CN110261188A - A kind of flue gas pollutant alternately concentration release device online - Google Patents
A kind of flue gas pollutant alternately concentration release device online Download PDFInfo
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- CN110261188A CN110261188A CN201910696852.1A CN201910696852A CN110261188A CN 110261188 A CN110261188 A CN 110261188A CN 201910696852 A CN201910696852 A CN 201910696852A CN 110261188 A CN110261188 A CN 110261188A
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- 239000003546 flue gas Substances 0.000 title claims abstract description 44
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 19
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 116
- 238000005070 sampling Methods 0.000 claims abstract description 114
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 98
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000012159 carrier gas Substances 0.000 claims description 28
- 230000005540 biological transmission Effects 0.000 claims description 17
- 238000002347 injection Methods 0.000 claims description 17
- 239000007924 injection Substances 0.000 claims description 17
- 238000004817 gas chromatography Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 7
- 239000003708 ampul Substances 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000013076 target substance Substances 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 239000004615 ingredient Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 58
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 30
- 238000001514 detection method Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 17
- 239000000126 substance Substances 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 238000004056 waste incineration Methods 0.000 description 4
- 231100000770 Toxic Equivalency Factor Toxicity 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000003987 high-resolution gas chromatography Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 108090000371 Esterases Proteins 0.000 description 1
- 206010020843 Hyperthermia Diseases 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- CFQGDIWRTHFZMQ-UHFFFAOYSA-N argon helium Chemical compound [He].[Ar] CFQGDIWRTHFZMQ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 230000036031 hyperthermia Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 238000000844 transformation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2202—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
- G01N1/2205—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling with filters
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2202—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
- G01N1/2214—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling by sorption
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/38—Flow patterns
- G01N30/40—Flow patterns using back flushing
Abstract
A kind of flue gas pollutant alternately concentration release device online, belongs to concentrating sample technical field, is enriched with release module including the connected gas source ducting module of sequence, water removal module, first order enrichment release module and the second level；Eight ways valve, the first sampling trap and the second sampling trap are equipped in the first order enrichment release module；The first sampling trap both ends and the second sampling trap both ends are all connected with eight ways valve；By the switching of eight ways valve, the first sampling trap and the second sampling trap are alternately passed through sample.The present apparatus uses secondary absorption, the first order samples cold-trap with large volume, adsorb big quantity of material, the second level focuses cold-trap with small size, the defect for overcoming the target substance ingredient of traditional flue gas sampler very few, meanwhile, the present apparatus is that release device is concentrated in alternative expression online, the enrichment of alternative expression can be realized to flue gas pollutant, to realize that continuous sampling is analyzed.
Description
Technical field
The invention belongs to concentrating sample technical fields, and in particular to for a kind of flue gas pollutant, alternately concentration release is filled online
It sets.
Background technique
Currently, the relevant technologies that China's waste incineration utilizes have been used widely, and will be protected in coming 10 years
Hold the trend of high speed development.Waste incineration bring secondary pollution emission problem, the especially emission problem of dioxin, also get over
To get over the concern by government, the common people, in addition it is entire as many waste incineration power generation project addressings, construction, operation etc. is perplexed
The thorny problem of process.
According to the requirement of " Convention of Stockholm about persistence organic pollutant " emission reduction dioxin, the various rows in China
The source of putting must effectively accomplish dioxin emission reducing control.Dioxin belongs to trace level substance, and concentration is generally 10 in flue gas-10 g/
m3Left and right is lower, therefore accurately measures its concentration technical difficulty with higher, currently, other flue gases in addition to dioxin
Pollutant, detection method is mostly highly developed, and the detection of the dioxin of incinerator can't realize it is online quick
Detection.
At present in China's incineration flue gas dioxin detection mainstream technology, be a kind of offline inspection technology.The technology
Dependent on dioxin measuring method " surrounding air as defined in " consumer waste incineration contamination control standard " (GB 18485-2014)
With measurement isotopic dilution high-resolution chromatography of gases-high resolution mass spectrometry of exhaust gas dioxin ".This is using spot sampling knot
The off-line checking method of laboratory pretreatment with analysis test is closed, can be measured for incinerator dioxin and accurate detection is provided
Data.This analysis of dioxins samples at the scene first, later send sample to the dioxin laboratory of national authentication, warp
Divided offline after the series of steps such as purification, purification using high-resolution gas-chromatography/high-resolution mass spectrometer (HRGC/HRMS)
Analysis；Several weeks or more need to be generally reached through the sample pretreatment process of very complicated, measurement period.The time-consuming serious, expense of this method
Valuableness, and test result to operation without directive function, become at present comprehensively effectively control dioxin important restriction factor.
In addition, can not in time, accurately understand the dioxin data of waste incinerator, also brought to government regulation, supervision by the public
The technology barrier that can not go beyond.
Serve the target and demand of dioxin emission reducing rapidly based on testing result, research and development is quick, real-time two
Disliking English online test method, technology and equipment, micro, trace persistence organic pollutant detects and controls hair as burning process
One of main trend of exhibition.Dioxin online measuring technique has dioxin concentration in the online flue gas of reflection in real time, refers to rapidly
It leads burning Operating condition adjustment and gas cleaning parameter optimization in furnace, assist the advantages that dioxin generating process mechanism study and effect.
Because existing analytical technology cannot achieve the direct detection of dioxin, thus the dioxin of current main-stream is examined online
Survey technology route, which is taken, the intermediary for determining that associated online concentration is relatively large or is easy to detect to some and dioxin
Matter (or precursor) is detected, and then evaluates the online concentration of dioxin.Dioxin predecessor concentration in flue gas is low, right
Temperature requirement is high.Complicated component in flue gas is overcome required for this indirect detection mode, and concentration is irregular, and moisture content is high, adopts
The problems such as sample flow path is complicated.
Therefore, release device is alternately concentrated in a kind of flue gas pollutant of the technical program online, solves above-mentioned difficult point, makes flue gas
Middle target contaminant can be concentrated and impurity is less, lose less into detection system.
Summary of the invention
It is an object of the invention to overcome defect and deficiency mentioned above, and a kind of flue gas pollutant is provided and is replaced online
Release device is concentrated.
The present invention realizes its purpose, and the technical solutions adopted are as follows.
A kind of flue gas pollutant alternately concentration release device online, including the connected gas source ducting module of sequence, water removal mould
Block, first order enrichment release module and the second level are enriched with release module；Be equipped in the first order enrichment release module eight ways valve,
First sampling trap and the second sampling trap；The first sampling trap both ends and the second sampling trap both ends are all connected with eight ways valve；Pass through eight
The switching of port valve, the first sampling trap and the second sampling trap are alternately passed through sample.
