CN110333313B - Treatment method for online alternate concentration and release of smoke pollutants - Google Patents

Abstract

A treatment method for online alternate concentration and release of smoke pollutants belongs to the technical field of concentrated samples and comprises the debugging of working conditions; removing waste gas in a pipeline of the device; measuring standard gas; and (4) measuring the sample. The method adopts two-stage adsorption, the first stage uses a large-volume sampling cold trap to adsorb a large amount of substances, and the second stage uses a small-volume accumulation coke cold trap to overcome the defect of too few target substance components of the traditional flue gas sampling device.

Description

Treatment method for online alternate concentration and release of smoke pollutants

Technical Field

The invention belongs to the technical field of concentrated samples, and particularly relates to a treatment method for online alternate concentration and release of smoke pollutants.

Background

At present, the related technology of waste incineration utilization in China is widely applied, and the trend of high-speed development is still kept in the next 10 years. The problem of secondary pollutant emission caused by waste incineration, especially the problem of dioxin emission, is more and more concerned by governments and people, and even becomes a troublesome problem which puzzles the whole processes of site selection, construction, operation and the like of many waste incineration power generation projects.

According to the requirement of reducing dioxin emission from the 'Stockholm convention on persistent organic pollutants', various emission sources in China must effectively achieve dioxin emission reduction control. Dioxin belongs to trace-level substances and has a concentration of 10 in flue gas^-10g/m³About or lower, therefore, the accurate measurement of the concentration has higher technical difficulty, at present,most of the detection methods for other smoke pollutants except dioxin are very mature, and the dioxin emission detection of the incinerator cannot realize on-line rapid detection.

At present, the mainstream technology for detecting the emission of dioxin in incineration smoke in China is an off-line detection technology. The technology depends on a dioxin determination method defined in the standard for controlling pollution caused by incineration of household garbage (GB 18485-2014), namely isotope dilution high-resolution meteorological chromatography-high-resolution mass spectrometry for determining dioxins in ambient air and waste gas. The method adopts an off-line detection method combining field sampling with laboratory pretreatment and analysis testing, and can provide accurate detection data for the measurement of the dioxin emission of the incinerator. The dioxin detection method comprises the steps of firstly sampling on site, then sending the sample to a dioxin laboratory certified by the country, and carrying out off-line analysis by applying a high-resolution gas chromatography/high-resolution mass spectrometer (HRGC/HRMS) after a series of steps such as purification and purification; complicated sample pretreatment process is needed, and the measurement period usually reaches more than several weeks. The method is time-consuming and expensive, and the test result has no guiding effect on the operation, so that the method becomes an important restriction factor for comprehensively and effectively controlling the dioxin emission at present. In addition, dioxin emission data of the garbage incinerator cannot be known timely and accurately, and technical barriers which cannot be overcome are brought to government supervision and public supervision.

The method and the device can rapidly serve the aim and the requirement of dioxin emission reduction based on the detection result, and research and development of a rapid and real-time online dioxin detection method, technology and equipment become one of the main trends of trace and trace persistent organic pollutant detection and control development in the incineration process. The online detection technology for the dioxin has the advantages and effects of reflecting the concentration of the dioxin in the flue gas in real time on line, rapidly guiding the adjustment of the combustion condition in the furnace and the optimization of the flue gas purification parameters, assisting the research on the mechanism of the generation process of the dioxin and the like.

Because the existing analysis technology can not realize the direct detection of the dioxin, the current mainstream dioxin online detection technology route adopts the detection of intermediate substances (or precursor substances) which have relatively high online concentration or are easy to detect and are in definite association with the dioxin, so as to evaluate the online concentration of the dioxin. The dioxin precursor has low concentration in the flue gas and high requirement on temperature. The indirect detection mode needs to solve the problems of complex components in the flue gas, uneven concentration, high water content, complex sampling flow path and the like.

Therefore, the treatment method for online alternate concentration and release of the smoke pollutants solves the difficulties, and enables the target pollutants in the smoke to be concentrated, and to enter the detection system with less impurities and less loss.

Disclosure of Invention

The invention aims to overcome the defects and shortcomings and provide a treatment method for online alternate concentration and release of smoke pollutants.

The technical scheme adopted by the invention for achieving the purpose is as follows.

A processing method for online alternate concentration and release of smoke pollutants adopts an online alternate concentration and release device for smoke pollutants, and the device comprises an air source pipeline module, a water removal module, a first-stage enrichment and release module and a second-stage enrichment and release module which are sequentially connected;

the gas source pipeline module comprises a blank pipeline, a standard gas pipeline, a sampling pipeline, a back-blowing gas pipeline and a sample introduction switching valve; the sample introduction switching valve is provided with a sample outlet, a back flushing port and four sample inlets, and the number of the sample inlets communicated with the sample outlet is always one; a first sample inlet of the sample introduction switching valve is connected with a blank pipeline; the blank pipeline is connected with a blank source; a second sample inlet of the sample introduction switching valve is connected with a standard gas pipeline; the standard gas pipeline is connected with a standard gas source; the third sample inlet of the sample introduction switching valve is connected with a sampling pipeline; the sampling pipeline is connected with a sampling gun and is provided with a heating filter;

