CN106645501A - Continuous automatic sampling and analyzing method and continuous automatic sampling and analyzing device for measuring atmospheric carbonate - Google Patents
Continuous automatic sampling and analyzing method and continuous automatic sampling and analyzing device for measuring atmospheric carbonate Download PDFInfo
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- CN106645501A CN106645501A CN201710101537.0A CN201710101537A CN106645501A CN 106645501 A CN106645501 A CN 106645501A CN 201710101537 A CN201710101537 A CN 201710101537A CN 106645501 A CN106645501 A CN 106645501A
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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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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
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- G—PHYSICS
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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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Abstract
The invention discloses a continuous automatic sampling and analyzing method for measuring atmospheric carbonate. The continuous automatic sampling and analyzing method includes: a sampling unit is used for continuous automatic sampling of the atmospheric carbonate; a first analyzing module of an analyzing unit is used for analyzing samples by dry analysis so as to obtain a first result; a second analyzing module of the analyzing unit is used for analyzing the samples by wet analysis so as to obtain a second result; a processing unit is used for comparing and statistically analyzing the first result and the second result so as to obtain an analysis result. The invention further discloses a continuous automatic sampling and analyzing device applying the continuous automatic sampling and analyzing method. The continuous automatic sampling and analyzing method and the continuous automatic sampling and analyzing method for measuring the atmospheric carbonate have the advantages that continuous automatic sampling can be realized, a whole sampling and analyzing period is shortened, data frequency is increased, interferences of organic carbon and elemental carbon to a measured result is avoided, the carbonate in collected atmospheric fine particulate matters can be analyzed by a dry analysis method and a wet analysis method at the same time, and precision and relative accuracy of analysis of carbonate concentration in the atmospheric fine particulate matters can be increased remarkably.
Description
Technical field
The present invention relates to atmosphere environment supervision and ecological environment research field.Atmospheric carbon is determined more particularly, to a kind of
The continuous automatic sampling analysis method and apparatus of hydrochlorate.
Background technology
Atmospheric particulates (Atmospheric Particulate Matters) are various solid-states and liquid present in air
The general name of state particulate material, various particulate materials are evenly dispersed in one metastable huge suspension of composition in air
System, i.e. aerosol system, therefore Atmospheric particulates are also referred to as atmospheric aerosol (Atmospheric Aerosols).Air
Relatively fine particle thing is very big to health and ambient influnence in grain thing, and wherein carbonaceous material content in aerosol is very high, right
The larger fine fraction ratio of Human health effects is bigger.These carbonaceous materials can adsorb the pollutant in air, wherein
Some have carcinogenic, teratogenesis, mutagenic effect, but also can affect the transparency and intensity of solar radiation of air.Airborne particulate
Carbonaceous material in thing is divided three classes：Organic carbon (organic carbon, abbreviation OC), elemental carbon (element carbon, letter
Claim EC) and carbonate (carbonate carbon, abbreviation CC), wherein carbonate content is less, elemental carbon and organic carbon chemical combination
Thing is the main component of aerosol.Not only physics, chemical property are different for three class carbonaceous materials, originate also different.Such as：EC easily inhales
Light, chemical property is relatively stable；OC absorption effects and chemical stability are poor compared with EC.
Impact of the carbonate in airborne fine particulate matter to neutralization and the global balance of solar radiation generation of acid rain is more next
More paid close attention to by scientist.Due to its basic character, carbonate easily with air in sour gas (including sulfur dioxide and
Oxynitrides) reaction, and accelerate SO on its surface2And NOxConversion of the gas to sulfate and nitrate；Additionally, it is in air
In also directly carry out with sulfuric acid, nitric acid and other organic acid (such as acetic acid) gases or particle various homogeneous and heterogeneous changes
Learn reaction.Carbonate can transmit the alkalescence for increasing surface seawater in airborne fine particulate matter, change its acid-base balance, promote seawater to inhale
Receive the CO in air2, therefore " alkali pump " and " bio-pump " role that carbon in atmosphere hydrochlorate is played the part of in seawater and rainwater.Additionally,
Although the usual content of carbonate in ambient air is very low, content is outstanding in northern China air, particularly sandstorm air
For higher.Therefore, carbonate is all played an important role in air, ocean, land system, to carbonate in airborne fine particulate matter
Research be of great significance.
At present, both at home and abroad the analysis of carbonate mass concentration in airborne fine particulate matter is still to be sent after sampler samples
Enter based on the conventional offline analytical technology of lab analysis, lack in airborne fine particulate matter carbonate continuous automatic sampling device with
Obtain high time resolution observation data.Existing sample mode has the disadvantages that：
1), sampling process needs to put into substantial amounts of man power and material.Generally, laboratory technician adopts blank according to sample requirement
Sample film is placed in atmospheric aerosol sampler and sets the sampling time, and laboratory technician takes sample film after the sampling time terminates
Return, with watery hydrochloric acid reaction CO is produced2And to CO2It is analyzed, obtains the mass concentration of CC.