The gas source ducting module, including the switching of blank pipeline, standard gas pipeline, sample lines, blowback air pipe, sample introduction
Valve；The sampling switching valve is provided with an outlet, a back blow port and at least one injection port, wherein back blow port and into
Sample mouth is connected；First injection port of sampling switching valve connects blank pipeline；The blank pipeline is connected with blank source；Sample introduction is cut
Change second injection port connection standard gas pipeline of valve；The standard gas piping connection has standard gas source；The third of sampling switching valve into
Sample mouth connects sample lines；The sample lines are connected with sampling gun, and sample lines are equipped with hot filtration apparatus；Sample introduction switching
The 4th injection port emptying of valve is reserved；The back blow port of sampling switching valve connects blowback air pipe；The blowback air piping connection
There is blowback gas source, and blowback air pipe is equipped with the first solenoid valve；The outlet connection water removal module of sampling switching valve.
The water removal module, including it is the first four-way, the first evacuated tube road, the first six-way valve, the first water removal trap, the two or six logical
Valve, the second water removal trap, the first gas-carrier pipeline, the first threeway, the first triple valve, the second evacuated tube road；
The sampling switching valve, the first six-way valve that gas source ducting module is separately connected there are four connector is arranged in first four-way
1st interface, the 1st interface of the second six-way valve, the first evacuated tube road；
First evacuated tube road is provided with the first MFC and the first drain pump；
First six-way valve and the second six-way valve, are provided with 6 interfaces, respectively the 1st interface, the 2nd interface, interface 3,
4th interface, the 5th interface, the 6th interface, there are two states for tool: when being in A condition, the 1st interface and the 6th orifice, and the 2nd
Interface is connected to interface 3, the 4th interface and the 5th orifice；When being in B state, the 1st interface and the 2nd orifice, the 3rd
Interface and the 4th orifice, the 5th interface and the 6th orifice；
The 2nd interface connection first order of first six-way valve is enriched with release module；The interface 3 pipeline of first six-way valve
The first water removal of connection trap one end, the first water removal trap other end connect the 6th interface of the first six-way valve；The of first six-way valve
4 the first triple valves of interface piping connection；5th the first threeway of interface piping connection of first six-way valve；
The 2nd interface connection first order of second six-way valve is enriched with release module；The interface 3 pipeline of second six-way valve
The second water removal of connection trap one end, the second water removal trap other end connect the 6th interface of the second six-way valve；The of second six-way valve
4 the first triple valves of interface piping connection；5th the first threeway of interface piping connection of second six-way valve；
First gas-carrier pipeline one end connects the first threeway, and the other end connects the second threeway, and the first gas-carrier pipeline is provided with
Second solenoid valve；
There are three connectors for the first threeway setting, are separately connected the first gas-carrier pipeline, the 5th interface of the first six-way valve, second
5th interface of six-way valve；
There are three connectors for the second threeway setting, are connected separately with carrier gas source, the first gas-carrier pipeline and the second gas-carrier pipeline；
First triple valve is connected with the 4th interface and the second evacuated tube of the 4th interface of the first six-way valve, the second six-way valve
Road；
Second evacuated tube road is provided with the first activated carbon tube.
The first order is enriched with release module, further includes the first three-way switch valve, the second three-way switch valve, the second carrier gas pipe
Road, third emptying pipeline, the 4th emptying pipeline, third activated carbon tube；
First three-way switch valve is provided with 3 interfaces, including connecting the A interface of the first six-way valve, the B of the second six-way valve
The C interface of interface, eight ways valve.First three-way switch valve is led to by control AC or BC leads to carry out gas circuit switching (connection
Or resistance is but).
The eight ways valve is provided with 8 interfaces, and there are two states for tool: when being in A condition, the 1st interface and the 7th interface
Connection, the 2nd interface and the 8th orifice, interface 3 and the 5th orifice, the 4th interface and the 6th orifice；When in B shape
When state, the 1st interface is connected to interface 3, the 2nd interface and the 4th orifice, the 5th interface and the 7th orifice, the 6th interface and
8th orifice；
The 1st interface connection third of eight ways valve empties pipeline；2nd interface of eight ways valve connects the first three-way switch valve；Eight ways valve
Interface 3 connection second sampling trap one end；The other end of the 4th interface connection the second sampling trap of eight ways valve；Eight ways valve
5th interface connects the second gas-carrier pipeline；6th interface of eight ways valve connects the second three-way switch valve；7th interface of eight ways valve connects
One end of first sampling trap；The other end of the 8th interface connection the first sampling trap of eight ways valve；
The third emptying pipeline is provided with the 2nd MFC, the second activated carbon tube and the second drain pump；
Second gas-carrier pipeline includes the 3rd MFC；Described 3rd one end MFC connects the second threeway, and the other end connects eight ways valve
The 5th interface；
The 4th emptying pipeline is provided with third activated carbon tube.
The second level enrichment release module includes third six-way valve, the 5th emptying pipeline, the 4th activated carbon tube, focuses
Trap, gas-chromatography module and transmission line；
The third six-way valve is provided with 6 interfaces: the 1st interface connects the second three-way switch valve, the 5th emptying of the 2nd interface connection
Pipeline, interface 3 connection focus trap one end, the 4th interface connection gas-chromatography module, the 5th interface connection transmission line, the 6th interface
Connection focuses the trap other end；
The third six-way valve has two states of A and B；When being in A condition, the 1st interface of third six-way valve and the 6th is connect
Mouth connection, the 2nd interface of third six-way valve are connected to interface 3, the 4th interface of third six-way valve and the 5th orifice；Work as place
When B state, the 1st interface of third six-way valve and the 2nd orifice, the interface 3 of third six-way valve and the 4th orifice,
5th interface of third six-way valve and the 6th orifice；
The gas-chromatography module is connected with transmission line；
The 5th emptying pipeline is provided with the 4th activated carbon tube；
The transmission line is a packless quartz ampoule of inner wall, internal diameter 0.25mm.
The present apparatus uses secondary absorption, and the first order is sampled cold-trap with large volume, can be sampled with large volume, adsorb a large amount of objects
Matter, the second level focus cold-trap with small size, play focusing, overcome the target substance ingredient of traditional flue gas sampler is very few to lack
It falls into, meanwhile, the present apparatus is that release device is concentrated in alternative expression online, the enrichment of alternative expression can be realized to flue gas pollutant, thus real
Existing continuous sampling analysis.