an eight-way valve, a first sampling trap and a second sampling trap are arranged in the first-stage enrichment and release module; two ends of the first sampling trap and two ends of the second sampling trap are both connected with an eight-way valve;

the second-stage enrichment and release module comprises a third six-way valve, a fourth activated carbon tube, a focusing trap, a gas chromatography module and a transmission line;

the third six-way valve is provided with 6 interfaces: the 1 st interface is connected with the first-stage enrichment release module, the 2 nd interface is connected with a fifth emptying pipeline, the 3 rd interface is connected with one end of the focusing trap, the 4 th interface is connected with the gas chromatography module, the 5 th interface is connected with the transmission line, and the 6 th interface is connected with the other end of the focusing trap;

the third six-way valve has two states of A and B; when the state is A, the 1 st port and the 6 th port of the third six-way valve are communicated, the 2 nd port and the 3 rd port of the third six-way valve are communicated, and the 4 th port and the 5 th port of the third six-way valve are communicated; when the state is in the B state, the 1 st port and the 2 nd port of the third six-way valve are communicated, the 3 rd port and the 4 th port of the third six-way valve are communicated, and the 5 th port and the 6 th port of the third six-way valve are communicated;

the gas chromatography module is connected with a transmission line;

the processing method comprises the following steps:

step 1, debugging the working state: heating the air inlet pipeline and the valve body to 150-210 ℃; starting the refrigeration state of the dewatering module, and enabling the first dewatering trap and the second dewatering trap to reach the low temperature of-20-30 ℃;

step 2, removing waste gas in the device pipeline:

communication of blank pipelines: a blank pipeline of the gas source pipeline module is communicated with the water removal module, and blank gas stored in a blank source is discharged outside after flowing through the water removal module and the first sampling trap to replace waste gas in the pipeline;

step 3, measuring standard gas: a standard gas pipeline of the gas source pipeline module is communicated with the dewatering module, and after the standard gas is dewatered by the dewatering module and a first-stage target object of the first sampling trap is enriched, the rest standard gas is discharged outside; after the enriched target object is heated and released, the enriched target object flows into a second-stage enrichment release module along with carrier gas to carry out enrichment adsorption on the second-stage target object, and the rest first-stage target object is discharged; finally, after the second-stage target object is heated and released, the second-stage target object enters a gas chromatography module for detection after passing through a transmission line;

and 4, determination of a sample: the sampling pipeline of the gas source pipeline module is communicated with the water removal module, and after the sample is subjected to water removal by the water removal module and the first-stage target enrichment of the first sampling trap, the rest sample is discharged outside; after the enriched target object is heated and released, the enriched target object flows into a second-stage enrichment release module along with carrier gas to carry out enrichment adsorption on the second-stage target object, and the rest first-stage target object is discharged; and finally, after the second-stage target object is heated and released, the second-stage target object enters the gas chromatography module for detection after passing through the transmission line.

The water removal of the water removal module in the steps 3 and 4 comprises the following steps:

the water removal module comprises a first four-way, a first emptying pipeline, a first six-way valve, a first water removal trap, a second six-way valve, a second water removal trap, a first gas carrying pipeline, a first three-way valve and a second emptying pipeline;

the first four-way joint is provided with four joints which are respectively connected with a sample introduction switching valve of the gas source pipeline module, a 1 st interface of the first six-way valve, a 1 st interface of the second six-way valve and a first emptying pipeline;

the first emptying pipeline is provided with a first MFC and a first emptying pump;

the first six-way valve and the second six-way valve are both provided with 6 interfaces, namely a 1 st interface, a 2 nd interface, a 3 rd interface, a 4 th interface, a 5 th interface and a 6 th interface, and the first six-way valve and the second six-way valve have two states: when the device is in the A state, the 1 st interface is communicated with the 6 th interface, the 2 nd interface is communicated with the 3 rd interface, and the 4 th interface is communicated with the 5 th interface; when the device is in the state B, the 1 st interface is communicated with the 2 nd interface, the 3 rd interface is communicated with the 4 th interface, and the 5 th interface is communicated with the 6 th interface; the 2 nd interface of the first six-way valve is connected with the first-stage enrichment release module; the 3 rd interface pipeline of the first six-way valve is connected with one end of a first water removing trap, and the other end of the first water removing trap is connected with the 6 th interface of the first six-way valve; the 4 th interface pipeline of the first six-way valve is connected with a first three-way valve; the 5 th interface pipeline of the first six-way valve is connected with a first tee joint; the 2 nd interface of the second six-way valve is connected with the first-stage enrichment release module; the 3 rd interface pipeline of the second six-way valve is connected with one end of a second water removing trap, and the other end of the second water removing trap is connected with the 6 th interface of the second six-way valve; the 4 th interface pipeline of the second six-way valve is connected with the first three-way valve; the 5 th interface pipeline of the second six-way valve is connected with a first tee joint;