2) damage can be produced to equipment in, sampling.Because atmospheric aerosol carbon analyzer is not used exclusively for CC analyses, do not have
Have through anti-acid treatment, therefore to causing equipment loss greatly during the analysis of CC, have a strong impact on the service life of instrument.
3), low-frequency observation data are not suitable for the foundation and checking of process model.Limited by sample mode, it is existing
Low-frequency sampled data is inevitably generated observation error so as to CC discharge process and its environmental key-element controlling mechanism
Research is very difficult to carry out.
4), the inaccuracy of measurement result.Although current some researchs show can pass through the method for heating semi-continuously
CC concentration is determined, but due to being disturbed by elemental carbon and organic carbon, there is very big uncertainty in analysis result.
Therefore, existing artificial observation technology can not the in situ long-term simultaneous observation valid data for obtaining CC, need development badly
Automatic Observation technology in situ is observed to CC, with study city, rural area or background areas CC variation characteristics, Evolution with
Effect played in atmosphere pollution Forming Mechanism, obtains the measured data and parameter of checking model, it is desirable to provide one kind is used for
Determine the continuous automatic sampling analysis method and apparatus of air carbonate.
The content of the invention
In order to solve the above problems, it is an object of the present invention to provide a kind of determine the continuous automatic of air carbonate
Sampling analysis method.
To reach above-mentioned purpose, the present invention adopts following technical proposals：
A kind of continuous automatic sampling analysis method for determining air carbonate, the method is comprised the following steps：
S1：Sampling unit carries out the continuous automatic sampling of air carbonate；
S2：The analysis module of analytic unit first carries out dry analysis and obtains the first result to sample；
S3：The analysis module of analytic unit second carries out humid analysis and obtains the second result to sample；
S4：Processing unit is contrasted and statistical analysis to the first and second results, obtains analysis result.
Preferably, sampling unit includes sampling head, sampling box and sampling pump, and step S1 is specifically included：
S101：Control unit Central Control Module sends sampling instruction；
S102：Control unit industrial control module receives sampling instruction by communication module, by logic controller control
Gas circuit is opened and closed, into sample states；
S103：Sampling pump startup, sampling head extracts fine particle in air；
S104：Sampled with setting time resolution ratio, sample is stored in sampling box；Temporal resolution is to divide
Clock, hour or day；
S105：Centralized control unit arranges and monitors the flow value of gas；
S106：After the completion of sampling, industrial control module receives signal by communication module, and path magnetic valve is cut
Change, enclosed sampling case.
It is further preferred that the first analysis module includes heating furnace, the first gas, the first carrier gas, the first quantitative loop and the
One detector, dry analysis in step S2 is specifically included：
S201：Control unit Central Control Module sends dry analysis instruction；Control unit industrial control module is by logical
News module receives dry analysis instruction, gas circuit opening and closing is controlled by logic controller, into dry analysis state；
S202：Heating furnace carries out scheduled time heating to the sampling box containing sample, the carbonate into sample
All decompose and produce CO2, heating-up temperature is 900 DEG C；
S203：Industrial control module controls gas circuit opening and closing by logic controller, makes the first carrier gas enter sampling box；Flow
Sensor detects the first flow rate of carrier gas；
S204：Industrial control module controls gas circuit opening and closing by logic controller, the CO of generation will be decomposed in sampling box2With
First carrier gas pushes the first quantitative loop；
S205：The gas that industrial control module is controlled in the first quantitative loop is detected into the first detector；
S206：Industrial control module controls gas circuit opening and closing by logic controller, makes the first gas enter the first quantitative loop
And by the detection of the first detector；
S207：First detector is sent testing result to Central Control Module by communication module.
Preferably, the second analysis module includes that denuder, sampler chamber, enrichment room, the second gas, the second carrier gas, second are determined
Amount ring and the second detector, sampler chamber includes being arranged at the sampler inside sampler chamber and the peristaltic pump, the acid that are connected with sampler chamber
Fog chamber and the first waste liquid pool, be enriched with room include alkali lye pond and be connected with alkali lye pond PH meters, NaOH alkali liquid tanks, HCl acid solution tanks, stir
Device and the second waste liquid pool are mixed, humid analysis in step S3 is specifically included：
S301：Control unit Central Control Module sends humid analysis instruction；Control unit industrial control module is by logical
News module receives humid analysis instruction, gas circuit opening and closing is controlled by logic controller, into humid analysis state；
S302：Sampling pump startup, sampling head extracts the fine particle in air, and fine particle Jing denuders enter sampling
Room；Denuder absorbs the CO of interference test sample2And SO2Deng gas, for removing the interference gas being mixed in aerosol；
S303：Deionized water leacheate is added sampler chamber by peristaltic pump；Acid mist room produces HCl acid mists and is passed through sampler
In, waste liquid tank is flowed into the liquid after the indoor liquid reactant mixture of sampling, reacted gas enters enrichment room alkali lye pond；Go from
Sub- water is used to will be attached to the particulate matter at sampler center and rinses, and carbonate generates CO with the reaction of HCl acid mists2Gas, together
When undissolved organic carbon and elemental carbon with leacheate enter the first waste liquid pool；
S304：NaOH alkali liquid tanks add NaOH solution, agitator to be stirred the liquid in alkali lye pond into alkali lye pond,
PH is counted the pH value to liquid in alkali lye pond and is detected and sent to Central Control Module by communication module；
S305：When Central Control Module detects that liquid pH value rises to PH=10 in alkali lye pond, HCl acid solution tanks are to alkali lye
HCl solution is added in pond；
S306：When Central Control Module detects that liquid pH value drops to PH=5 in alkali lye pond, industrial control module passes through
Logic controller control gas circuit opening and closing, makes the second carrier gas enter enrichment room；
S307：Industrial control module controls gas circuit opening and closing by logic controller, by the CO in enrichment room2With the second carrier gas
Push the second quantitative loop；Gas in second quantitative loop is detected into the second detector；Second detector is by communication
Module sends testing result to Central Control Module；
S308：NaOH alkali liquid tanks add NaOH solution to Central Control Module to detect liquid in alkali lye pond in alkali lye pond
PH value is 10；
S309：After repeat the above steps S302-S308 complete 10 test sample cycles, industrial control module passes through logic control
Device control gas circuit opening and closing, makes the second gas enter enrichment room and repeat step S304-S307.
