CN106645501B - Continuous automatic sampling analysis method and device for determining atmospheric carbonate - Google Patents
Continuous automatic sampling analysis method and device for determining atmospheric carbonate Download PDFInfo
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- 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
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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
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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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- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
Abstract
The invention discloses a continuous automatic sampling analysis method for measuring atmospheric carbonate, wherein a sampling unit is used for continuously and automatically sampling the atmospheric carbonate; the analysis unit first analysis module performs dry analysis on the sampling sample to obtain a first result; the second analysis module of the analysis unit performs wet analysis on the sampling sample and obtains a second result; and the processing unit compares and statistically analyzes the first result and the second result to obtain an analysis result. The invention also discloses a continuous automatic sampling analysis device for measuring the atmospheric carbonate by applying the method. The automatic sampling method and the device can complete automatic continuous sampling, shorten the whole sampling and analyzing period, increase the frequency of data, remove the interference of organic carbon and element carbon on the detection result, simultaneously analyze the carbonate in the collected atmospheric fine particulate matters by adopting two analysis methods, namely a dry method and a wet method, and can greatly improve the accuracy and the relative accuracy of the analysis of the carbonate concentration in the atmospheric fine particulate matters.
Description
Technical Field
The invention relates to the field of atmospheric environment monitoring and ecological environment research. And more particularly, to a continuous automatic sampling analysis method and apparatus for measuring atmospheric carbonate.
Background
Atmospheric particulates (Atmospheric Particulate materials) are a general term for various solid and liquid Particulate materials present in the atmosphere, and various Particulate materials are uniformly dispersed in the air to form a relatively stable and bulky suspension system, i.e., an aerosol system, so the Atmospheric particulates are also called Atmospheric Aerosols (Atmospheric Aerosols). The fine particles in the atmospheric particulates have great influence on human health and environment, wherein the content of carbon-containing substances in the aerosol is very high, and the proportion of the fine particles which have great influence on human health is larger. These carbonaceous materials can adsorb pollutants in the atmosphere, some of which have carcinogenic, teratogenic, mutagenic effects, and also affect the transparency of the atmosphere and the intensity of solar radiation. The carbonaceous materials in the atmospheric particulates fall into three categories: organic Carbon (OC), elemental Carbon (EC), and carbonate (CC), wherein the carbonate content is low, and the elemental carbon and organic carbon compounds are the main components of the aerosol. The three types of carbon-containing substances have different physical and chemical properties and different sources. Such as: EC is easy to absorb light, and the chemical property is relatively stable; OC absorption and chemical stability are inferior to EC.
The effect of carbonates in atmospheric fine particulates on acid rain neutralization and global solar radiation balance is of increasing interest to scientists. Due to its basic character, carbonates readily react with atmospheric acidic gases (including sulfur dioxide and nitrogen oxides) and accelerate SO at their surface 2 And NO x Conversion of gases to sulfates and nitrates; in addition, it is also subjected to various homogeneous and heterogeneous chemical reactions in the atmosphere directly with sulfuric acid, nitric acid and other organic acid (e.g., acetic acid, etc.) gases or particles. The carbonate in the atmospheric fine particles can be transmitted to increase the alkalinity of the surface seawater, change the acid-base balance of the seawater and promote the seawater to absorb CO in the atmosphere 2 Thus, the carbonates in the atmosphere play the role of "alkali pumps" and "biological pumps" in seawater and rain. In addition, although the content of carbonate in the ambient atmosphere is usually very low, the content is particularly high in the northern atmosphere of China, especially in the atmosphere of a sand storm. Therefore, the carbonate plays an important role in the atmospheric system, the ocean system and the land system, and has very important significance for researching the carbonate in the atmospheric fine particulate matters.
At present, the analysis of the mass concentration of the carbonate in the atmospheric fine particulate matters at home and abroad is still mainly based on the traditional offline analysis technology of sampling by a sampler and then sending the sampled sample into a laboratory for analysis, and a continuous automatic sampling device for the carbonate in the atmospheric fine particulate matters is lacked to obtain high-time-resolution observation data. The existing sampling mode has the following disadvantages:
1) The sampling process needs a great deal of manpower and materialsForce. Generally, a laboratory technician places a blank sampling membrane in an atmospheric aerosol sampler according to sampling requirements and sets sampling time, and after the sampling time is over, the laboratory technician retrieves the sample membrane to react with dilute hydrochloric acid to generate CO 2 And to CO 2 And analyzing to obtain the mass concentration of CC.
2) Damage to the equipment during sampling. Because the atmospheric aerosol carbon analyzer is not specially used for CC analysis and is not subjected to acid-proof treatment, the equipment loss is extremely high during the CC analysis, and the service life of the analyzer is seriously influenced.
3) Low frequency observation data are not suitable for establishing and verifying a process model. Due to the limitation of a sampling mode, observation errors are inevitably generated in the existing low-frequency sampling data, so that researches on a CC emission process and an environmental element control mechanism thereof are very difficult to develop.
4) Inaccuracy of the measurement results. Although some current studies show that CC concentration can be determined semi-continuously by heating, there is a great uncertainty in the analysis results due to interference from elemental carbon and organic carbon.