Detailed description of the invention
Fig. 1 is structural schematic diagram of the invention；
Fig. 2 is the structural schematic diagram of gas source ducting module；
Fig. 3 is the structural schematic diagram for removing water module；
Fig. 4 is the structural schematic diagram of first order enrichment release module；
Fig. 5 is the structural schematic diagram of second level enrichment release module；
In figure: gas source ducting module 100, blank pipeline 101, blank source 102, standard gas pipeline 103, standard gas source 104, sample lines
105, sampling gun 106, blowback air pipe 107, blowback gas source 108, the first solenoid valve 109, sampling switching valve 110, heating and filtering
Device 111,
Remove water module 200, the first four-way 201, the first evacuated tube road 202, the first MFC202a, the first drain pump 202b, the one or six
Port valve 203, first removes water trap 204, the second six-way valve 205, second removes water trap 206, the first gas-carrier pipeline 207, second solenoid valve
207a, the first threeway 208, the second threeway 209, carrier gas source 210, the first triple valve 211, second the 212, first activity of evacuated tube road
Charcoal pipe 213,
The first order is enriched with release module 300, the first three-way switch valve 301, eight ways valve 302, first and samples trap 303, second and sample
Trap 304, the second three-way switch valve 305, the second gas-carrier pipeline 306, the 3rd MFC307, third empty pipeline 308, second
MFC309, the second drain pump the 310, the 4th emptying pipeline 311, the second activated carbon tube 312, third activated carbon tube 313,
The second level is enriched with release module 400, third six-way valve the 401, the 5th empties pipeline 402, focuses trap 403, gas-chromatography mould
Block 404, transmission line 405, the 4th activated carbon tube 406.
Specific embodiment
With reference to the accompanying drawing, invention is further described in detail.
A kind of flue gas pollutant alternately concentration release device online, including the connected gas source ducting module 100 of sequence, water removal
Module 200, first order enrichment release module 300 and the second level are enriched with release module 400.
The gas source ducting module 100, including blank pipeline 101, standard gas pipeline 103, sample lines 105, blowback tracheae
Road 107, sampling switching valve 110；The sampling switching valve 110 be provided with an outlet, a back blow port and at least one into
Sample mouth, wherein back blow port is connected with injection port.Described preferred, the sampling switching valve 110 is provided with an outlet, one
Back blow port and four injection ports, and the injection port quantity being connected to outlet is always one.In the technical program, sample introduction switching
Valve 110 can be using -1/4 inch of fittings, 4.0mm of the valco common outlet selectors of Switzerland
ports。
First injection port of sampling switching valve 110 connects blank pipeline 101；The blank pipeline 101 is connected with blank
Source 102.The blank pipeline 101 is provided with heating tape.Blank pipeline 101 need to be heated to 180 DEG C with heat tracing.The blank source
Nitrogen or argon gas etc. are contained in 102.
Second injection port of sampling switching valve 110 connects standard gas pipeline 103；The standard gas pipeline 103 is connected with standard gas
Source 104.Standard gas pipeline 103 and standard gas source 104 need to be heated to 180 DEG C.Standard gas source 104 is calibration effect, makees standard curve, has
Standard curve can just obtain target concentration in flue gas.Standard gas is exactly standard substance in the state of gaseous state.
The third injection port of sampling switching valve 110 connects sample lines 105；The sample lines 105 are connected with sampling
Rifle 106, and sample lines 105 are equipped with hot filtration apparatus 111.The sample lines 105, sampling gun 106, hot filtration apparatus
111 and sampling switching valve 110 will need to be heated to 180 DEG C.
4th injection port of sampling switching valve 110 is vented, and is reserved.The reserved injection port give over to it is spare, to be passed through
Other flue gases.
The back blow port of sampling switching valve 110 connects blowback air pipe 107；The blowback air pipe 107 is connected with blowback air
Source 108, and blowback air pipe 107 is equipped with the first solenoid valve 109.
The outlet connection water removal module 200 of sampling switching valve 110.
Sampling switching valve 110 switches different states, and different gas sources can be made to enter subsequent instrumentation.Pass through sampling switching valve
110, so that leading to water removal module 200 is standard gas, sample or blank gas.
The water removal module 200, including the first four-way 201, the first evacuated tube road 202, the first six-way valve 203, first remove
Water trap 204, the second six-way valve 205, second remove water trap 206, the first gas-carrier pipeline 207, the first threeway 208, the first triple valve
211, the second evacuated tube road 212.
First four-way 201 setting there are four connector, be separately connected gas source ducting module 100 sampling switching valve 110,
The 1st interface, the 1st interface of the second six-way valve 205, the first evacuated tube road 202 of first six-way valve 203.
First evacuated tube road 202 is provided with the first MFC202a and the first drain pump 202b.
MFC is MASS FLOW CONTROLLER, i.e. mass flow controller.
First evacuated tube road 202 is main exhaust pipe, is constantly in flowing shape to the gas inside holding meanss pipeline
State becomes dead volume after avoiding long-time of the gas in pipeline from stopping.
First six-way valve 203 and the second six-way valve 205, are provided with 6 interfaces, and respectively the 1st interface, the 2nd connects
Mouth, interface 3, the 4th interface, the 5th interface, the 6th interface, to arrange clockwise in figure, there are two states for tool: when in A
When state, the 1st interface and the 6th orifice, the 2nd interface are connected to interface 3, the 4th interface and the 5th orifice；When in B
When state, the 1st interface and the 2nd orifice, interface 3 and the 4th orifice, the 5th interface and the 6th orifice.
The 2nd interface connection first order of first six-way valve 203 is enriched with release module 300；
The interface 3 piping connection first of first six-way valve 203 removes water 204 one end of trap, and first water removal 204 other end of trap connects
Connect the 6th interface of the first six-way valve 203；
4th the first triple valve of interface piping connection 211 of first six-way valve 203；
5th the first threeway of interface piping connection 208 of first six-way valve 203.
The 2nd interface connection first order of second six-way valve 205 is enriched with release module 300；
The interface 3 piping connection second of second six-way valve 205 removes water 206 one end of trap, and second water removal 206 other end of trap connects
Connect the 6th interface of the second six-way valve 205；
4th the first triple valve of interface piping connection 211 of second six-way valve 205；
5th the first threeway of interface piping connection 208 of second six-way valve 205.
Described first gas-carrier pipeline, 207 one end connects the first threeway 208, and the other end connects the second threeway 209, and first carries
Air pipe 207 is provided with second solenoid valve 207a.
First threeway 208 setting is separately connected the first gas-carrier pipeline 207, the first six-way valve 203 there are three connector
5th interface of the 5th interface, the second six-way valve 205.
Second threeway 209 setting is connected separately with carrier gas source 210, the first gas-carrier pipeline 207 and the there are three connector
Two gas-carrier pipelines 306.
First triple valve 211 is connected with the 4th interface of the 4th interface of the first six-way valve 203, the second six-way valve 205
With the second evacuated tube road 212.
Second evacuated tube road 212 is provided with the first activated carbon tube 213.