one end of the first gas carrying pipeline is connected with the first tee joint, the other end of the first gas carrying pipeline is connected with the second tee joint, and the first gas carrying pipeline is provided with a second electromagnetic valve;

the first tee joint is provided with three joints which are respectively connected with the first gas carrying pipeline, the 5 th interface of the first six-way valve and the 5 th interface of the second six-way valve;

the second tee joint is provided with three joints which are respectively connected with a loaded gas source, a first loaded gas pipeline and a second loaded gas pipeline;

the first three-way valve is connected with a 4 th port of the first six-way valve, a 4 th port of the second six-way valve and a second emptying pipeline;

the second emptying pipeline is provided with a first activated carbon pipe;

the first and second six-way valves are in opposite states:

when the first six-way valve is in the A state, the second six-way valve is in the B state; at the moment, part of the standard gas or the sample gas from the gas source pipeline module enters a 1 st interface of the first six-way valve through the first four-way valve and then enters a first water removal trap from a 6 th interface of the first six-way valve for water removal operation, the first water removal trap is in a low-temperature state and is used for freezing water removal, and water is frozen into liquid or condensed; the standard gas or the sample gas subjected to the water removal treatment enters a 3 rd interface of the first six-way valve and enters a first-stage enrichment and release module from a 2 nd interface of the first six-way valve; part of standard gas or sample gas enters a 1 st interface of the second six-way valve through the first four-way valve, then enters the first-stage enrichment release module from a 2 nd interface of the second six-way valve and is blocked, the channel is closed, and the gas cannot circulate;

meanwhile, carrier gas in the carrier gas source passes through the second tee joint, the first carrier gas pipeline and the first tee joint, and part of the carrier gas passes through a 5 th interface of the first six-way valve and a 4 th interface of the first six-way valve to enter the first three-way valve; part of carrier gas passes through a 5 th interface of the second six-way valve, a 6 th interface of the second six-way valve and the second water removal trap, is heated and blown to remove moisture, and then enters a second emptying pipeline from a 3 rd interface of the second six-way valve, a 4 th interface of the second six-way valve and the first three-way valve and is discharged outside; the second emptying pipeline is provided with a first activated carbon pipe for adsorbing pollutants and preventing the pollutants from being directly discharged into the air;

when the first six-way valve is in the B state, the second six-way valve is in the A state; at the moment, the standard gas or the sample gas from the gas source pipeline module enters the 1 st interface of the first six-way valve through the first four-way joint, and then enters the first-stage enrichment release module from the 2 nd interface of the first six-way valve and is blocked, so that the channel is closed, and the gas cannot circulate; the standard gas or the sample gas from the gas source pipeline module enters a 1 st interface of the second six-way valve through the first four-way joint and then enters a second water removal trap from a 6 th interface of the second six-way valve to carry out water removal operation, the second water removal trap is in a low-temperature state and is used for freezing water removal, and water is frozen into liquid or condensed; the standard gas or the sample gas subjected to the water removal treatment enters a 3 rd interface of the second six-way valve and enters the first-stage enrichment and release module from a 2 nd interface of the second six-way valve;

meanwhile, carrier gas in the carrier gas source passes through a second tee joint, a first carrier gas pipeline and a first tee joint, part of the carrier gas passes through a 5 th interface of a first six-way valve and a 6 th interface of the first six-way valve and then comes to a first water removal trap, is heated and blown to remove moisture, and then enters a second evacuation pipeline from a 3 rd interface of the first six-way valve, a 4 th interface of the first six-way valve and a first three-way valve and is discharged outside; and part of the carrier gas passes through the 5 th interface and the 4 th interface of the second six-way valve and then enters the first three-way valve to be blocked.

The first stage target enrichment of the first sampling well in steps 3 and 4, comprising the steps of:

the first-stage enrichment and release module further comprises a first three-way switching valve, a second gas carrying pipeline, a third emptying pipeline, a fourth emptying pipeline and a third activated carbon pipe;

the first three-way switching valve is provided with 3 interfaces, including an interface A connected with the first six-way valve, an interface B connected with the second six-way valve and an interface C connected with the eight-way valve;

the eight-way valve is provided with 8 interfaces, which have two states: when the state is A, the 1 st interface is communicated with the 7 th interface, the 2 nd interface is communicated with the 8 th interface, the 3 rd interface is communicated with the 5 th interface, and the 4 th interface is communicated with the 6 th interface; when the device is in the state B, the 1 st interface is communicated with the 3 rd interface, the 2 nd interface is communicated with the 4 th interface, the 5 th interface is communicated with the 7 th interface, and the 6 th interface is communicated with the 8 th interface;

the 1 st interface of the eight-way valve is connected with a third emptying pipeline; the 2 nd interface of the eight-way valve is connected with a first three-way switching valve; the 3 rd interface of the eight-way valve is connected with one end of the second sampling trap; the 4 th interface of the eight-way valve is connected with the other end of the second sampling trap; the 5 th interface of the eight-way valve is connected with a second gas carrying pipeline; the 6 th interface of the eight-way valve is connected with a second three-way switching valve; the 7 th interface of the eight-way valve is connected with one end of the first sampling trap; the 8 th interface of the eight-way valve is connected with the other end of the first sampling trap;