Therefore, the existing artificial observation technology cannot acquire effective data of long-term synchronous observation of the CC in situ, and it is urgently needed to develop an in-situ automatic observation technology to observe the CC, so as to research the functions of the CC change characteristics, evolution rules and atmospheric pollution formation mechanisms in cities, villages or background areas, acquire the measured data and parameters of a verification model, and provide a continuous automatic sampling analysis method and device for measuring the atmospheric carbonate.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a continuous automatic sampling analysis method for measuring carbonate in the atmosphere.
In order to achieve the purpose, the invention adopts the following technical scheme:
a continuous automatic sampling analysis method for determining atmospheric carbonate, which comprises the following steps:
s1: the sampling unit is used for continuously and automatically sampling the atmospheric carbonate;
s2: the analysis unit first analysis module performs dry analysis on the sampling sample to obtain a first result;
s3: the second analysis module of the analysis unit performs wet analysis on the sampling sample and obtains a second result;
s4: the processing unit compares and statistically analyzes the first and second results to obtain an analysis result.
Preferably, the sampling unit includes a sampling head, a sampling box and a sampling pump, and step S1 specifically includes:
s101: the control unit central control module sends out a sampling instruction;
s102: the control unit industrial control module receives a sampling instruction through the communication module, controls the opening and closing of the gas circuit through the logic controller and enters a sampling state;
s103: starting a sampling pump, and extracting fine particles in the atmosphere by a sampling head;
s104: sampling at a set time resolution, and storing sampling samples in a sampling box; the time resolution is minutes, hours or days;
s105: the central control unit sets and monitors the flow value of the gas;
s106: after sampling is completed, the industrial control module receives signals through the communication module, the passage electromagnetic valve is switched, and the sampling box is sealed.
Further preferably, the first analysis module includes a heating furnace, a first standard gas, a first carrier gas, a first quantitative ring, and a first detector, and the dry analysis in step S2 specifically includes:
s201: the control unit central control module sends out a dry analysis instruction; the control unit industrial control module receives a dry analysis instruction through the communication module, controls the opening and closing of the gas path through the logic controller and enters a dry analysis state;
s202: the heating furnace heats the sampling box containing the sampling sample for a preset time until carbonate in the sampling sample is completely decomposed to generate CO 2 The heating temperature is 900 ℃;
s203: the industrial control module controls the gas circuit to be opened and closed through the logic controller, so that the first carrier gas enters the sampling box; a flow sensor detects a first carrier gas flow rate;
s204: the industrial control module controls the opening and closing of the gas circuit through the logic controller to decompose CO generated in the sampling box 2 And a first carrier gas into the first dosing ring;
s205: the industrial control module controls gas in the first quantitative ring to enter the first detector for detection;
s206: the industrial control module controls the gas circuit to be opened and closed through the logic controller, so that the first standard gas enters the first quantitative ring and is detected by the first detector;
s207: the first detector sends the detection result to the central control module through the communication module.
Preferably, the second analysis module includes corrosion ware, sampling chamber, enrichment chamber, second mark gas, second carrier gas, second ration ring and second detector, and the sampling chamber is including setting up in the inside sample thief of sampling chamber and the peristaltic pump, the acid fog room and the first waste liquid pond that link to each other with the sampling chamber, and the enrichment chamber includes alkali lye pond and the PH meter that links to each other with alkali lye pond, naOH alkali lye tank, HCl acid tank, agitator and second waste liquid pond, and wet method analysis specifically includes in step S3:
s301: the control unit central control module sends out a wet analysis instruction; the control unit industrial control module receives the wet analysis instruction through the communication module, controls the opening and closing of the gas path through the logic controller and enters a wet analysis state;
s302: starting a sampling pump, extracting fine particles in the atmosphere by a sampling head, and enabling the fine particles to enter a sampling chamber through an erosion device; the corrosion device absorbs CO interfering with sample measurement 2 And SO 2 An isogas for removing the interfering gas mixed in the aerosol;
s303: adding deionized water leacheate into the sampling chamber by using a peristaltic pump; the acid mist chamber generates HCl acid mist and is introduced into the sampler, the liquid mixed and reacted with the liquid in the sampling chamber flows into the waste liquid tank, and the reacted gas enters the alkali liquor pool of the enrichment chamber; deionized water is used for washing off the particles attached to the center of the sampler, and carbonate reacts with HCl acid mist to generate CO 2 The gas, the insoluble organic carbon and the elemental carbon are eluted with the eluentEntering a first waste liquid pool;
s304: the NaOH solution is added into the alkali liquor tank by the NaOH alkali liquor tank, the liquid in the alkali liquor tank is stirred by the stirrer, and the PH value of the liquid in the alkali liquor tank is detected by the PH meter and is sent to the central control module through the communication module;
s305: when the central control module detects that the PH value of liquid in the alkali liquor pool rises to PH =10, adding an HCl solution into the alkali liquor pool by an HCl acid liquor tank;
s306: when the central control module detects that the pH value of the liquid in the alkali liquor pool is reduced to PH =5, the industrial control module controls the gas circuit to be opened and closed through the logic controller, and the second carrier gas enters the enrichment chamber;
s307: the industrial control module controls the gas circuit to be opened and closed through the logic controller to enrich CO in the chamber 2 And a second carrier gas into a second dosing ring; the gas in the second quantitative ring enters a second detector for detection; the second detector sends the detection result to the central control module through the communication module;
s308: adding NaOH solution into the alkali liquor pool by the NaOH alkali liquor tank until the central control module detects that the pH value of the liquid in the alkali liquor pool is 10;
s309: after repeating the steps S302-S308 to complete 10 sample measurement periods, the industrial control module controls the gas circuit to be opened and closed through the logic controller, so that the second standard gas enters the enrichment chamber, and the steps S304-S307 are repeated.