Pipeline, the first six-way valve 203 to the first between first four-way, 201 to the first six-way valve 203 remove water trap 204
Between pipeline, first water removal trap 204 to the first order be enriched with release module 300 between pipeline be provided with heating tape, with companion
Torrid zone heating, 180 DEG C of heat tracing.
Pipeline, the second six-way valve 205 to the second between first four-way, 201 to the second six-way valve 205 remove water trap 206
Between pipeline, second water removal trap 206 to the first order be enriched with release module 300 between pipeline be provided with heating tape, with companion
Torrid zone heating, 180 DEG C of heat tracing.
When removing water the work of module 200, the state of first six-way valve 203 and the second six-way valve 205 is opposite:
When the first six-way valve 203 is in A condition, the second six-way valve 205 is in B state；At this point, from gas source ducting module 100
The standard gas or sample gas to come over, part standard gas or sample gas enter the 1st of the first six-way valve 203 by the first four-way 201
Then interface enters the first water removal trap 204 from the 6th interface of the first six-way valve 203 and carries out water removal operation, the first water removal trap 204
In low-temperature condition and water removal is freezed, moisture is frozen into liquid or condensation；By removing the standard gas or sample gas of water process,
Into the first six-way valve 203 interface 3 and from the 2nd interface of the first six-way valve 203 enter the first order enrichment release module
300；Part standard gas or sample gas enter the 1st interface of the second six-way valve 205 by the first four-way 201, then from the two or six
2nd interface of port valve 205 is hindered but after entering first order enrichment release module 300, which closes, and gas can not circulate；
Meanwhile the carrier gas in carrier gas source 210, by the second threeway 209, the first gas-carrier pipeline 207 and the first threeway 208, part
Carrier gas comes the first triple valve 211 by the 5th interface of the first six-way valve 203, the 4th interface of the first six-way valve 203；Part carries
For gas by the 5th interface of the second six-way valve 205, the 6th interface of the second six-way valve 205, the second water removal trap 206, heating is dry to blow band
Moisture is walked, is then entered from the interface 3 of the second six-way valve 205, the 4th interface of the second six-way valve 205, the first triple valve 211
Outlet after to the second evacuated tube road 212；Second evacuated tube road 212 is provided with the first activated carbon tube 213, to adsorb pollution
Object avoids pollution object and is directly discharged into aerial；
When the first six-way valve 203 is in B state, the second six-way valve 205 is in A condition, and the first three-way switch valve 301 also switches
The air inlet of ventilation；At this point, the standard gas or sample gas that come from gas source ducting module 100, enter by the first four-way 201
Then 1st interface of the first six-way valve 203 enters first order enrichment release module 300 from the 2nd interface of the first six-way valve 203
It is hindered but afterwards, so that the channel is closed, gas can not circulate；The standard gas or sample gas to come from gas source ducting module 100, warp
The 1st interface that the first four-way 201 enters the second six-way valve 205 is crossed, then enters second from the 6th interface of the second six-way valve 205
Remove water trap 206 carry out water removal operation, second water removal trap 206 is in low-temperature condition and freezes water removal, moisture be frozen into liquid or
Person's condensation；By removing the standard gas or sample gas of water process, into the second six-way valve 205 interface 3 and from the second six-way valve
205 the 2nd interface enters first order enrichment release module 300；
Meanwhile the carrier gas in carrier gas source 210, by the second threeway 209, the first gas-carrier pipeline 207 and the first threeway 208, part
Carrier gas, later to the first water removal trap 204, adds by the 5th interface of the first six-way valve 203 and the 6th interface of the first six-way valve 203
Hot dry blow takes away moisture, then from the interface 3 of the first six-way valve 203, the 4th interface, the first triple valve of the first six-way valve 203
211 enter outlet behind the second evacuated tube road 212；Part carrier gas is later by the 5th interface, the 4th interface of the second six-way valve 205
But to the resistance of the first triple valve 211.
By be arranged it is arranged side by side remove water pipeline, and two six-way valves are reasonably set, so that two-way replaces work except water pipeline
Make, that is to say, that when a water removal trap is when carrying out water removal operation, another water removal trap then passes through carrier gas and takes away extra water
Point, it is ready for its subsequent water removal operation.
Preferably, the water removal trap internal diameter 3mm, non-filling, and use deactivation quartz ampoule.Effect: internal diameter is small advantageous
In substance quickly through reduction is adsorbed probability.
When water removal, water removal trap is in low-temperature condition；When blowback, water removal trap be in the condition of high temperature heat when water become gaseous state with
Carrier gas is taken away.
The first order enrichment release module 300 includes the first three-way switch valve 301, the sampling trap of eight ways valve 302, first
303, the second sampling trap 304, the second three-way switch valve 305, the second gas-carrier pipeline 306, third emptying pipeline the 308, the 4th empty
Pipeline 311, third activated carbon tube 313.
First three-way switch valve 301 is provided with 3 interfaces, including connect the first six-way valve 203 A interface, second
The C interface of the B interface of six-way valve 205, eight ways valve 302.First three-way switch valve 301 by control AC is logical or BC it is logical come
Carry out gas circuit switching (connection or resistance are but).
The eight ways valve 302 is provided with 8 interfaces, and there are two states for tool: when being in A condition, the 1st interface and the 7th
Orifice, the 2nd interface and the 8th orifice, interface 3 and the 5th orifice, the 4th interface and the 6th orifice；Work as place
When B state, the 1st interface is connected to interface 3, the 2nd interface and the 4th orifice, the 5th interface and the 7th orifice, and the 6th
Interface and the 8th orifice.
The 1st interface connection third of eight ways valve 302 empties pipeline 308；2nd interface of eight ways valve 302 connects the first threeway
Switching valve 301；One end of interface 3 connection the second sampling trap 304 of eight ways valve 302；The 4th interface connection the of eight ways valve 302
The other end of two sampling traps 304；5th interface of eight ways valve 302 connects the second gas-carrier pipeline 306；6th interface of eight ways valve 302
Connect the second three-way switch valve 305；One end of the 7th interface connection the first sampling trap 303 of eight ways valve 302；The of eight ways valve 302
The other end of 8 interfaces connection the first sampling trap 303.
The third emptying pipeline 308 is provided with the 2nd MFC309, the second activated carbon tube 312 and the second drain pump 310.
Gas requires power by water removal trap, into sampling trap.Third empty pipeline 308 be gas sampling, water removal,
Enrichment provides power.
Second gas-carrier pipeline 306 includes the 3rd MFC307；Described 3rd one end MFC307 connects the second threeway 209,
5th interface of other end connection eight ways valve 302.
The first sampling trap 303, second samples the quartz ampoule that trap 304 is built-in filler, outer package ceramic heat set,
Ceramic heat set is placed in semiconductor refrigerating box, has the function of cryogenic absorption, high temperature release.