the third emptying pipeline is provided with a second MFC, a second activated carbon pipe and a second emptying pump;

the second carrier gas line comprises a third MFC; one end of the third MFC is connected with the second tee joint, and the other end of the third MFC is connected with the 5 th interface of the eight-way valve;

the fourth emptying pipeline is provided with a third activated carbon pipe;

when the eight-way valve is in the state A, the standard gas or the sample gas conveyed by the water removal module enters the first-stage target object of the first sampling trap through the 2 nd interface and the 8 th interface of the eight-way valve to be adsorbed, and the rest of the standard gas or the sample gas enters the third evacuation pipeline from the 7 th interface and the 1 st interface of the eight-way valve to be discharged;

meanwhile, the carrier gas in the second carrier gas pipeline enters the second sampling trap through the 5 th interface and the 3 rd interface of the eight-way valve, takes out the concentrated gas enriched in the second sampling trap, and then enters the second three-way switching valve through the 4 th interface and the 6 th interface of the eight-way valve;

when the eight-way valve is switched to the state B, the standard gas or the sample gas conveyed by the water removal module enters the first-stage target object of the second sampling trap through the 2 nd interface and the 4 th interface of the eight-way valve to be adsorbed, and the rest of the standard gas or the sample gas enters the third evacuation pipeline from the 3 rd interface and the 1 st interface of the eight-way valve to be discharged;

meanwhile, the carrier gas in the second carrier gas pipeline enters the first sampling trap through a 5 th interface and a 7 th interface of the eight-way valve, takes out the concentrated gas enriched in the first sampling trap, and then enters the second three-way switching valve through an 8 th interface and a 6 th interface of the eight-way valve;

the second three-way switching valve is provided with 3 interfaces which are respectively connected with the 6 th interface of the eight-way valve, the second-stage enrichment release module and the fourth emptying pipeline; and the second three-way switching valve is used for conveying the carrier gas enriched with the first-stage target object to the second-stage enrichment release module.

The method adopts two-stage adsorption, the first stage uses a large-volume sampling cold trap to sample in large volume and adsorb a large amount of substances, and the second stage uses a small-volume accumulation coke cold trap to focus, so that the defect of too few target substance components of the traditional flue gas sampling device is overcome.

Drawings

FIG. 1 is a schematic structural view of the present invention;

FIG. 2 is a schematic structural view of an air supply line module;

FIG. 3 is a schematic view of a water removal module;

FIG. 4 is a schematic structural diagram of a first stage enrichment and release module;

FIG. 5 is a schematic structural diagram of a second stage enrichment and release module;

in the figure:

the system comprises an air source pipeline module 100, a blank pipeline 101, a blank source 102, a standard gas pipeline 103, a standard gas source 104, a sampling pipeline 105, a sampling gun 106, a back-blowing gas pipeline 107, a back-blowing gas source 108, a first electromagnetic valve 109, a sample introduction switching valve 110, a heating filter 111, a sample collection device,

The system comprises a water removal module 200, a first four-way valve 201, a first emptying pipeline 202, a first MFC202a, a first emptying pump 202b, a first six-way valve 203, a first water removal trap 204, a second six-way valve 205, a second water removal trap 206, a first gas carrying pipeline 207, a second electromagnetic valve 207a, a first tee joint 208, a second tee joint 209, a gas carrying source 210, a first three-way valve 211, a second emptying pipeline 212, a first activated carbon pipe 213, a second activated carbon pipe 213,

A first-stage enrichment release module 300, a first three-way switching valve 301, an eight-way valve 302, a first sampling trap 303, a second sampling trap 304, a second three-way switching valve 305, a second carrier gas pipeline 306, a third MFC307, a third emptying pipeline 308, a second MFC309, a second emptying pump 310, a fourth emptying pipeline 311, a second activated carbon pipe 312, a third activated carbon pipe 313, a,

A second-stage enrichment and release module 400, a third six-way valve 401, a fifth evacuation pipe 402, a focusing trap 403, a gas chromatography module 404, a transmission line 405 and a fourth activated carbon pipe 406.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings.

A processing method for online alternate concentration and release of smoke pollutants adopts a device comprising an air source pipeline module 100, a water removal module 200, a first-stage enrichment and release module 300 and a second-stage enrichment and release module 400 which are sequentially connected.

The gas source pipeline module 100 comprises a blank pipeline 101, a standard gas pipeline 103, a sampling pipeline 105, a back-blowing pipeline 107 and a sample introduction switching valve 110; the sample switching valve 110 is provided with a sample outlet, a back-flushing port and at least one sample inlet, wherein the back-flushing port is connected with the sample inlet. Preferably, the sample switching valve 110 is provided with one sample outlet, one back flushing port and four sample inlets, and the number of the sample inlets communicated with the sample outlet is always one. In the technical scheme, the sample introduction switching valve 110 can adopt-1/4 inch fits, 4.0mmports of valco common outlet selectors of Switzerland.