Further preferably, the first and second standard gases are CO 2 The standard gas, the first and second carrier gases are He gas, and the first and second detectors are gas chromatography detectors.
Further preferably, CO 2 The standard gas is 5% of CO by mass 2 A mixture of gas and He gas. CO 2 2 The standard gas is used for accurately measuring and calibrating the system, evaluating the detection mode of the working stability of the system and also used as an internal standard for evaluating the working conditions of the first detector and the second detector.
Another object of the present invention is to provide a continuous automatic sampling analyzer for measuring carbonate in the atmosphere.
In order to achieve the purpose, the invention adopts the following technical scheme:
a continuous automatic sampling and analyzing device for measuring carbonate in the atmosphere comprises a sampling unit, a control unit, an analyzing unit and a processing unit, wherein the sampling unit, the control unit, the analyzing unit and the processing unit are arranged in the sampling unit
The sampling unit comprises a sampling head, a sampling box and a sampling pump, the sampling head and the sampling pump are respectively connected with the sampling box through a logic controller, and the logic controller is set to be a two-way electromagnetic valve or a four-way electromagnetic valve according to the connection condition of a gas circuit; the sampling passage further comprises a two-way electromagnetic valve which is set as a mass flow controller;
the control unit comprises a central control module, a communication module and an industrial control module, wherein the central control module sends sampling, switching and analyzing instructions which are transmitted to the industrial control module through the communication module, and the industrial control module controls the sampling unit to perform sampling operation and the analyzing unit to perform sample analysis; the industrial control module comprises a first industrial control module, a second industrial control module and a third industrial control module, wherein the first industrial control module is used for receiving the instruction information of the communication module, controlling the opening or closing of the mass flow controller and the logic controller and accurately controlling the collection time of the atmospheric fine particle sample; the second industrial control module is used for receiving the instruction information of the communication module to control the on or off of the logic controller and accurately control the start and the off of the heating furnace and the on-off time of the first carrier gas; the third industrial control module is used for receiving the instruction information of the communication module, controlling the opening or closing of the corresponding logic controller and the flow sensor and controlling the starting or closing of the second carrier gas, the acid mist and the liquid;
the analysis unit comprises a first analysis module and a second analysis module, wherein the first analysis module is used for carrying out dry analysis on the sample and obtaining a first result, the second analysis module is used for carrying out wet analysis on the sample and obtaining a second result, and the analysis unit sends the first result and the second result to the central control module through the communication module;
the processing unit compares and statistically analyzes the first and second results to obtain an analysis result.
Preferably, the sampling head comprises a sampling mould frame and a sampling film arranged on the sampling mould frame; the sampling mould frame is made of quartz; the sampling film is a quartz film; a cutter and a rainwater separator are also arranged between the sampling head and the sampling box; and a third flow sensor is also arranged between the sampling box and the sampling pump.
Preferably, the first analysis module comprises a heating furnace, a first standard gas, a first carrier gas, a first quantitative ring and a first detector;
the second analysis module comprises an erosion apparatus, a sampling chamber, an enrichment chamber, a second standard gas, a second carrier gas, a second quantitative ring and a second detector, wherein
The sampling chamber comprises a sampling chamber inlet, a sampling chamber outlet, a sampler arranged in the sampling chamber, a peristaltic pump connected with the sampling chamber, an acid mist chamber and a first waste liquid pool;
the enrichment chamber comprises an enrichment chamber inlet, an enrichment chamber outlet, an alkali liquor pool, a PH meter, a NaOH alkali liquor tank, an HCl acid liquor tank, a stirrer and a second waste liquor pool, wherein the PH meter, the NaOH alkali liquor tank, the HCl acid liquor tank, the stirrer and the second waste liquor pool are connected with the alkali liquor pool;
the device also comprises a first flow sensor arranged in the gas circuit and used for measuring the flow of the first standard gas, a second flow sensor used for measuring the flow of the second standard gas, a first pressure sensor used for measuring the pressure of the first carrier gas and a second pressure sensor used for measuring the pressure of the second carrier gas.
Further preferably, the first and second standard gases are CO 2 The standard gas, the first and second carrier gases are He gas, and the first and second detectors are gas chromatography detectors; CO 2 2 The standard gas is 5% of CO by mass 2 A mixture of gas and He gas.