It is further preferred that first, second gas is CO2Standard Gases, first, second carrier gas is He gas, and first, second examines
Survey device is gas chromatography detector.
It is further preferred that CO2Standard Gases are CO that mass ratio is 5%2The mixture of gas and He gases.CO2Standard Gases
For the calibration of system Accurate Determining, the detection mode of assessment system job stability, it is additionally operable to as internal standard, evaluation first, the
The working condition of two detectors.
Further object is that providing a kind of continuous automatic sampling and analyzing device for determining air carbonate.
To reach above-mentioned purpose, the present invention adopts following technical proposals：
It is a kind of determine air carbonate continuous automatic sampling and analyzing device, the device include sampling unit, control unit,
Analytic unit and processing unit, wherein
Sampling unit includes sampling head, sampling box and sampling pump, sampling head and sampling pump respectively by logic controller with
Sampling box is connected, and logic controller is set to two-way electromagnetic valve or four way solenoid valve according to gas circuit connection；Sampling path is also
Including the two-way electromagnetic valve for being set to mass flow controller；
Control unit include Central Control Module, communication module and industrial control module, Central Control Module send sampling,
Switch and analysis instruction, are transmitted to industrial control module by communication module, and industrial control module control sampling unit is adopted
Sample is operated and analytic unit carries out sample analysis；Industrial control module includes the first industrial control module, the second Industry Control mould
Block and the 3rd industrial control module, wherein, the first industrial control module is used to receive the command information of communication module and control matter
Amount flow controller and logic controller are turned on and off, precise control airborne fine particulate matter sample collection time；Second work
Industry control module is used to receive being turned on and off for the command information control logic controller of communication module, precise control heating furnace
Startup with close, the switch time of the first carrier gas；3rd industrial control module is used to receive the command information of communication module, control
Respective logic controller processed and flow sensor are turned on and off, the second carrier gas of control, acid mist, the startup of liquid or closing；
Analytic unit includes the first analysis module and the second analysis module, wherein the first analysis module is used to carry out sample
Dry analysis simultaneously obtains the first result, and the second analysis module is used to carry out humid analysis to sample and obtain the second result, analyzes
Unit sends the first and second results to Central Control Module by communication module；
Processing unit is contrasted and statistical analysis to the first and second results, obtains analysis result.
Preferably, the sampling film that sampling head includes sampling mould bases and is arranged on sampling mould bases；Sampling mould bases material is stone
English；Sampling film is quartz film；Also include cutter and rainwater separator between sampling head and sampling box；Sampling box and sampling pump it
Between also include the 3rd flow sensor.
Preferably, the first analysis module includes heating furnace, the first gas, the first carrier gas, the first quantitative loop and the first detection
Device；
Second analysis module includes denuder, sampler chamber, enrichment room, the second gas, the second carrier gas, the second quantitative loop and the
Two detectors, wherein
Sampler chamber include sampling chamber inlet, sampler chamber outlet, the sampler that is arranged inside sampler chamber and with sampler chamber phase
Peristaltic pump even, acid mist room and the first waste liquid pool；
Enrichment room includes enrichment chamber inlet, the outlet of enrichment room, alkali lye pond and the PH meters, the NaOH alkali lye that are connected with alkali lye pond
Tank, HCl acid solution tanks, agitator and the second waste liquid pool；
Device also includes being arranged in gas circuit is used for the first flow sensor for determining the first gas flow, for determining the
The second flow sensor of two gas flows, for determine the first nebulizer gas pressure first pressure sensor and for determine second
The second pressure sensor of nebulizer gas pressure.
It is further preferred that first, second gas is CO2Standard Gases, first, second carrier gas is He gas, and first, second examines
Survey device is gas chromatography detector；CO2Standard Gases are CO that mass ratio is 5%2The mixture of gas and He gases.