The 4th emptying pipeline 311 is provided with third activated carbon tube 313, adsorbs unadsorbed gas, plays filtering
Effect.
When needing to empty, gas removes inside by third activated carbon tube 313 by the 4th emptying 311 outlet of pipeline
Unadsorbed substance or moisture.
Pipeline between first three-way switch valve 301 and eight ways valve 302, the first sampling trap 303 into sample inlet,
Second sampling trap 304 into the pipeline between sample inlet, eight ways valve 302 and the second three-way switch valve 305, be provided with heat tracing
Band is heated to 180 DEG C or so with heating tape.
When eight ways valve 302 is in A condition, water removal module 200 conveys the standard gas to come or sample gas, by eight ways valve
302 the 2nd interface and the 8th interface enter 303 first order object of the first sampling trap and are adsorbed, remaining standard gas or sample
Gas enters third emptying 308 outlet of pipeline from the 7th interface of eight ways valve 302 and the 1st interface.
Meanwhile the second carrier gas in gas-carrier pipeline 306 passes through the 5th interface and interface 3 of eight ways valve 302, enters the
Two sampling traps 304 simultaneously sample the concentrated gas that is enriched in trap 304 for second and take out of, then the 4th interface Jing Guo eight ways valve 302 with
6th interface comes the second three-way switch valve 305；
When eight ways valve 302 switches to B state, water removal module 200 conveys the standard gas to come or sample gas, by eight ways valve
302 the 2nd interface and the 4th interface enter 304 first order object of the second sampling trap and are adsorbed, remaining standard gas or sample
Gas enters third emptying 308 outlet of pipeline from the interface 3 of eight ways valve 302 and the 1st interface；
Meanwhile the second carrier gas in gas-carrier pipeline 306 passes through the 5th interface and the 7th interface of eight ways valve 302, into the first sampling
Trap 303 simultaneously takes the concentrated gas being enriched in the first sampling trap 303 out of, and then the 8th interface and the 6th Jing Guo eight ways valve 302 connects
Mouthful, come the second three-way switch valve 305；
Second three-way switch valve 305 is provided with 3 interfaces, discharges mould with the 6th interface of eight ways valve 302, second level enrichment respectively
Block 400 and the 4th emptying pipeline 311 connect；The carrier gas for being enriched with first order object is delivered to the by the second three-way switch valve 305
Second level is enriched with release module 400.
The technical program passes through the switching of eight ways valve 302, so that the first sampling trap 303 and the second sampling trap 304 are alternately inhaled
Release is echoed, the continuous concentration to flue gas pollutant is realized.
The connection of carrier gas source 210: so that carrier gas source 210 is enriched with release module 300 with the first order and be connected to, in carrier gas source 210
Carrier gas flows through outlet after first order enrichment release module 300 and second level enrichment release module 400, the thing not being enriched with
(gas, particle and water) is blown away.
Preferably, the sampling trap, 1/4 inch of internal diameter.Its role is to large volume samples trap and cooperates filler, can
More acquisition target substances, increase the concentration of object, promote precision of analysis.
The second level enrichment release module 400 includes that third six-way valve the 401, the 5th empties pipeline 402, the 4th active carbon
Pipe 406 focuses trap 403, gas-chromatography module 404 and transmission line 405.
The third six-way valve 401 is provided with 6 interfaces: the 1st interface connects the second three-way switch valve 305, the 2nd interface connects
Connect the 5th emptying pipeline 402, interface 3 connection focuses 403 one end of trap, the 4th interface connection gas-chromatography module 404, the 5th interface
Connect transmission line 405, the connection of the 6th interface focuses 403 other end of trap.
The third six-way valve 401 has two states of A and B；When being in A condition, the 1st of third six-way valve 401 is connect
Mouthful and the 6th orifice, the 2nd interface of third six-way valve 401 be connected to interface 3, the 4th interface of third six-way valve 401 with
5th orifice；When being in B state, the 1st interface of third six-way valve 401 and the 2nd orifice, third six-way valve 401
Interface 3 and the 4th orifice, the 5th interface of third six-way valve 401 and the 6th orifice.
The gas-chromatography module 404 and transmission line 405 connect.
The 5th emptying pipeline 402 is provided with the 4th activated carbon tube 406, adsorbs unadsorbed gas, plays filtering
Effect.
The transmission line 405 is a packless quartz ampoule of inner wall, and internal diameter 0.25mm, one end connects third six-way valve
1/16 inch of stainless steel tube of 401 outlets, one end connect gas-chromatography module 404, play and connect excessive and focussing force.
Second three-way switch valve 305 between third six-way valve 401 pipeline, focus trap 403 into sample pipe,
Third six-way valve 401 is provided with heating tape to the pipeline between transmission line 405, is heated to 180 DEG C or so with heating tape.
In the present apparatus, carrier gas is nitrogen or helium argon gas.
Preferably, 403 one end wide-mouth of focusing trap, the thin mouth in one end, when sample focuses sample from thin mouth to
Wide-mouth, diffusion more sufficiently, it is easier to be adsorbed.Sample, from wide-mouth to thin mouth, focuses more sufficient, promotion point when parsing
Analyse accuracy.Further, wide-mouth the internal diameter 3mm, thin mouth internal diameter 1.2mm of trap 403 are focused.
Release device is alternately concentrated online without flue gas pollutant on the market at present, possessed on the market is surrounding air
Online concentration release device, but Air pollutant ingredient is simple, interferent concentration is low, and moisture content is low, sample acquisition stream
Road is low to temperature requirement (general sampling line temperature is consistent with sample original temperature).Smoke components are complicated, lead to the substance of absorption
Very much, increase analysis difficulty.The technical program passes through multi-stage absorption and selects different fillers, selective absorption respective substance.
Smoke components concentration is irregular, if sampling cold-trap with small size, leads to the target substance ingredient mistake needed for us
It is few.The technical program uses secondary absorption instead, and the first order samples cold-trap with large volume, adsorbs a large amount of first order objects, the second level
Cold-trap, which is focused, with small size adsorbs a small amount of second level mark object.
Flue gas moisture content is high, leads to that instrument can be damaged, sample accuracy is greatly reduced.The technical program is using freezing water removal
Water removal module, continuous dewatering esterase, guarantee detection continuity.Cold-trap freezing enrichment concentration, different material optimal adsorption temperature is not
Together, it uses freezing enrichment concentration instead, makes to be enriched with wide temperature range, improve enrichment thickening efficiency.
It is high to sample flow path temperature requirement: sample flow path temperature is consistent with sample original temperature, prevent organic matter due to
Temperature is low to be attracted to sampling pipe surface.In the technical program, sample flow path is controlled at 180 DEG C or so.