The invention has the following beneficial effects:
1. according to the invention, the acid mist is directly added into the closed container, so that errors and pollution caused by manual operation are eliminated, the acid mist reacts with the atmospheric carbonate sample to improve the trapping efficiency, automatic sampling is completed, the whole sampling and analyzing period is shortened, and the frequency of data is increased.
2. The heating method, but the CC concentration is analyzed singly, the interference of substances which are greatly present in the organic carbon and the element carbon in the two types of atmosphere to the CC determination (caused by the selection of the observed cutting point and the volatility of the organic carbon) can be removed, and the temperature-raising program selection and the amplitude have obvious difference.
3. The continuous and automatic sampling method and the device for the carbonate in the atmospheric fine particulate matters can finish the sampling work of the atmospheric fine particulate matters under the unattended condition, and realize continuous and uninterrupted sampling of the atmospheric fine particulate matters for a period of time.
4. According to the continuous automatic sampling method and device for the carbonate in the atmospheric fine particulate matters, provided by the invention, the carbonate in the collected atmospheric fine particulate matters is analyzed by adopting a dry analysis method and a wet analysis method.
5. The continuous automatic sampling method and the device for carbonate in the atmospheric fine particulate matters avoid sample loss caused by membrane sample transportation in the traditional off-line analysis, and the quantitative analysis of the carbonate is separated from the elemental carbon and the organic carbon by using the property difference among substances in the whole process, so that the accuracy and the relative accuracy of the analysis of the carbonate concentration in the atmospheric fine particulate matters are greatly improved.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 shows a block diagram of a continuous automatic sampling analyzer.
Fig. 2 shows a schematic diagram of a sampling unit structure of the continuous automatic sampling analysis device.
Fig. 3 shows a schematic diagram of a sampling chamber structure in an analysis unit of the continuous automatic sampling analysis device.
FIG. 4 shows a schematic diagram of the enrichment chamber structure in the analysis unit of the continuous automatic sampling analyzer.
Fig. 5 shows a schematic diagram of a continuous automatic sampling analyzer.
Detailed Description
In order to more clearly illustrate the present invention, the present invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
As shown in fig. 1, the continuous automatic sampling and analyzing device for measuring carbonate in the atmosphere comprises a sampling unit 1, a control unit 2, an analyzing unit 3 and a processing unit 4.
As shown in fig. 2, the sampling unit 1 includes a sampling head 110, a sampling box 120 and a sampling pump 130, the sampling head 100 and the sampling pump 130 are respectively connected to the sampling box 120 through a logic controller, and the logic controller is set as a two-way solenoid valve or a four-way solenoid valve according to the gas path connection condition; the sampling path also includes a two-way solenoid valve configured as a mass flow controller. The sampling head 110 comprises a sampling mould frame 111 and a sampling film 112 arranged on the sampling mould frame; the sampling mould frame 111 is made of quartz; the sampling film 112 is a quartz film; a cutter 113 and a rainwater separator 114 are also arranged between the sampling head 110 and the sampling box 120; a third flow sensor is also included between the sampling tank 120 and the sampling pump 130.
The control unit 2 comprises a central control module 210, a communication module 220 and an industrial control module 230, the central control module 210 sends out sampling, switching and analyzing instructions which are transmitted to the industrial control module 230 through the communication module 220, and the industrial control module 230 controls the sampling unit 1 to perform sampling operation and the analyzing unit 3 to perform sample analysis; the communication module 220 is configured to receive a control instruction of the central control module 210, send the control instruction to the first, second, and third industrial control modules, and send data information to the central control module 210; the industrial control module 230 comprises a first industrial control module 231, a second industrial control module 232 and a third industrial control module 233, wherein the first industrial control module 231 is used for receiving the instruction information of the communication module 220 and controlling the opening or closing of the mass flow controller and the logic controller, and accurately controlling the collection time of the atmospheric fine particle sample; the second industrial control module 232 is used for receiving the instruction information of the communication module 220 to control the on or off of the logic controller, and accurately controlling the start and the off of the heating furnace and the on-off time of the first carrier gas; the third industrial control module 233 is used for receiving the instruction information of the communication module 220, controlling the on/off of the corresponding logic controller and the flow sensor, and controlling the on/off of the second carrier gas, the acid mist and the liquid.
The analysis unit 3 includes a first analysis module 310 and a second analysis module 320, wherein the first analysis module 310 is configured to perform dry analysis on the sample and obtain a first result, the second analysis module 320 is configured to perform wet analysis on the sample and obtain a second result, and the analysis unit 3 sends the first and second results to the central control module 210 through the communication module.
The first analysis module 310 includes a heating furnace 311, a first target gas 312, a first carrier gas 313, a first quantification ring 314, and a first detector 315. The second analysis module 320 comprises an erosion apparatus 321, a sampling chamber 322, an enrichment chamber 323, a second standard gas 324, a second carrier gas 325, a second quantitative ring 326 and a second detector 327, wherein the sampling chamber 322 comprises a sampler 3221 arranged inside the sampling chamber, and a peristaltic pump 3222, an acid mist chamber 3223 and a first waste liquid pool 3224 connected with the sampling chamber; the enrichment chamber 323 comprises an alkali liquor pool 3231, and a pH meter 3232, a NaOH alkali liquor pool 3233, an HCl acid liquor pool 3234, a stirrer 3235 and a second waste liquor pool 3236 which are connected with the alkali liquor pool.