A first sample inlet of the sample introduction switching valve 110 is connected with the blank pipeline 101; the blank pipe 101 is connected with a blank source 102. The blank pipe 101 is provided with a heat tracing band. The blank line 101 is heated to 180 ℃ with heat tracing. The blank source 102 may be filled with nitrogen or argon, for example.

The second sample inlet of the sample introduction switching valve 110 is connected with the standard gas pipeline 103; the standard gas pipeline 103 is connected with a standard gas source 104. The standard gas pipeline 103 and the standard gas source 104 need to be heated to 180 ℃. The standard gas source 104 is used for calibration, and a standard curve is drawn, so that the concentration of the target object in the flue gas can be obtained only by the standard curve. The standard gas is the state of the standard substance in the gaseous state.

The third sample inlet of the sample switching valve 110 is connected with the sampling pipeline 105; the sampling pipe 105 is connected with a sampling gun 106, and the sampling pipe 105 is provided with a heating filter 111. The sampling pipe 105, the sampling gun 106, the heating filter 111 and the sample switching valve 110 are all heated to 180 ℃.

And the fourth sample inlet of the sample introduction switching valve 110 is vented and reserved. The reserved sample inlet is reserved for standby application and used for introducing other flue gas.

A back flushing port of the sample introduction switching valve 110 is connected with a back flushing pipeline 107; the back-blowing pipeline 107 is connected with a back-blowing air source 108, and the back-blowing pipeline 107 is provided with a first electromagnetic valve 109.

The sample outlet of the sample switching valve 110 is connected to the water removal module 200.

The sample switching valve 110 switches different states, so that different gas sources can enter subsequent instruments. The sample, or blank gas is passed to the water removal module 200 through the sample switching valve 110.

The water removal module 200 includes a first four-way 201, a first evacuation line 202, a first six-way valve 203, a first water removal trap 204, a second six-way valve 205, a second water removal trap 206, a first carrier gas line 207, a first three-way valve 208, a first three-way valve 211, and a second evacuation line 212.

The first four-way valve 201 is provided with four connectors, which are respectively connected to the sample introduction switching valve 110 of the gas source pipeline module 100, the 1 st interface of the first six-way valve 203, the 1 st interface of the second six-way valve 205, and the first evacuation pipeline 202.

The first drain line 202 is provided with a first MFC202a and a first drain pump 202 b.

The MFC is a MASS FLOW CONTROLLER, i.e. a MASS FLOW CONTROLLER.

The first evacuation line 202 is a main pumping line for keeping the gas inside the device pipeline in a flowing state all the time, so as to avoid the gas from becoming a dead volume after staying in the pipeline for a long time.

The first six-way valve 203 and the second six-way valve 205 are both provided with 6 interfaces, which are respectively the 1 st interface, the 2 nd interface, the 3 rd interface, the 4 th interface, the 5 th interface and the 6 th interface, and are arranged clockwise in the figure, and have two states: when the device is in the A state, the 1 st interface is communicated with the 6 th interface, the 2 nd interface is communicated with the 3 rd interface, and the 4 th interface is communicated with the 5 th interface; when in the B state, the 1 st interface is communicated with the 2 nd interface, the 3 rd interface is communicated with the 4 th interface, and the 5 th interface is communicated with the 6 th interface.

The 2 nd interface of the first six-way valve 203 is connected with the first-stage enrichment and release module 300;

the 3 rd interface pipeline of the first six-way valve 203 is connected with one end of a first dewatering trap 204, and the other end of the first dewatering trap 204 is connected with the 6 th interface of the first six-way valve 203;

the 4 th port pipeline of the first six-way valve 203 is connected with the first three-way valve 211;

the 5 th port pipe of the first six-way valve 203 is connected with a first tee 208.

The 2 nd interface of the second six-way valve 205 is connected with the first stage enrichment and release module 300;

a 3 rd interface pipeline of the second six-way valve 205 is connected with one end of a second dewatering trap 206, and the other end of the second dewatering trap 206 is connected with a 6 th interface of the second six-way valve 205;

the 4 th port pipeline of the second six-way valve 205 is connected with the first three-way valve 211;

the 5 th port pipe of the second six-way valve 205 is connected with the first three-way valve 208.

One end of the first carrier gas pipeline 207 is connected with a first tee joint 208, the other end of the first carrier gas pipeline is connected with a second tee joint 209, and the first carrier gas pipeline 207 is provided with a second electromagnetic valve 207 a.

The first tee 208 is provided with three joints, which are respectively connected with the first carrier gas pipeline 207, the 5 th port of the first six-way valve 203 and the 5 th port of the second six-way valve 205.

The second tee 209 is provided with three joints which are respectively connected with a carrier gas source 210, a first carrier gas pipeline 207 and a second carrier gas pipeline 306.

The first three-way valve 211 is connected to the 4 th port of the first six-way valve 203, the 4 th port of the second six-way valve 205, and a second drain line 212.

The second evacuation line 212 is provided with a first activated carbon tube 213.