Alternately concentration release device, application method are as follows online for a kind of flue gas pollutant:
The debugging of working condition: S1 is heated to 150 DEG C ~ 210 DEG C to air inlet pipeline and valve body；Open the system of water removal module 200
First water removal trap 204 and the second water removal trap 206 are reached -20 DEG C ~ 30 DEG C of low temperature by cold state.
In the present solution, being high-temperature flue gas due to being passed through, therefore, it is necessary to samples to maintain temperature identical with high-temperature flue gas,
Prevent high boiling component from condensing, to ensure that detection accuracy.
Temperature control, is an innovative point of this programme.Acquisition surrounding air only needs equipment flow path temperature and surrounding air
Source is consistent, and common solenoid valve can be realized.But acquisition flue gas (180 DEG C of flue gas) if flow path temperature be lower than gas source temperature,
Object can be adsorbed on flow path.
Containing lubricating oil, rubber ring etc. inside solenoid valve, lubricating oil, rubber ring can volatilize organic matter at high temperature, do
Disturb detection.And solenoid valve, it is easy to fail under the working environment of high temperature, influences the stability of system.In addition, electromagnetic valve structure has
There is dead volume, there is one section to there is dead volume always.
Therefore, flue gas can only be acquired using the valve in the technical program.
S2, the exclusion of exhaust gas in device pipeline:
The connection of blank pipeline 101: it is connected to the blank pipeline 101 of gas source ducting module 100 with water removal module 200, blank source
The blank gas stored in 102 flows through water removal module 200, first and samples outlet after trap 303, is detection previous group with blank sample introduction
Whether sampling has residual, if having residual with regard to several groups of blank of multi-pass or changing instrumental method, as noresidue carries out next group of sampling.
Precision of analysis is promoted with blank sample introduction, is one of quality control method.
S3, the measurement of standard gas: being connected to the standard gas pipeline 103 of gas source ducting module 100 with water removal module 200, standard gas warp
After crossing the water removal of water removal module 200 and the first order object enrichment of the first sampling trap 303, remaining standard gas outlet；Enrichment
After object heating release, adsorbs, remain with the enrichment that carrier gas flows into the second level enrichment progress second level object of release module 400
Remaining first order object outlet；Finally, after the heating release of second level object,
Then enter gas-chromatography module 404 after transmission line 405 to be detected.
S4, the measurement of sample: being connected to the sample lines 105 of gas source ducting module 100 with water removal module 200, sample warp
After crossing the water removal of water removal module 200 and the first order object enrichment of the first sampling trap 303, remaining sample outlet；Enrichment
After object heating release, adsorbs, remain with the enrichment that carrier gas flows into the second level enrichment progress second level object of release module 400
Remaining first order object outlet；Finally, then entering gas phase after transmission line 405 after the heating release of second level object
Chromatography module 404 is detected.
Above-mentioned water removal trap samples trap, focuses trap, cryogenic temperature range (- 20 DEG C ~ 30 DEG C), 1 DEG C of accuracy of temperature control, low temperature is logical
Cross semiconductor refrigerating.1 DEG C of accuracy of temperature control of hyperthermia temperature range (30 DEG C ~ 380 DEG C), high temperature are heated by ceramic heating pipe, heating
Heating rate is greater than 40 DEG C/s, the substance that abrupt release when parsing cold-trap that is rapidly heated is adsorbed.
Embodiment 1:
The present apparatus, cooperation dioxin on-line detecting system measure the toxic equivalent of dioxin in flue gas, comprising the following steps:
Alternately enrichment discharges canbe used on line flue gas organic matter of the present invention, and two dislike in cooperation dioxin on-line detecting system measurement flue gas
The toxic equivalent of English is divided into three steps: standard fit working curve is established in first step target substance (standard gas) calibration.Second step
Target substance in actually detected flue gas, the toxic equivalent that third step passes through correlation model conversion dioxin.
Gas source and sampling module pipeline heating:
In order to avoid target detection substance is lost during flowing through pipeline because of condensation adsorption, the accurate of testing result is influenced
Property, it is necessary to pipeline, the valve body flowed through to gas circuit in gas source and sampling process heats.When being demarcated, each section heating
Process is as follows:
1, it opens standard gas holding vessel (Soviet Union's Ma tank) and the heating of blank (high pure nitrogen) holding vessel, Soviet Union's Ma tank is organic to flue gas
Object alternately 1, No. 2 six-way valve heating of enrichment release device water removal module, heating temperature reach 180 DEG C of setting value, and heating pipeline is used
Heating tape package.
2, water removal 200 refrigerating function of module is opened, so that it is cooled to -10 DEG C with semiconductor cooling device.
3, opening flue gas organic matter, alternately the enrichment release device inner sample first order is enriched with release module 300；Sample
Second level is enriched with pipeline and valve body heating all in 400 gas sampling flow path of release module.
4, gas-chromatography module 404 is opened, flow rate of carrier gas is opened, flow rate of carrier gas is made to be adjusted to 2mL/min.Open dioxin
On-line detecting system.
The calibration of target substance standard gas, establishes standard fit working curve, steps are as follows:
1, the valve of standard gas holding vessel is opened, adjusting sampling switching valve 110 is connected to standard gas pipeline 103 with water removal module 200, beats
It opens the first MFC202a control gas and enters main line flow velocity, open the first drain pump 202b and draft is provided.Adjust main road first
MFC202a flow velocity 50mL/min.The purpose for designing the road main road is in order to switch different sampling sources and in the feelings of sampling gap
Under condition, guarantee that gas circulates always in sample lines, prevents dead volume, that is, prevents static volume.
2, water removal module 200 is entered by the standard gas of gas source ducting module 100.It removes water module 200 and removes water trap setting freezing
- 10 DEG C of cryogenic temperature, the first water removal trap 204 and the second water removal trap 206 work alternatively.Corresponding first sampling of first water removal trap 204
Trap 303, the second water removal trap 206 is corresponding, second samples trap 304.
3, standard gas enters the first sampling trap 303.
When standard gas is by entering the first sampling trap 303, the first 30 DEG C of 303 set temperature of trap of sampling, mesh behind water removal module 200
Mark substance is filled in the filling adsorption of the first sampling trap 303.The sampling flow velocity is controlled by the 2nd MFC309, the second drain pump
310 provide power.Sample flow velocity 10ml/Min, sampling time 15min.
4, the first sampling 303 blowback of trap.
Blowback flow velocity is controlled with the 3rd MFC307, the carrier gas (Ar) in gas storage tank be used as blowback air, blowback pipeline with
And the first unadsorbed substance (gaseous state, liquid, solid-state) in sampling trap 303.The road blowback purpose promotes the pure of acquisition substance
Degree reduces the interference of other substances.50 ml/Min of blowback flow velocity, blowback time 2Min.