The processing unit 4 compares and statistically analyzes the first and second results to obtain an analysis result. In the invention, the first result and the second result are compared and statistically analyzed by adopting a data statistical method, large error data are eliminated, and the accuracy of a sampling result is improved.
The device also comprises a first flow sensor arranged in the gas path and used for measuring the flow of the first standard gas 312, a second flow sensor used for measuring the flow of the second standard gas 324, a first pressure sensor used for measuring the pressure of the first carrier gas 313 and a second pressure sensor used for measuring the pressure of the second carrier gas 325.
In the invention, the first and second standard gases are CO 2 The standard gas, the first and second carrier gases are He gas, and the first and second detectors are gas chromatography detectors; CO 2 2 The standard gas is 5% of CO by mass 2 A mixture of gas and He gas. Because of small He relative molecular weight, large thermal conductivity coefficient, small viscosity and large linear velocity in use, the stability of the gas is better than that of other inert gases such as nitrogen and the like.
The following detailed description is made with reference to the accompanying drawings
As shown in FIG. 3, the present invention relies primarily on the sampling chamber 322 for the collection of carbonate from the wet analysis of atmospheric fine particulates. The whole sampling chamber 322 is composed of a sampler 3221, a peristaltic pump 3222, an acid mist chamber 3223, and a first waste liquid pool 3224. The main body of the sampler 322 is made of glass and is a cylindrical left closing-in, and after the fine atmospheric particulates enter the passage, the fine atmospheric particulates enter the sampling chamber 322 from the left port of the sampler through the erosion device 321. The peristaltic pump 3222 enables the leacheate to enter the sampling chamber 322 from an upper opening of the sampling chamber 322, the acid mist chamber 3223 generates hydrochloric acid mist, the hydrochloric acid mist enters the sampling chamber 322 from a lower left opening of the sampling chamber 322, and waste liquid generated after reaction enters the first waste liquid pool 3224 from a lower right opening. Carbonate in the atmospheric fine particulate matter reacts with acid and then becomes gas which enters the carbon dioxide enrichment chamber 323 through a three-way pipe connected with the sampling pump from a passage on the right side.
As shown in fig. 4, the carbon dioxide enrichment chamber 323 is mainly composed of an alkali solution tank 3231, a PH meter 3232, a NaOH alkali solution tank 3233, an HCl acid solution tank 3234, a stirrer 3235, and a second waste solution tank 3226. CO generated in the sampler 3221 2 The NaOH solution enters the alkali solution pool 3231 through the logic controller to be absorbed, the NaOH solution can 3233 adds 0.4mol/L NaOH solution into the alkali solution pool 3234, the PH meter 3232 is inserted into the bottom of the alkali solution pool 3231 from the upper part of the alkali solution pool 3231, the change of the PH value in the solution is continuously monitored, and the data are transmitted back to the central control module 210 through the communication module 220. When the PH value does not fluctuate but stably and slowly rises to PH =10, the third industrial control module 233 receives the processing signal through the communication module 220, and the HCl acid solution tank 3234 starts to drop 0.4mol/LHCl solution into the alkali solution tank from above the alkali solution pool 3231. When the PH =5 in the cell is detected, the central control module 210 sends an instruction, a channel electromagnetic valve connected with the second carrier gas He is opened according to the sampling instruction, a flow sensor monitors the flow rate of the second carrier gas He, the enrichment chamber 323 is connected with a second detector 327 through a port on the right side of an alkali liquor cell 3231, and CO in the enrichment chamber 323 is mixed with the He gas 2 The gas pushes against the second dosing ring 326. After 10 sample measurement periods, the central control module 210 issues an instruction to the third industrial control module 233 through the communication module 220, and switches the four-way valve to make a certain amount of CO 2 Standard gas propulsion of CO 2 The enrichment chamber 323 for repeating the operation of adding alkali and acid for measuring the sampleThen, the four-way valve is switched to He and CO again 2 The enrichment chamber 323 is communicated, and the second carrier gas He pushes CO 2 The standard gas enters the second dosing ring 326 and is detected by the second detector 327.
In the present invention, the communication module 220 is divided into a communication output module 221 and a communication input module 222. The central control module 210 sends a switch instruction to start the starting of the sampling pump 130 through the communication output module 221; the communication input module 222 mainly converts the collected analog values of temperature, PH value, flow rate, etc. into digital values and returns the digital values to the central control module 210. In the invention, the communication output module 221 adopts Hua Advantech with model number of ADAM 4060, and the communication input module 222 adopts Hua Advantech with model number of ADAM-4017.