Beneficial effects of the present invention are as follows：
1st, it is direct in the present invention to add acid mist in closed container, the error and pollution caused during manual operation had both been eliminated,
Acid mist improves arresting efficiency with air carbonate example reaction, completes sampling automatically, shortens whole sampling and analytical cycle, increases
The frequency of data is added.
2nd, the method for heating, but single analysis CC concentration, can remove in organic carbon and elemental carbon this two classes air in a large number
The interference (caused by the selection of observation cut point and organic carbon volatility) that the material of presence is determined to CC, and heating schedule choosing
Select and there is notable difference with amplitude.
3rd, the carbonate continuous method of sampling and device automatically in a kind of airborne fine particulate matter that the present invention is provided, can be at nobody
The sampling work to airborne fine particulate matter sample is completed in the case of on duty, and realizes the airborne fine particulate matter for a period of time
Carry out continuous uninterrupted sampling.
4th, the present invention provide a kind of airborne fine particulate matter in carbonate the continuous automatic method of sampling and device, while adopting
It is analyzed with the carbonate in two kinds of airborne fine particulate matters to collection of dry analysis and humid analysis.
5th, the continuous automatic method of sampling and device of the carbonate in a kind of airborne fine particulate matter that the present invention is provided, it is to avoid
The sample loss that the transport of film sample is caused in conventional offline analysis, using the nature difference between material in the whole process, will
The quantitative and elemental carbon of carbonate, organic carbon are separated, and greatly improve carbonate concentration analysis in airborne fine particulate matter
Accuracy and relative precision.
Description of the drawings
The specific embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 illustrates continuous sampling and analyzing device structured flowchart automatically.
Fig. 2 illustrates continuous sampling and analyzing device sampling unit structural representation automatically.
Fig. 3 illustrates sampler chamber structural representation in continuous sampling and analyzing device analytic unit automatically.
Fig. 4 is illustrated in continuous sampling and analyzing device analytic unit automatically and is enriched with cell structure schematic diagram.
Fig. 5 illustrates continuous sampling and analyzing device structural representation automatically.
Specific embodiment
In order to be illustrated more clearly that the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.Similar part is indicated with identical reference in accompanying drawing.It will be appreciated by those skilled in the art that below institute is concrete
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
As shown in figure 1, it is a kind of determine air carbonate continuous automatic sampling and analyzing device, the device include sampling unit
1st, control unit 2, analytic unit 3 and processing unit 4.
As shown in Fig. 2 sampling unit 1 includes sampling head 110, sampling box 120 and sampling pump 130, sampling head 100 and sampling
Pump 130 is connected respectively by logic controller with sampling box 120, and logic controller is set to two energizations according to gas circuit connection
Magnet valve or four way solenoid valve；Sampling path also includes being set to the two-way electromagnetic valve of mass flow controller.Sampling head 110 includes
Sampling mould bases 111 and the sampling film 112 being arranged on sampling mould bases；Sampling mould bases 111 material is quartz；Sampling film 112 is stone
Capsule；Also include cutter 113 and rainwater separator 114 between sampling head 110 and sampling box 120；Sampling box 120 and sampling pump
Also include the 3rd flow sensor between 130.
Control unit 2 includes Central Control Module 210, communication module 220 and industrial control module 230, center control mould
Block 210 sends sampling, switch and analysis instruction, is transmitted to industrial control module 230, Industry Control mould by communication module 220
The control sampling unit 1 of block 230 carries out sampling operation and analytic unit 3 carries out sample analysis；Communication module 220 is used to receive center
The control instruction of control module 210, control instruction is sent to first, second, third industrial control module, and by data message
Send to Central Control Module 210；Industrial control module 230 includes the first industrial control module 231, the second industrial control module
232 and the 3rd industrial control module 233, wherein, the first industrial control module 231 is used to receive the instruction letter of communication module 220
Being turned on and off for mass flow controller and logic controller is ceased and controls, during precise control airborne fine particulate matter sample collection
Between；Second industrial control module 232 is used for the unlatching of the command information control logic controller for receiving communication module 220 or pass
Close, startup and closing, the switch time of the first carrier gas of precise control heating furnace；3rd industrial control module 233 is used to receive
Being turned on and off for the command information of communication module 220, control respective logic controller and flow sensor, controls second and carries
Gas, acid mist, the startup of liquid or closing.
Analytic unit 3 includes the first analysis module 310 and the second analysis module 320, wherein the first analysis module 310 is used for
Dry analysis is carried out to sample and the first result is obtained, the second analysis module 320 is used to carry out sample humid analysis and obtain
Second result, analytic unit 3 sends the first and second results to Central Control Module 210 by communication module.