The pipelines between the first four-way valve 201 and the first six-way valve 203, between the first six-way valve 203 and the first water removing trap 204, and between the first water removing trap 204 and the first-stage enrichment and release module 300 are all provided with heat tracing bands which are used for heating, and the heat tracing bands are used for heating at 180 ℃.

The pipeline between the first four-way valve 201 and the second six-way valve 205, the pipeline between the second six-way valve 205 and the second water removing trap 206, and the pipeline between the second water removing trap 206 and the first-stage enrichment and release module 300 are all provided with heat tracing bands which are used for heating, and the heat tracing bands are used for heating at 180 ℃.

When the water removal module 200 is in operation, the states of the first six-way valve 203 and the second six-way valve 205 are opposite:

through setting up the dewatering pipeline that parallels to two six-way valves of reasonable setting for two way dewatering pipeline alternate work, that is to say, when one removes the water trap and is carrying out the dewatering operation, another removes the water trap and then takes away unnecessary moisture through the carrier gas, makes ready for its subsequent dewatering operation.

Preferably, the inner diameter of the water removal trap is 3mm, no filler is used, and a deactivated quartz tube is adopted. The function is as follows: the small inner diameter is beneficial to the rapid passing of substances and reduces the adsorption probability.

When water is removed, the water removal trap is in a low-temperature state; during back flushing, the water is changed into gas state and taken away along with the carrier gas when the water trap is heated in a high-temperature state.

The first-stage enrichment releasing module 300 comprises a first three-way switching valve 301, an eight-way valve 302, a first sampling trap 303, a second sampling trap 304, a second three-way switching valve 305, a second carrier gas pipeline 306, a third emptying pipeline 308, a fourth emptying pipeline 311 and a third activated carbon pipeline 313.

The first three-way switching valve 301 is provided with 3 interfaces, including an interface a connected to the first six-way valve 203, an interface B connected to the second six-way valve 205, and an interface C connected to the eight-way valve 302. The first three-way switching valve 301 switches (communicates or blocks) the gas path by controlling the AC path or the BC path.

The eight-way valve 302 is provided with 8 interfaces, which have two states: when the state is A, the 1 st interface is communicated with the 7 th interface, the 2 nd interface is communicated with the 8 th interface, the 3 rd interface is communicated with the 5 th interface, and the 4 th interface is communicated with the 6 th interface; when in the B state, the 1 st interface is communicated with the 3 rd interface, the 2 nd interface is communicated with the 4 th interface, the 5 th interface is communicated with the 7 th interface, and the 6 th interface is communicated with the 8 th interface.

The 1 st port of the eight-way valve 302 is connected with a third emptying pipeline 308; the 2 nd interface of the eight-way valve 302 is connected with the first three-way switching valve 301; the 3 rd interface of the eight-way valve 302 is connected with one end of the second sampling trap 304; the 4 th interface of the eight-way valve 302 is connected with the other end of the second sampling trap 304; the 5 th interface of the eight-way valve 302 is connected with a second gas carrying pipeline 306; the 6 th interface of the eight-way valve 302 is connected with a second three-way switching valve 305; the 7 th interface of the eight-way valve 302 is connected with one end of the first sampling trap 303; the 8 th interface of the eight-way valve 302 is connected to the other end of the first sampling well 303.

The third purge line 308 is provided with a second MFC309, a second charcoal tube 312, and a second purge pump 310.

The gas passes through the water removal trap and enters the sampling trap, and power is needed. The third evacuation line 308 provides power for sampling, water removal, and enrichment of the gas.

The second carrier gas line 306 includes a third MFC 307; one end of the third MFC307 is connected to the second tee 209, and the other end is connected to the 5 th port of the eight-way valve 302.

The first sampling trap 303 and the second sampling trap 304 are both quartz tubes with built-in fillers, and are wrapped by ceramic heating sleeves, and the ceramic heating sleeves are placed in the semiconductor refrigerating box and have the functions of low-temperature adsorption and high-temperature release.

The fourth evacuation line 311 is provided with a third activated carbon tube 313 for adsorbing the unadsorbed gas to perform a filtering function.

When the air is required to be exhausted, the air is discharged out through the fourth exhaust pipeline 311, and the unadsorbed substances or moisture in the air are removed through the third activated carbon pipe 313.

The pipeline between the first three-way switching valve 301 and the eight-way valve 302, the sample inlet pipeline of the first sampling trap 303, the sample inlet pipeline of the second sampling trap 304, and the pipeline between the eight-way valve 302 and the second three-way switching valve 305 are all provided with heat tracing belts which are used for heating to about 180 ℃.

According to the technical scheme, the first sampling trap 303 and the second sampling trap 304 are alternately adsorbed and released by switching the eight-way valve 302, so that the continuous concentration of the smoke pollutants is realized.

Communication of carrier gas source 210: the carrier gas source 210 is communicated with the first-stage enrichment and release module 300, and the carrier gas in the carrier gas source 210 flows through the first-stage enrichment and release module 300 and the second-stage enrichment and release module 400 and then is discharged outside, so that the things (gas, particles and water) which are not enriched are blown away.