Fig. 5 shows a schematic structural diagram of a continuous automatic sampling analysis device, and a continuous automatic sampling analysis method for determining carbonate in the atmosphere by using the device, wherein the method comprises the following steps:
s1: the continuous automatic sampling of atmosphere carbonate is carried out to the sampling unit, specifically includes:
s101: the control unit central control module sends out a sampling instruction;
s102: the control unit industrial control module receives a sampling instruction through the communication module, controls the gas circuit to be opened and closed through the logic controller and enters a sampling state;
s103: starting a sampling pump, and extracting fine particles in the atmosphere by a sampling head;
s104: sampling at a set time resolution, and storing sampling samples in a sampling box; the time resolution is minutes, hours or days;
s105: the central control unit sets and monitors the flow value of the gas;
s106: after sampling is completed, the industrial control module receives signals through the communication module, the passage electromagnetic valve is switched, and the sampling box is sealed.
S2: the analysis unit includes a first analysis module, which performs dry analysis on the sample and obtains a first result, and specifically includes:
s201: the control unit central control module sends out a dry analysis instruction; the control unit industrial control module receives a dry analysis instruction through the communication module, controls the opening and closing of the gas path through the logic controller and enters a dry analysis state;
s202: the heating furnace heats the sampling box containing the sampling sample for a preset time until all the carbonate in the sampling sample is decomposed to generate CO 2 The heating temperature is 900 ℃;
s203: the industrial control module controls the gas circuit to be opened and closed through the logic controller, so that the first carrier gas enters the sampling box; a flow sensor detects a first carrier gas flow rate;
s204: the industrial control module controls the opening and closing of the gas circuit through the logic controller to decompose CO generated in the sampling box 2 And a first carrier gas into the first dosing ring;
s205: the industrial control module controls gas in the first quantitative ring to enter the first detector for detection;
s206: the industrial control module controls the gas circuit to be opened and closed through the logic controller, so that the first standard gas enters the first quantitative ring and is detected by the first detector;
s207: the first detector sends the detection result to the central control module through the communication module.
S3: the second analysis module of the analysis unit performs wet analysis on the sample and obtains a second result, and the method specifically includes:
s301: the control unit central control module sends out a wet analysis instruction; the control unit industrial control module receives the wet analysis instruction through the communication module, controls the opening and closing of the gas path through the logic controller and enters a wet analysis state;
s302: starting a sampling pump, extracting fine particles in the atmosphere by a sampling head, and enabling the fine particles to enter a sampling chamber through an erosion device; the corrosion device absorbs CO interfering with sample measurement 2 And SO 2 An isogas for removing the interfering gas mixed in the aerosol;
s303: adding deionized water leacheate into the sampling chamber by a peristaltic pump; heating by a heating wire to enable the acid mist chamber to generate HCl acid mist, introducing the HCl acid mist into the sampler, enabling liquid mixed and reacted with liquid in the sampling chamber to flow into a waste liquid tank, and enabling gas after reaction to enter an alkali liquor pool of the enrichment chamber; eluent rinse wet method analysisThe inner tube of the sampler dissolves and washes the aerosol attached to the tube wall and the inner tube, the dissolved soluble salt is dissolved in water, the insoluble carbonate, the element carbon and the organic carbon also float in the water, and when the HCl steam is added and rises to enter the wet sampler, the carbonate and the insoluble carbonate in the solution react to generate CO 2 And the rest substances, including element carbon and organic carbon, enter the waste liquid tank along with the leacheate so as to achieve the purpose of separating and removing impurities, wherein the solution contains the following components: naOH, naCl and Na 2 CO 3 ；
According to the invention, the acid mist is directly added into the closed container, so that errors and pollution caused by manual operation are eliminated, the acid mist reacts with the carbonate sample in the atmosphere, the trapping efficiency is improved, automatic sampling is completed, the whole sampling and analyzing period is shortened, and the frequency of data is increased;
s304: the industrial control module receives signals through the communication module, the NaOH alkali liquor tank adds NaOH solution into the alkali liquor tank, a PH meter inserted into the bottom of the alkali liquor tank continuously monitors the change of PH value in the solution, data are transmitted back to the central control unit through the communication module, and the magnetic stirrer in the alkali liquor tank continuously works to uniformly mix the solution;
s305: when the central control module detects that the PH value of the liquid in the alkali liquor pool rises to PH =10, the HCl acid liquor tank adds HCl solution into the alkali liquor pool;
in the present invention, for convenience of CO 2 Dissolving with HCl gas, adding NaOH into the alkali solution tank, and lowering pH value after acid gas enters, resulting in subsequent CO 2 Difficult to absorb, so the process is carried out until HCl is dissolved in liquid, CO 2 All conversion to Na 2 CO 3 The pH value is not fluctuated any more, and the acid gas is completely absorbed at the moment, and the pH value is about 10; at this point, addition of HCl solution can reduce Na content in the solution 2 CO 3 Conversion to CO 2 Gas, enriched in CO 2 For detecting;
s306: when the central control module detects that the pH value of the liquid in the alkali liquor pool is reduced to PH =5, the industrial control module controls the gas circuit to be opened and closed through the logic controller, so that the second carrier gas enters the enrichment chamber;
CO in air at normal temperature and pressure 2 Dissolved in water, saturated solution PH =5.60, to avoid CO formation 2 Dissolution, slightly increasing the acidity of the solution, determined at PH =5;
s307: the industrial control module controls the gas circuit to be opened and closed through the logic controller to enrich CO in the chamber 2 And a second carrier gas into the second dosing ring; the gas in the second quantitative ring enters a second detector for detection; the second detector sends the detection result to the central control module through the communication module;
s308: adding NaOH solution into the alkali liquor pool by the NaOH alkali liquor tank until the central control module detects that the pH value of the liquid in the alkali liquor pool is 10;
s309: after repeating the steps S302-S308 to complete 10 sample measurement periods, the industrial control module controls the gas circuit to be opened and closed through the logic controller, so that the second standard gas enters the enrichment chamber, and the steps S304-S307 are repeated.