First analysis module 310 includes heating furnace 311, the first gas 312, the first carrier gas 313, the and of the first quantitative loop 314
First detector 315.Second analysis module 320 include denuder 321, sampler chamber 322, enrichment room 323, the second gas 324, the
Two carrier gas 325, the second quantitative loop 326 and the second detector 327, wherein sampler chamber 322 include being arranged at adopting inside sampler chamber
Sample device 3221 and the peristaltic pump 3222 being connected with sampler chamber, the waste liquid pool 3224 of acid mist room 3223 and first；Enrichment room 323 includes alkali
Liquid pool 3231 and the PH meters 3232, NaOH alkali liquid tanks 3233, the HCl acid solutions tank 3234, agitator 3235 and that are connected with alkali lye pond
Two waste liquid pools 3236.
4 pairs of the first and second results of processing unit are contrasted and statistical analysis, obtain analysis result.It is right in the present invention
First and second results are contrasted using the method for data statistics and statistical analysis, rejected big error information, improved sampling
As a result accuracy.
Device also includes being arranged in gas circuit for determining the first flow sensor of the flow of the first gas 312, for surveying
The second flow sensor of the fixed flow of second gas 324, the first pressure sensor for determining the pressure of the first carrier gas 313 and use
In the second pressure sensor for determining the pressure of the second carrier gas 325.
In the present invention, first, second gas is CO2Standard Gases, first, second carrier gas be He gas, first, second detector
For gas chromatography detector；CO2Standard Gases are CO that mass ratio is 5%2The mixture of gas and He gases.Divide because He is relative
Son measures that little, thermal conductivity coefficient is big, viscosity is little, linear velocity is big when using, and the good stability of gas is in other inert gases such as nitrogen.
It is described as follows below in conjunction with the accompanying drawings
As shown in figure 3, the carbonate in the present invention in humid analysis airborne fine particulate matter to rely primarily on sampler chamber 322 complete
Into collection.Whole sampler chamber 322 is made up of sampler 3221, peristaltic pump 3222, acid mist room 3223, the first waste liquid pool 3224.Adopt
The main body of sample device 322 is glass material, in cylindrical left closing in, after airborne fine particulate matter entering path, through denuder 321
From sampler left side, mouth enters sampler chamber 322.Leacheate is entered sampler chamber by peristaltic pump 3222 from the upper square opening of sampler chamber 322
322, acid mist room 3223 produces hydrochloric acid mist, enters sampler chamber 322 from the lower-left mouth of sampler chamber 322, the waste liquid produced after reaction
The first waste liquid pool 3224 is entered from bottom right mouth.Become gas from the logical of right side after carbonate in airborne fine particulate matter and acid reaction
Road, is entered in carbon dioxide enriched room 323 by the threeway being connected with sampling pump.
As shown in figure 4, carbon dioxide enriched room 323 it is main by alkali lye pond 3231, PH meter 3232, NaOH alkali liquid tanks 3233,
HCl acid solutions tank 3234, the waste liquid pool 3226 of agitator 3235 and second are constituted.The CO produced in sampler 32212Via logic control
Device processed is absorbed into alkali lye pond 3231, and NaOH alkali liquid tanks 3233 add 0.4mol/L NaOH solutions, PH into alkali lye pond 3234
Meter 3232 does not stop the change for monitoring the pH value in solution from the bottom of the top of alkali lye pond 3231 insertion alkali lye pond 3231, and by number
Central Control Module 210 is transmitted back to according to by communication module 220.Treat that pH value occurs without fluctuation, but be steadily raised slowly to PH
=10, by the reception processing signal of communication module 220, HCl acid solutions tank 3234 is from alkali lye pond 3231 for the 3rd industrial control module 233
Top starts that 0.4mol/LHCl solution is added dropwise into alkaline tank.The PH=5 in pond is treated, Central Control Module 210 sends instruction,
According to the passage magnetic valve that sampling instruction unpack is connected with the second carrier gas He, flow sensor monitors the flow velocity of the second carrier gas He,
Enrichment room 323 is connected by the port on the right side of alkali lye pond 3231 with the second detector 327, the CO that He gas will be enriched with room 3232Gas
Body advances the second quantitative loop 326.After 10 test sample cycles, Central Control Module 210 is by communication module 220 to the 3rd work
Industry control module 233 issues instruction, switches cross valve, makes a certain amount of CO2Standard Gases advance CO2Enrichment room 323, repeats plus alkali adds
After sour test sample operation, cross valve switches to again He and CO2Enrichment room 323 communicates, and the second carrier gas He promotes CO2Standard Gases enter
Enter the second quantitative loop 326 and detected by the second detector 327.
In the present invention, 220 points of communication module is communication output module 221 and communication input module 222.Central Control Module
210 send switch order starts the functions such as the unlatching of sampling pump 130 by communication output module 221；Communication input module 222 is led
The analog quantitys such as temperature, pH value and flow collection are converted into numeral and return to Central Control Module 210.In the present invention, lead to
News output module 221 is selected and grinds China from magnificent Advantech, model ADAM 4060, communication input module 222 is ground
Advantech, model ADAM-4017.