5, the first sampling 303 adsorbed material heating desorption of trap, which enters, focuses trap 403.
The first sampling 303 to 300 DEG C of trap (in heating time 20s) of heating, opens simultaneously the 3rd MFC307, and adjusting flow velocity makes
Blowback air 50 ml/Min, duration 5min take away the substance being adsorbed by the first sampling trap 303 and enter focusing trap 403
In.Focus 30 DEG C of 403 temperature of trap.
6, the heating parsing of trap 403 is focused
Heating focuses 403 to 300 DEG C of trap (in heating time 5s), while switching third six-way valve 401, is passed through carrier gas (Ar) 2ml/
Min, duration 5min flow through and focus trap 403, take away the capillary that the substance being adsorbed entered gas-chromatography module 404
In chromatographic column.It is 1/32 English of being transferred by 1/16 inch inner diameter that this, which focuses the transmission line 405 that trap 403 is connected with capillary chromatographic column,
The chromatographic column of very little (internal diameter 0.25mm) sky connects, this purpose is focusing function (from thick thin to internal diameter of internal diameter).
First water removal trap 204, second removes water trap 206, first and samples the sampling trap 304 of trap 303, second, focuses trap 403 and replaces
Sampling, water removal, it is dry blow, parse, realize without blank, all standing, real-time sampling.
7, gas-chromatography separates
Chromatographic column of the substance released through over-focusing trap 403 Jing Guo gas-chromatography module 404 is segregated into subsequent detection
System.
Sampling is accessed with the standard gas holding vessel of various concentration gradient (0.5ppb, 2ppb, 4ppb, 6ppb, 8ppb, 10ppb)
Ducting module, switch sampling valve carry out sample introduction.Flow velocity 10ml/min, time 15min acquire the volume of 150mL altogether.Each volume
The object standard gas of concentration carries out 6 repetition measurements respectively, and the result detected passes through the letter of data acquisition device respectively
Number input terminal is input to data acquisition device, shows data.
According to above-mentioned steps, each volumetric concentration and the corresponding testing result of each concentration draw working curve, then root
It is fitted to obtain regression equation Y=ax+b of standard working curve according to least square method, be obtained by the Fitting Calculation: a=
0.0011, b=0.0012, R2=0.9675, i.e. standard fit working curve y=0.0011x+0.0012.
Detection limit
FormulaCalculation method detection limit MDL.Method detection limit 0.11ppb
Cocnentration factor
By flue gas organic matter, alternately enrichment release device acquires target substance and is directly passed through in dioxin on-line measuring device
Target substance.The ratio of the two is flue gas organic matter alternately enrichment release device cocnentration factor.
The corresponding testing result of different sampling volumes draws working curve, then is fitted to obtain according to least square method
Regression equation Y=ax+b of standard working curve, obtains by the Fitting Calculation: a=0.01446, b=- 0.1685, R2=
0.9988, i.e. standard fit working curve y=0.1446x-0.1685.
Accuracy
Accuracy: 8.8%
Precision (relative standard deviation): 2.3%
The drift of 24 hour concentrations
Under instrument normal operating conditions, it is passed through 10ppb standard gas, instrument to be measured continuous 6 times is calculated and measures mean concentration, ventilation knot
Shu Hou after analysis instrument continuous operation to be measured (period does not allow any maintenance and calibration) for 24 hours, repeats aforesaid operations, and calculate
The average value of 3 measurement concentration after for 24 hours.
The 0.4ppb of concentration drift for 24 hours under the standard gas concentration of 10ppb.
Drying tube moisture removal property.
10ppb, 180 DEG C of flue gas moisture contents 22%, from configured Soviet Union's Ma tank and standard gas in 180 DEG C of different water cuts
Hybrid test.
It moisture content 30% and hereinafter, crosses within de-watering apparatus standard gas loss 15%, but de-watering apparatus standard gas contains in 10% water
The lower loss 61% of amount.De-watering apparatus is very necessary for high-humidity flue gas test.
The technical program is illustrated in the detection that the present embodiment uses dioxin, it is worth noting that, this technology
Scheme is not only limited to the detection of dioxin, applies also for the detection of other gases.
This eight ways valve 302 is two commercially available eight ways valves, such as can be special using the China of publication number CN105938130A
Two eight ways valves in benefit application.
The technical program, by the reasonable setting of pipeline, so that water removal trap and sampling the airintake direction and blowback air of trap
It is contrary, to promote the effect of blowback air.
The present invention is illustrated according to embodiment, under the premise of not departing from present principles, if the present apparatus can also make
Dry modification and improvement.It should be pointed out that it is all using modes technical solutions obtained such as equivalent substitution or equivalent transformations, all fall within this
In the protection scope of invention.
Claims (5)
1. release device is alternately concentrated in a kind of flue gas pollutant online, which is characterized in that including the connected gas source pipeline mould of sequence
Block (100), water removal module (200), first order enrichment release module (300) and second level enrichment release module (400)；Described
Level-one, which is enriched in release module (300), is equipped with eight ways valve (302), the first sampling trap (303) and the second sampling trap (304)；It is described
First sampling trap (303) both ends and second sampling trap (304) both ends are all connected with eight ways valve (302)；Pass through cutting for eight ways valve (302)
It changes, the first sampling trap (303) and the second sampling trap (304) are alternately passed through sample.
2. release device is alternately concentrated in a kind of flue gas pollutant as described in claim 1 online, which is characterized in that the gas source
Ducting module (100), including blank pipeline (101), standard gas pipeline (103), sample lines (105), blowback air pipe (107),
Sampling switching valve (110)；The sampling switching valve (110) is provided with an outlet, a back blow port and at least one sample introduction
Mouthful, wherein back blow port is connected with injection port；First injection port of sampling switching valve (110) connects blank pipeline (101)；Institute
It states blank pipeline (101) and is connected with blank source (102)；Second injection port of sampling switching valve (110) connects standard gas pipeline
(103)；The standard gas pipeline (103) is connected with standard gas source (104)；The third injection port connection of sampling switching valve (110) is adopted
Sample pipeline (105)；The sample lines (105) are connected with sampling gun (106), and sample lines (105) are equipped with heating and filtering
Device (111)；The 4th injection port emptying of sampling switching valve (110) is reserved；The back blow port of sampling switching valve (110) connects blowback
Air pipe (107)；The blowback air pipe (107) is connected with blowback gas source (108), and blowback air pipe (107) is equipped with
One solenoid valve (109)；Outlet connection water removal module (200) of sampling switching valve (110).
