection tube, and conveying the sample eluent to the sample introduction device to obtain a sample to be detected;
the input end of the waste liquid storage device is respectively connected with the output end of the second multi-position valve and the output end of the fourth multi-position valve;
the input end of the sample feeding device is respectively connected with the output end of the second multi-position valve and the output end of the fourth multi-position valve, and the sample feeding device is used for storing the sample to be detected and inputting the sample to be detected into the separation detection device; and
and the input end of the separation detection device is connected with the output end of the sample feeding device, and the separation detection device is used for separating and detecting the sample to be detected.
2. The method of claim 1,
the online coating device also comprises a first gas flow controller, wherein a gas inlet of the first gas flow controller is connected with a gas outlet of the gas container; the gas outlet of the first gas flow controller is connected with the input end of the first multi-position valve.
3. The method of claim 1,
the in-line coating apparatus further comprises a second gas flow controller; the gas inlet of the second flow controller is connected with the gas outlet of the gas container; and the air outlet of the second flow controller is connected with the input end of the third multi-position valve.
4. The method of claim 1,
the online sampling device further comprises a gas flowmeter unit, and a gas outlet of the gas pump unit is connected with a gas inlet of the gas flowmeter unit.
5. The method of claim 1,
the system also comprises a first liquid pump, wherein a liquid inlet of the first liquid pump is connected with a liquid outlet of the solution storage container; and the liquid inlet of the first liquid pump is connected with the input end of the first multi-position valve.
6. The method of claim 1,
the system comprises a third liquid pump, wherein a liquid inlet of the third liquid pump is connected with a liquid outlet of the solution storage container; and a liquid inlet of the third liquid pump is connected with an input end of a third multi-position valve.
7. The method of claim 1,
the system also comprises a second liquid pump, wherein a liquid inlet of the second liquid pump is connected with a liquid outlet of the reagent storage container; and the liquid inlet of the second liquid pump is connected with the input end of the first multi-position valve.
8. The method of claim 1,
the system also comprises a fourth liquid pump, wherein a liquid inlet of the fourth liquid pump is connected with a liquid outlet of the reagent storage container; and a liquid inlet of the fourth liquid pump is connected with an input end of the third multi-position valve.
9. The method of claim 1,
the separation detection device comprises a high performance liquid chromatography separation part and a detection part which are connected;
wherein the high performance liquid chromatography detection part is an ultraviolet detector or a mass spectrum detector.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201085A (en) * | 2014-08-25 | 2014-12-10 | 暨南大学 | Direct mass spectrometric analysis method for stinking organic matters discharged from landfill |
| CN104807899A (en) * | 2015-04-07 | 2015-07-29 | 上海大学 | On-line analysis device for volatile carbonyl compounds |
| CN109406231A (en) * | 2018-12-18 | 2019-03-01 | 广州广电计量检测股份有限公司 | It is a kind of mist product in VOC measurement pretreating device and pre-treating method |
| CN209132061U (en) * | 2018-11-07 | 2019-07-19 | 江苏省环境科学研究院 | A kind of VOC dilution sampling device |
| CN111060360A (en) * | 2019-12-10 | 2020-04-24 | 无锡市产品质量监督检验院 | Aldehyde ketone sampling device generated by hot melting of additive manufacturing wire and determination method thereof |
| WO2021016374A1 (en) * | 2019-07-23 | 2021-01-28 | Snapdna | System and method for detecting and monitoring pathogens |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7257987B2 (en) * | 2000-01-25 | 2007-08-21 | State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Portland State University | Method and apparatus for sample analysis |
-
2021
- 2021-03-31 CN CN202110353186.9A patent/CN113092613B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201085A (en) * | 2014-08-25 | 2014-12-10 | 暨南大学 | Direct mass spectrometric analysis method for stinking organic matters discharged from landfill |
| CN104807899A (en) * | 2015-04-07 | 2015-07-29 | 上海大学 | On-line analysis device for volatile carbonyl compounds |
| CN209132061U (en) * | 2018-11-07 | 2019-07-19 | 江苏省环境科学研究院 | A kind of VOC dilution sampling device |
| CN109406231A (en) * | 2018-12-18 | 2019-03-01 | 广州广电计量检测股份有限公司 | It is a kind of mist product in VOC measurement pretreating device and pre-treating method |
| WO2021016374A1 (en) * | 2019-07-23 | 2021-01-28 | Snapdna | System and method for detecting and monitoring pathogens |
| CN111060360A (en) * | 2019-12-10 | 2020-04-24 | 无锡市产品质量监督检验院 | Aldehyde ketone sampling device generated by hot melting of additive manufacturing wire and determination method thereof |
Non-Patent Citations (4)
| Title |
|---|
| A new device for formaldehyde and total aldehydes real-time monitoring;Maria Sassine 等;《Environ Sci Pollut Res》;20130728;第1-12页 * |
| Optimization of an automated DNPH cartridge system for continuous measurement of ambient gaseous carbonyls;Wang, Pei.;《Library and Archives Canada》;20081231;第44-48页 * |
| 螺旋管- 高效液相色谱法在线检测甲醛的研究;马亿园 等;《环境科学与技术》;20100531;第33卷(第5期);第109-112页 * |
| 赛默飞环境空气挥发性有机物监测解决方案;赛默飞世尔科技;《Thermo Fisher Scientific》;20171231;第25-29页 * |
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