Fig. 5 illustrates continuous sampling and analyzing device structural representation automatically, and a kind of using the device determines air carbonate
Continuous automatic sampling analysis method, the method comprises the following steps：
S1：Sampling unit carries out the continuous automatic sampling of air carbonate, specifically includes：
S101：Control unit Central Control Module sends sampling instruction；
S102：Control unit industrial control module receives sampling instruction by communication module, by logic controller control
Gas circuit is opened and closed, into sample states；
S103：Sampling pump startup, sampling head extracts fine particle in air；
S104：Sampled with setting time resolution ratio, sample is stored in sampling box；Temporal resolution is to divide
Clock, hour or day；
S105：Centralized control unit arranges and monitors the flow value of gas；
S106：After the completion of sampling, industrial control module receives signal by communication module, and path magnetic valve is cut
Change, enclosed sampling case.
S2：The analysis module of analytic unit first carries out dry analysis and obtains the first result to sample, specifically includes：
S201：Control unit Central Control Module sends dry analysis instruction；Control unit industrial control module is by logical
News module receives dry analysis instruction, gas circuit opening and closing is controlled by logic controller, into dry analysis state；
S202：Heating furnace carries out scheduled time heating to the sampling box containing sample, the carbonate into sample
All decompose and produce CO2, heating-up temperature is 900 DEG C；
S203：Industrial control module controls gas circuit opening and closing by logic controller, makes the first carrier gas enter sampling box；Flow
Sensor detects the first flow rate of carrier gas；
S204：Industrial control module controls gas circuit opening and closing by logic controller, the CO of generation will be decomposed in sampling box2With
First carrier gas pushes the first quantitative loop；
S205：The gas that industrial control module is controlled in the first quantitative loop is detected into the first detector；
S206：Industrial control module controls gas circuit opening and closing by logic controller, makes the first gas enter the first quantitative loop
And by the detection of the first detector；
S207：First detector is sent testing result to Central Control Module by communication module.
S3：The analysis module of analytic unit second carries out humid analysis and obtains the second result to sample, specifically includes：
S301：Control unit Central Control Module sends humid analysis instruction；Control unit industrial control module is by logical
News module receives humid analysis instruction, gas circuit opening and closing is controlled by logic controller, into humid analysis state；
S302：Sampling pump startup, sampling head extracts the fine particle in air, and fine particle Jing denuders enter sampling
Room；Denuder absorbs the CO of interference test sample2And SO2Deng gas, for removing the interference gas being mixed in aerosol；
S303：Deionized water leacheate is added sampler chamber by peristaltic pump；Heated by heater strip, make acid mist room produce HCl
Acid mist is simultaneously passed through in sampler, and with the liquid after the indoor liquid reactant mixture of sampling waste liquid tank is flowed into, and reacted gas is entered
Enrichment room alkali lye pond；Leacheate rinses humid analysis sampler inner tube, will be attached to aerosol dissolving, punching on tube wall and in pipe
Brush, the soluble-salt of dissolving is dissolved in water, and insoluble carbonate, elemental carbon and organic carbon are also swum in water, and HCl steam adds
When entering to ascend into wet method sampler, the carbonate and insoluble carbonate in solution all reacts generation CO2, and remaining
Material, including elemental carbon and organic carbon all enter waste liquid cylinder, so as to reach the purpose of separation, impurity removal, now solution with leacheate
Containing following compositions：NaOH, NaCl and Na2CO3；
In the present invention, acid mist is directly added in closed container, both eliminated the error and pollution caused during manual operation, acid
Mist improves arresting efficiency with air carbonate example reaction, completes sampling automatically, shortens whole sampling and analytical cycle, increases
The frequency of data；
S304：Industrial control module receives signal by communication module, and NaOH alkali liquid tanks add NaOH molten into alkali lye pond
Liquid, the PH meters for inserting alkaline tank bottom do not stop to monitor the change of the pH value in solution, and data are transmitted by communication module
Centralized control unit is returned, magnetic stirring apparatus is not stopped work work in alkaline tank, is well mixed solution；
S305：When Central Control Module detects that liquid pH value rises to PH=10 in alkali lye pond, HCl acid solution tanks are to alkali lye
HCl solution is added in pond；
In the present invention, for the ease of CO2With the dissolving of HCl gases, first allow in alkali lye pond and add NaOH, sour gas is entered
Afterwards, pH value can decline, and cause CO below2It is difficult to absorb, so this process is slowly adding alkali always, until HCl is dissolved in
Liquid, CO2It is completely converted into Na2CO3, PH no longer fluctuates, and now sour gas is absorbed thoroughly, and pH value is about 10；Now,
Addition HCl solution can be by the Na in solution2CO3It is converted into CO2Gas, is enriched with CO2For detecting；
S306：When Central Control Module detects that liquid pH value drops to PH=5 in alkali lye pond, industrial control module passes through
Logic controller control gas circuit opening and closing, makes the second carrier gas enter enrichment room；
CO under normal temperature and pressure, in air2Water is dissolved in, its saturated solution PH=5.60, in order to avoid the CO for generating2Dissolving,
The acidity of solution is slightly increased, it is determined that in PH=5；
S307：Industrial control module controls gas circuit opening and closing by logic controller, by the CO in enrichment room2With the second carrier gas
Push the second quantitative loop；Gas in second quantitative loop is detected into the second detector；Second detector is by communication
Module sends testing result to Central Control Module；
S308：NaOH alkali liquid tanks add NaOH solution to Central Control Module to detect liquid in alkali lye pond in alkali lye pond
PH value is 10；
S309：After repeat the above steps S302-S308 complete 10 test sample cycles, industrial control module passes through logic control
Device control gas circuit opening and closing, makes the second gas enter enrichment room and repeat step S304-S307.