S4: the processing unit compares and statistically analyzes the first and second results to obtain an analysis result. Because the content of carbonate in the atmosphere is low, a single observation method can not obtain effective observation data sometimes; in order to reduce measurement errors and obtain effective observation results, the two analysis methods are used for obtaining observation data and then carrying out comparison and statistical analysis, and finally obtaining effective results.
During the actual operation process, a single-channel sampling mode is started to sample PM2.5 in a target area, and the central control module 210 issues an industrial control instruction for sampling the fine atmospheric particulates; the sampling pump 130 is started, the channel electromagnetic valve is opened, the flow rate is controlled at 16.7 liters/minute, the flow rate value (generally 16.7 liters/minute) of gas is set on a computer interface, and the mass flow controller is calibrated uniformly to ensure that the actual flow rate is consistent with the experimental design; when the sampling time reaches a set value, the electromagnetic valve is switched, the sampling box is isolated from the outside, and the heating of the heating furnace is waited.
It should be understood that the above-described embodiments of the present invention are examples for clearly illustrating the invention, and are not to be construed as limiting the embodiments of the present invention, and it will be obvious to those skilled in the art that various changes and modifications can be made on the basis of the above description, and it is not intended to exhaust all embodiments, and obvious changes and modifications can be made on the basis of the technical solutions of the present invention.
Claims (8)
1. A continuous automatic sampling analysis method for measuring atmospheric carbonate is characterized by comprising the following steps:
s1: the sampling unit is used for continuously and automatically sampling the atmospheric carbonate;
s2: the analysis unit first analysis module performs dry analysis on the sampling sample to obtain a first result;
s3: the second analysis module of the analysis unit performs wet analysis on the sampling sample and obtains a second result;
s4: the processing unit compares and statistically analyzes the first result and the second result to obtain an analysis result;
the second analysis module includes corrosion ware, sampling chamber, enrichment room, second mark gas, second carrier gas, second ration ring and second detector, the sampling chamber including set up in the inside sample thief of sampling chamber and with peristaltic pump, acid fog room and the first waste liquid pond that the sampling chamber links to each other, the enrichment room include the alkali lye pond and with PH meter, naOH alkali lye tank, HCl acid liquid tank, agitator and the second waste liquid pond that the alkali lye pond links to each other, wet method analysis specifically includes in step S3:
s301: the control unit central control module sends out a wet analysis instruction; the control unit industrial control module receives the wet analysis instruction through the communication module, controls the gas circuit to be opened and closed through the logic controller and enters a wet analysis state;
s302: starting a sampling pump, extracting fine particles in the atmosphere by a sampling head, and enabling the fine particles to enter a sampling chamber through an erosion device;
s303: adding deionized water leacheate into the sampling chamber by a peristaltic pump; the acid mist chamber generates HCl acid mist and introduces the HCl acid mist into the sampler, the liquid mixed and reacted with the liquid in the sampling chamber flows into the waste liquid tank, and the reacted gas enters the alkali liquor pool of the enrichment chamber;
s304: the NaOH alkaline solution tank is used for adding NaOH solution into the alkaline solution tank, the stirrer is used for stirring the liquid in the alkaline solution tank, and the PH meter is used for detecting the PH value of the liquid in the alkaline solution tank and sending the PH value to the central control module through the communication module;
s305: when the central control module detects that the PH value of liquid in the alkali liquor pool rises to PH =10, adding an HCl solution into the alkali liquor pool by an HCl acid liquor tank;
s306: when the central control module detects that the pH value of the liquid in the alkali liquor pool is reduced to PH =5, the industrial control module controls the gas circuit to be opened and closed through the logic controller, and the second carrier gas enters the enrichment chamber;
s307: the industrial control module controls the gas circuit to be opened and closed through the logic controller to enrich CO in the chamber 2 And a second carrier gas into a second dosing ring; the gas in the second quantitative ring enters a second detector for detection; the second detector sends the detection result to the central control module through the communication module;
s308: adding NaOH solution into the alkali liquor pool by the NaOH alkali liquor tank until the central control module detects that the pH value of the liquid in the alkali liquor pool is 10;
s309: after repeating the steps S302-S308 to complete 10 sample measurement periods, the industrial control module controls the gas circuit to be opened and closed through the logic controller, so that the second standard gas enters the enrichment chamber, and the steps S304-S307 are repeated.