3. release device is alternately concentrated in a kind of flue gas pollutant as claimed in claim 2 online, which is characterized in that the water removal
Module (200), including the first four-way (201), the first evacuated tube road (202), the first six-way valve (203), the first water removal trap
(204), the second six-way valve (205), the second water removal trap (206), the first gas-carrier pipeline (207), the first threeway (208), the one or three
Port valve (211), the second evacuated tube road (212)；
There are four connectors for first four-way (201) setting, are separately connected the sampling switching valve of gas source ducting module (100)
(110), the 1st interface of the first six-way valve (203), the 1st interface of the second six-way valve (205), the first evacuated tube road (202)；
First evacuated tube road (202) is provided with the first MFC(202a) and the first drain pump (202b)；
First six-way valve (203) and the second six-way valve (205), are provided with 6 interfaces, and respectively the 1st interface, the 2nd connects
Mouth, interface 3, the 4th interface, the 5th interface, the 6th interface, there are two states for tool: when being in A condition, the 1st interface and the 6th
Orifice, the 2nd interface are connected to interface 3, the 4th interface and the 5th orifice；When being in B state, the 1st interface and the 2nd
Orifice, interface 3 and the 4th orifice, the 5th interface and the 6th orifice；
The 2nd interface connection first order enrichment release module (300) of first six-way valve (203)；First six-way valve
(203) interface 3 piping connection first removes water trap (204) one end, and first water removal trap (204) other end connects the first six-way valve
(203) the 6th interface；4th the first triple valve of interface piping connection (211) of first six-way valve (203)；Described 1st
5th the first threeway of interface piping connection (208) of port valve (203)；
The 2nd interface connection first order enrichment release module (300) of second six-way valve (205)；Second six-way valve
(205) interface 3 piping connection second removes water trap (206) one end, and second water removal trap (206) other end connects the second six-way valve
(205) the 6th interface；4th the first triple valve of interface piping connection (211) of second six-way valve (205)；Described 2nd 6
5th the first threeway of interface piping connection (208) of port valve (205)；
Described first gas-carrier pipeline (207) one end connects the first threeway (208), and the other end connects the second threeway (209), and first
Gas-carrier pipeline (207) is provided with second solenoid valve (207a)；
There are three connectors for first threeway (208) setting, are separately connected the first gas-carrier pipeline (207), the first six-way valve (203)
The 5th interface, the second six-way valve (205) the 5th interface；
Second threeway (209) setting there are three connector, be connected separately with carrier gas source (210), the first gas-carrier pipeline (207) and
Second gas-carrier pipeline (306)；
First triple valve (211) is connected with the 4th interface of the first six-way valve (203), the second six-way valve (205) the 4th connects
Mouth and the second evacuated tube road (212)；
Second evacuated tube road (212) is provided with the first activated carbon tube (213).
4. release device is alternately concentrated in a kind of flue gas pollutant as claimed in claim 3 online, which is characterized in that
The first order is enriched with release module (300), further includes the first three-way switch valve (301), the second three-way switch valve
(305), the second gas-carrier pipeline (306), third emptying pipeline (308), the 4th emptying pipeline (311), third activated carbon tube
(313)；
First three-way switch valve (301), is provided with 3 interfaces, including connect the first six-way valve (203) A interface, second
The C interface of the B interface of six-way valve (205), eight ways valve (302)；
First three-way switch valve (301) is led to by control AC or BC leads to carry out gas circuit switching；
The eight ways valve (302) is provided with 8 interfaces, and there are two states for tool: when being in A condition, the 1st interface and the 7th is connect
Mouth connection, the 2nd interface and the 8th orifice, interface 3 and the 5th orifice, the 4th interface and the 6th orifice；When in B
When state, the 1st interface is connected to interface 3, the 2nd interface and the 4th orifice, the 5th interface and the 7th orifice, the 6th interface
With the 8th orifice；
The 1st interface connection third emptying pipeline (308) of eight ways valve (302)；The 2nd interface connection the one or three of eight ways valve (302)
Direction changeover valve (301)；One end of the second sampling trap (304) of interface 3 connection of eight ways valve (302)；The 4th of eight ways valve (302)
The other end of the second sampling trap (304) of interface connection；5th interface of eight ways valve (302) connects the second gas-carrier pipeline (306)；Eight
6th interface of port valve (302) connects the second three-way switch valve (305)；The 7th interface connection the first sampling trap of eight ways valve (302)
(303) one end；The other end of the first sampling trap (303) of the 8th interface connection of eight ways valve (302)；
Third emptying pipeline (308) is provided with the 2nd MFC(309), the second activated carbon tube (312) and the second drain pump
(310)；
Second gas-carrier pipeline (306) includes the 3rd MFC(307)；3rd MFC(307) one end the second threeway of connection
(209), the 5th interface of other end connection eight ways valve (302)；
4th emptying pipeline (311) is provided with third activated carbon tube (313).
5. release device is alternately concentrated in a kind of flue gas pollutant as claimed in claim 3 online, which is characterized in that described second
Grade enrichment release module (400) includes third six-way valve (401), the 5th emptying pipeline (402), the 4th activated carbon tube (406), gathers
Burnt trap (403), gas-chromatography module (404) and transmission line (405)；
The third six-way valve (401) is provided with 6 interfaces: the 1st interface connects the second three-way switch valve (305), the 2nd interface connects
Connect the 5th emptying pipeline (402), interface 3 connection focus trap (403) one end, the 4th interface connection gas-chromatography module (404),
5th interface connects transmission line (405), the connection of the 6th interface focuses trap (403) other end；
The third six-way valve (401) has two states of A and B；When being in A condition, the 1st of third six-way valve (401) is connect
Mouth and the 6th orifice, the 2nd interface of third six-way valve (401) are connected to interface 3, and the 4th of third six-way valve (401) connects
Mouth and the 5th orifice；When being in B state, the 1st interface and the 2nd orifice of third six-way valve (401), the three or six is logical
The interface 3 and the 4th orifice of valve (401), the 5th interface and the 6th orifice of third six-way valve (401)；
The gas-chromatography module (404) and transmission line (405) connection；
5th emptying pipeline (402) is provided with the 4th activated carbon tube (406)；
The transmission line (405) is a packless quartz ampoule of inner wall, internal diameter 0.25mm.
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| CN201910696852.1A CN110261188B (en) | 2019-07-30 | 2019-07-30 | Online alternative concentration and release device for smoke pollutants |
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| CN110261188B CN110261188B (en) | 2024-03-22 |
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| CN112924568A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Online pretreatment device and method for flue gas sample |
| WO2022089630A1 (en) * | 2020-11-02 | 2022-05-05 | 武汉天虹环保产业股份有限公司 | Cold trap preconcentration system and method |
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| CN110261188B (en) | 2024-03-22 |
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