S4：Processing unit is contrasted and statistical analysis to the first and second results, obtains analysis result.Due to carbonate
In an atmosphere content is less, and possible single observation method can not obtain effectively observation data sometimes；In order to reduce measure error and
Effective observed result is obtained, two kinds of analysis methods are finally obtained simultaneously using being contrasted and statistical analysis after acquisition observation data
Take effective result.
During actual mechanical process, objective area PM2.5 is sampled using single channel sampling configuration is opened, center control
Module 210 issues airborne fine particulate matter sampling industry control instruction；Sampling pump 130 is opened, and passage magnetic valve is opened, and flow control exists
16.7 liters/min, computer interface arranges the flow value (usually 16.7 liters/min) of gas, mass flow amount controller unification mark
Surely guarantee that actual flow is consistent with experimental design；When setting value is reached in the sampling time, electromagnetism Vavle switching, sampling box with it is extraneous every
Leave and, wait heating furnace to heat up.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not right
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, all of embodiment cannot be exhaustive here, it is every to belong to this
Obvious change that bright technical scheme is extended out changes row still in protection scope of the present invention.
Claims (10)
1. it is a kind of determine air carbonate continuous automatic sampling analysis method, it is characterised in that the method is comprised the following steps：
S1：Sampling unit carries out the continuous automatic sampling of air carbonate；
S2：The analysis module of analytic unit first carries out dry analysis and obtains the first result to sample；
S3：The analysis module of analytic unit second carries out humid analysis and obtains the second result to sample；
S4：Processing unit is contrasted and statistical analysis to first and second result, obtains analysis result.
2. sampling analysis method according to claim 1, it is characterised in that the sampling unit includes sampling head, sampling
Case and sampling pump, step S1 is specifically included：
S101：Control unit Central Control Module sends sampling instruction；
S102：Control unit industrial control module receives the sampling instruction by communication module, by logic controller control
Gas circuit is opened and closed, into sample states；
S103：Sampling pump startup, sampling head extracts fine particle in air；
S104：Sampled with setting time resolution ratio, sample is stored in sampling box；
S105：Centralized control unit arranges and monitors the flow value of gas；
S106：After the completion of sampling, enclosed sampling case.
3. sampling analysis method according to claim 2, it is characterised in that first analysis module include heating furnace,
First gas, the first carrier gas, the first quantitative loop and the first detector, dry analysis in step S2 is specifically included：
S201：Control unit Central Control Module sends dry analysis instruction；Control unit industrial control module is by communicating mould
Block receives the dry analysis instruction, gas circuit opening and closing is controlled by logic controller, into dry analysis state；
S202：Heating furnace carries out scheduled time heating to the sampling box containing sample, the carbonate whole into sample
Decompose and produce CO2, heating-up temperature is 900 DEG C；
S203：Industrial control module controls gas circuit opening and closing by logic controller, makes the first carrier gas enter sampling box；
S204：Industrial control module controls gas circuit opening and closing by logic controller, the CO of generation will be decomposed in sampling box2With first
Carrier gas pushes the first quantitative loop；
S205：The gas that industrial control module is controlled in the first quantitative loop is detected into the first detector；
S206：Industrial control module controls gas circuit opening and closing by logic controller, makes the first gas enter the first quantitative loop and quilt
First detector is detected；
S207：First detector is sent testing result to Central Control Module by communication module.
4. sampling analysis method according to claim 2, it is characterised in that second analysis module include denuder,
Sampler chamber, enrichment room, the second gas, the second carrier gas, the second quantitative loop and the second detector, the sampler chamber includes being arranged at adopting
Sampler inside specimen chamber and the peristaltic pump, acid mist room and the first waste liquid pool that are connected with the sampler chamber, the enrichment room includes
Alkali lye pond and the PH meters, NaOH alkali liquid tanks, HCl acid solution tanks, agitator and the second waste liquid pool that are connected with the alkali lye pond, the step
Humid analysis in rapid S3 is specifically included：
S301：Control unit Central Control Module sends humid analysis instruction；Control unit industrial control module is by communicating mould
Block receives the humid analysis instruction, gas circuit opening and closing is controlled by logic controller, into humid analysis state；
S302：Sampling pump startup, sampling head extracts the fine particle in air, and the fine particle Jing denuders enter sampling
Room；
S303：Deionized water leacheate is added sampler chamber by peristaltic pump；Acid mist room produces HCl acid mists and is passed through in sampler, with
Liquid after the indoor liquid reactant mixture of sampling flows into waste liquid tank, and reacted gas enters enrichment room alkali lye pond；
S304：NaOH alkali liquid tanks add NaOH solution, agitator to be stirred the liquid in alkali lye pond into alkali lye pond, PH meters
The pH value of liquid in alkali lye pond is detected and is sent to Central Control Module by communication module；
S305：When Central Control Module detects that liquid pH value rises to PH=10 in alkali lye pond, HCl acid solutions tank is in alkali lye pond
Add HCl solution；
S306：When Central Control Module detects that liquid pH value drops to PH=5 in alkali lye pond, industrial control module passes through logic
Controller control gas circuit opening and closing, makes the second carrier gas enter enrichment room；
S307：Industrial control module controls gas circuit opening and closing by logic controller, by the CO in enrichment room2Push with the second carrier gas
Second quantitative loop；Gas in second quantitative loop is detected into the second detector；Second detector passes through communication module
Testing result is sent to Central Control Module；
S308：NaOH alkali liquid tanks add NaOH solution to Central Control Module to detect liquid pH value in alkali lye pond in alkali lye pond
For 10；
S309：After repeat the above steps S302-S308 complete 10 test sample cycles, industrial control module passes through logic controller control
Gas circuit opening and closing processed, makes the second gas enter enrichment room and repeat step S304-S307.