2. The sampling analysis method according to claim 1, wherein the sampling unit comprises a sampling head, a sampling box and a sampling pump, and the step S1 specifically comprises:
s101: the control unit central control module sends out a sampling instruction;
s102: the control unit industrial control module receives the sampling instruction through the communication module, controls the opening and closing of the gas circuit through the logic controller and enters a sampling state;
s103: starting a sampling pump, and extracting fine particles in the atmosphere by a sampling head;
s104: sampling at a set time resolution, and storing sampling samples in a sampling box;
s105: the central control unit sets and monitors the flow value of the gas;
s106: and after sampling is finished, the sampling box is closed.
3. The sampling analysis method according to claim 2, wherein the first analysis module includes a heating furnace, a first standard gas, a first carrier gas, a first quantitative ring, and a first detector, and the dry analysis in step S2 specifically includes:
s201: the control unit central control module sends out a dry analysis instruction; the control unit industrial control module receives the dry analysis instruction through the communication module, controls the opening and closing of the gas path through the logic controller and enters a dry analysis state;
s202: the heating furnace heats the sampling box containing the sampling sample for a preset time until carbonate in the sampling sample is completely decomposed to generate CO 2 The heating temperature is 900 ℃;
s203: the industrial control module controls the gas circuit to be opened and closed through the logic controller, so that the first carrier gas enters the sampling box;
s204: the industrial control module controls the opening and closing of the gas circuit through the logic controller to decompose CO generated in the sampling box 2 And a first carrier gas into the first dosing ring;
s205: the industrial control module controls gas in the first quantitative ring to enter the first detector for detection;
s206: the industrial control module controls the gas circuit to be opened and closed through the logic controller, so that the first standard gas enters the first quantitative ring and is detected by the first detector;
s207: the first detector sends the detection result to the central control module through the communication module.
4. A sample analysis method as claimed in claim 3, wherein the first and second standard gases are CO 2 The first carrier gas and the second carrier gas are He gas, and the first detector and the second detector are gas chromatography detectors.
5. Root of herbaceous plantsThe sample analysis method of claim 4, wherein the CO is 2 The standard gas is 5% of CO by mass 2 A mixture of gas and He gas.
6. A continuous automatic sampling analysis device for measuring carbonate in the atmosphere is characterized by comprising a sampling unit, a control unit, an analysis unit and a processing unit, wherein the sampling unit, the control unit, the analysis unit and the processing unit are arranged in the device
The sampling unit comprises a sampling head, a sampling box and a sampling pump, the sampling head and the sampling pump are respectively connected with the sampling box through a logic controller, and the logic controller is set to be a two-way electromagnetic valve or a four-way electromagnetic valve according to the connection condition of a gas circuit;
the control unit comprises a central control module, a communication module and an industrial control module, wherein the central control module sends out a sampling and analyzing instruction and transmits the sampling and analyzing instruction to the industrial control module through the communication module, and the industrial control module controls the sampling unit to perform sampling operation and the analyzing unit to perform sample analysis;
the analysis unit comprises a first analysis module and a second analysis module, wherein the first analysis module is used for performing dry analysis on the sample and obtaining a first result, the second analysis module is used for performing wet analysis on the sample and obtaining a second result, and the analysis unit sends the first result and the second result to the central control module through the communication module;
the processing unit compares and statistically analyzes the first result and the second result to obtain an analysis result;
the first analysis module comprises a heating furnace, a first standard gas, a first carrier gas, a first quantitative ring and a first detector;
the second analysis module comprises an erosion apparatus, a sampling chamber, an enrichment chamber, a second standard gas, a second carrier gas, a second quantitative ring, and a second detector, wherein
The sampling chamber comprises a sampling chamber inlet, a sampling chamber outlet, a sampler arranged in the sampling chamber, a peristaltic pump connected with the sampling chamber, an acid mist chamber and a first waste liquid pool;
the enrichment chamber comprises an enrichment chamber inlet, an enrichment chamber outlet, an alkali liquor pool, a PH meter, a NaOH alkali liquor tank, an HCl acid liquor tank, a stirrer and a second waste liquor pool, wherein the PH meter, the NaOH alkali liquor tank, the HCl acid liquor tank, the stirrer and the second waste liquor pool are connected with the alkali liquor pool;
the device also comprises a first flow sensor arranged in the gas path and used for measuring the flow of the first standard gas, a second flow sensor used for measuring the flow of the second standard gas, a first pressure sensor used for measuring the pressure of the first carrier gas and a second pressure sensor used for measuring the pressure of the second carrier gas.
7. The sampling analysis device of claim 6, wherein the sampling head comprises a sampling die holder and a sampling membrane disposed on the sampling die holder; the sampling mould frame is made of quartz; the sampling film is a quartz film; a cutter and a rainwater separator are also arranged between the sampling head and the sampling box; and a third flow sensor is also arranged between the sampling box and the sampling pump.
8. The sample analysis device of claim 6,
the first standard gas and the second standard gas are CO 2 The first carrier gas and the second carrier gas are He gas, and the first detector and the second detector are gas chromatography detectors; the CO is 2 The standard gas is 5% of CO by mass 2 A mixture of gas and He gas.
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| CN111856048A (en) * | 2019-04-30 | 2020-10-30 | 中国石油化工股份有限公司 | Altered carbonate automatic analysis device and analysis method |
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