Preferably, the sampling well has an inner diameter of 1/4 inches. The large-volume sampling trap has the effects that the large-volume sampling trap is matched with the filler, more target substances can be collected, the concentration of the target substances is increased, and the analysis accuracy is improved.

The second stage enrichment and release module 400 includes a third six-way valve 401, a fifth evacuation conduit 402, a fourth activated carbon tube 406, a focusing trap 403, a gas chromatography module 404, and a transfer line 405.

The third six-way valve 401 is provided with 6 ports: a 1 st interface is connected with the second three-way switching valve 305, a 2 nd interface is connected with the fifth emptying pipeline 402, a 3 rd interface is connected with one end of the focusing trap 403, a 4 th interface is connected with the gas chromatography module 404, a 5 th interface is connected with the transmission line 405, and a 6 th interface is connected with the other end of the focusing trap 403.

The third six-way valve 401 has two states, a and B; when the state is in the a state, the 1 st port and the 6 th port of the third six-way valve 401 are communicated, the 2 nd port and the 3 rd port of the third six-way valve 401 are communicated, and the 4 th port and the 5 th port of the third six-way valve 401 are communicated; when the state is in the B state, the 1 st port and the 2 nd port of the third six-way valve 401 are communicated, the 3 rd port and the 4 th port of the third six-way valve 401 are communicated, and the 5 th port and the 6 th port of the third six-way valve 401 are communicated.

The gas chromatography module 404 is connected to a transmission line 405.

The fifth evacuation pipe 402 is provided with a third activated carbon pipe 406, which adsorbs unadsorbed gas and performs a filtering function.

The transmission line 405 is a quartz tube with an inner wall without filler, the inner diameter of the quartz tube is 0.25mm, one end of the transmission line is connected with the 1/16-inch stainless steel tube at the outlet of the third six-way valve 401, and the other end of the transmission line is connected with the gas chromatography module 404, so that the transitional focusing effect is achieved.

The pipeline between the second three-way switching valve 305 and the third six-way valve 401, the sample inlet pipeline of the focusing trap 403, and the pipeline between the third six-way valve 401 and the transmission line 405 are all provided with heat tracing bands, and the heat tracing bands are used for heating to about 180 ℃.

In the device, the carrier gas is nitrogen or helium.

Preferably, the focusing well 403 has a wide end and a narrow end, and the sample diffuses more sufficiently from the narrow end to the wide end during focusing of the sample, and is more easily adsorbed. The sample is from wide mouth to narrow mouth in the analytic time, and the focus is more sufficient, promotes the analysis accuracy. Further, the wide-mouth inner diameter of the focusing well 403 is 3mm, and the narrow-mouth inner diameter is 1.2 mm.

At present, no smoke pollutant online alternate concentration and release device is available on the market, the environment air online concentration and release device is available on the market, but the environment air pollutant components are simple, the concentration of interferents is low, the water content is low, and the temperature requirement of a sample collection flow path is low (the temperature of a general sampling pipeline is consistent with the original temperature of a sample). The smoke components are complex, so that a lot of adsorbed substances are caused, and the analysis difficulty is increased. According to the technical scheme, different fillers are selected through multi-stage adsorption, and corresponding substances are selectively adsorbed.

The concentration of smoke components is uneven, and if a small-volume sampling cold trap is used, the needed target substance components are too little. The technical scheme is changed into two-stage adsorption, the first stage uses a large-volume sampling cold trap to adsorb a large amount of first-stage target objects, and the second stage uses a small-volume accumulation coke cold trap to adsorb a small amount of second-stage target objects.

The moisture content of the flue gas is high, which causes the damage of the instrument and greatly reduces the accuracy of the sample. This technical scheme adopts the dewatering module of freezing dewatering, and the continuity of detection is guaranteed in the continuous dewatering. The cold trap freezing enrichment concentration is adopted instead of the freezing enrichment concentration, so that the enrichment temperature range is wide, and the enrichment concentration efficiency is improved.

The sampling flow path has high temperature requirement: the temperature of the sample sampling flow path is consistent with the original temperature of the sample, so that organic matters are prevented from being adsorbed on the surface of the sampling pipe due to low temperature. In the technical scheme, the sample flow path is controlled at about 180 ℃.

A treatment method for online alternate concentration and release of smoke pollutants is characterized by comprising the following steps:

s1, debugging of the working state: heating the air inlet pipeline and the valve body to 150-210 ℃; and starting the refrigeration state of the water removal module 200, and enabling the first water removal trap 204 and the second water removal trap 206 to reach the low temperature of-20-30 ℃.