5. the sampling analysis method according to any one of claim 1-4, it is characterised in that first, second gas
For CO2Standard Gases, first, second carrier gas is He gas, and first, second detector is gas chromatography detector.
6. sampling analysis method according to claim 5, it is characterised in that the CO2Standard Gases are 5% for mass ratio
CO2The mixture of gas and He gases.
7. it is a kind of determine air carbonate continuous automatic sampling and analyzing device, it is characterised in that the device include sampling unit,
Control unit, analytic unit and processing unit, wherein
Sampling unit includes sampling head, sampling box and sampling pump, and sampling head and sampling pump by logic controller and are sampled respectively
Case is connected, and the logic controller is set to two-way electromagnetic valve or four way solenoid valve according to gas circuit connection；
Control unit includes Central Control Module, communication module and industrial control module, and Central Control Module sends sampling and divides
Analysis instruction, is transmitted to industrial control module by communication module, industrial control module control sampling unit carry out sampling operation and
Analytic unit carries out sample analysis；
Analytic unit includes the first analysis module and the second analysis module, wherein the first analysis module is used to carry out dry method to sample
The first result is analyzed and obtains, the second analysis module is used to carry out humid analysis to sample and obtain the second result, analytic unit
First and second results are sent to Central Control Module by communication module；
Processing unit is contrasted and statistical analysis to first and second result, obtains analysis result.
8. sampling and analyzing device according to claim 7, it is characterised in that the sampling head includes sampling mould bases and setting
Sampling film on sampling mould bases；The sampling mould bases material is quartz；The sampling film is quartz film；The sampling head and adopt
Also include cutter and rainwater separator between sample case；Also include the 3rd flow sensor between the sampling box and sampling pump.
9. sampling and analyzing device according to claim 7, it is characterised in that first analysis module include heating furnace,
First gas, the first carrier gas, the first quantitative loop and the first detector；
Second analysis module includes denuder, sampler chamber, enrichment room, the second gas, the second carrier gas, the second quantitative loop and the
Two detectors, wherein
Sampler chamber include sampling chamber inlet, sampler chamber outlet, the sampler that is arranged inside sampler chamber and with the sampler chamber phase
Peristaltic pump even, acid mist room and the first waste liquid pool；
Enrichment room includes enrichment chamber inlet, the outlet of enrichment room, alkali lye pond and the PH meters, the NaOH alkali lye that are connected with the alkali lye pond
Tank, HCl acid solution tanks, agitator and the second waste liquid pool；
Described device also includes being arranged in gas circuit is used for the first flow sensor for determining the first gas flow, for determining the
The second flow sensor of two gas flows, for determine the first nebulizer gas pressure first pressure sensor and for determine second
The second pressure sensor of nebulizer gas pressure.
10. sampling and analyzing device according to claim 7, it is characterised in that
First, second gas is CO2Standard Gases, first, second carrier gas is He gas, and first, second detector is
Gas chromatography detector；The CO2Standard Gases are CO that mass ratio is 5%2The mixture of gas and He gases.
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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 |
| CN112378905A (en) * | 2020-12-02 | 2021-02-19 | 北京大学 | Accurate online monitoring method and system for ammonia content in ambient air |
| CN112763653A (en) * | 2020-12-14 | 2021-05-07 | 复旦大学 | Device and method for collecting atmospheric fine particulate concentrated solution on line and measuring total toxicity |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108760415A (en) * | 2018-08-13 | 2018-11-06 | 北京大学 | More grain size sections automatically switch sampling apparatus for atmospheric particulate matter and the automatic method of sampling |
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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 |
| CN112378905A (en) * | 2020-12-02 | 2021-02-19 | 北京大学 | Accurate online monitoring method and system for ammonia content in ambient air |
| CN112763653A (en) * | 2020-12-14 | 2021-05-07 | 复旦大学 | Device and method for collecting atmospheric fine particulate concentrated solution on line and measuring total toxicity |
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