The gas inlet pipelines to be heated comprise a blank pipeline 101, a standard gas pipeline 103, a sampling pipeline 105, a pipeline between the sample switching valve 110 and the first six-way valve 203, a pipeline between the sample switching valve 110 and the second six-way valve 205, a pipeline between the 6 th interface of the first six-way valve 203 and the first water trap 204, a pipeline between the 6 th interface of the second six-way valve 205 and the second water trap 206, a pipeline between the first six-way valve 203 and the first three-way switching valve 301, a pipeline between the second six-way valve 205 and the first three-way switching valve 301, a pipeline between the first three-way switching valve 301 and the eight-way valve 302, a pipeline between the 8 th interface of the eight-way valve 302 and the first sampling trap 303, a pipeline between the 4 th interface of the eight-way valve 302 and the second sampling trap 304, a pipeline between the eight-way valve 302 and the second three-way switching valve 305, a pipeline between the second three-way switching valve 305 and the third six-way valve 401, and a pipeline between the 6 th, the third six-way valve 401 to the line of transfer line 405, transfer line 405.

The valve body that needs heating includes: the sample injection switching valve 110, the first six-way valve 203, the second six-way valve 205, the first three-way switching valve 301, the eight-way valve 302, the second three-way switching valve 305, and the third six-way valve 401.

The pipelines are all provided with outer sleeves with heat tracing bands which are used for heating the pipelines.

In this scheme, owing to let in be high temperature flue gas, consequently, need the sample to maintain the temperature the same with high temperature flue gas, prevent the component condensation of high boiling to detection precision has been guaranteed.

Temperature control is an innovative point of the scheme. The collection of the ambient air can be realized only by the condition that the temperature of the equipment flow path is consistent with the ambient air source and by a common electromagnetic valve. However, if the temperature of the flow path of the collected flue gas (180 ℃) is lower than that of the air source, the target object can be adsorbed on the flow path. The smoke can only be collected by adopting the valve in the technical scheme.

The electromagnetic valve contains lubricating oil, rubber ring and the like inside, and the lubricating oil and the rubber ring volatilize organic matters at high temperature to interfere detection. And the solenoid valve is easy to lose efficacy under the high-temperature working environment, and the stability of the system is influenced. In addition, the electromagnetic valve structure has a dead volume, and the dead volume always exists in one section.

Therefore, the smoke can be collected only by adopting the valve in the technical scheme.

S2, exhaust gas removal in the plant line:

communication of blank pipe 101: the blank pipeline 101 of the gas source pipeline module 100 is communicated with the water removal module 200, blank gas stored in the blank source 102 flows through the water removal module 200 and the first sampling trap 303 and then is discharged outside, blank sampling is used for detecting whether a previous group of samples have residues, if so, a plurality of groups of blanks are passed or an instrument method is changed, and if not, the next group of samples are carried out. The utilization of blank sample introduction to improve the analysis accuracy is one of the quality control means.

S3, measuring standard gas: the standard gas pipeline 103 of the gas source pipeline module 100 is communicated with the water removal module 200, and after the standard gas is subjected to water removal by the water removal module 200 and the first-stage target object enrichment of the first sampling trap 303, the rest of the standard gas is discharged outside; after the enriched target is heated and released, the enriched target flows into the second-stage enrichment and release module 400 along with the carrier gas to perform enrichment and adsorption of the second-stage target, and the rest of the first-stage target is discharged; finally, after the second-stage target object is heated and released,

then enters the gas chromatography module 404 for detection after passing through the transmission line 405.

S4, determination of sample: the sampling pipeline 105 of the gas source pipeline module 100 is communicated with the water removal module 200, and after the sample is subjected to water removal by the water removal module 200 and the first-stage target object enrichment of the first sampling trap 303, the rest of the sample is discharged outside; after the enriched target is heated and released, the enriched target flows into the second-stage enrichment and release module 400 along with the carrier gas to perform enrichment and adsorption of the second-stage target, and the rest of the first-stage target is discharged; finally, the second stage target is released by heating and then enters the gas chromatography module 404 for detection after passing through the transmission line 405.

The water removal by the water removal module 200 in steps S3 and S4 includes the steps of:

the first and second six- way valves 203, 205 are in opposite states:

when the first six-way valve 203 is in the a state, the second six-way valve 205 is in the B state; at this time, part of the standard gas or the sample gas from the gas source pipeline module 100 enters the 1 st interface of the first six-way valve 203 through the first four-way 201, and then enters the first dewatering trap 204 from the 6 th interface of the first six-way valve 203 for dewatering operation, the first dewatering trap 204 is in a low-temperature state and freezes for dewatering, and the moisture is frozen into liquid or condensed; the standard gas or the sample gas subjected to the water removal treatment enters the 3 rd interface of the first six-way valve 203 and enters the first-stage enrichment and release module 300 from the 2 nd interface of the first six-way valve 203; part of the standard gas or the sample gas enters the 1 st interface of the second six-way valve 205 through the first four-way valve 201, then enters the first-stage enrichment release module 300 from the 2 nd interface of the second six-way valve 205 and is blocked, the channel is closed, and the gas cannot flow;

meanwhile, the carrier gas in the carrier gas source 210 passes through the second tee joint 209, the first carrier gas pipeline 207 and the first tee joint 208, and part of the carrier gas passes through the 5 th port of the first six-way valve 203 and the 4 th port of the first six-way valve 203 to reach the first three-way valve 211; part of the carrier gas passes through the 5 th interface of the second six-way valve 205, the 6 th interface of the second six-way valve 205 and the second water trap 206, is heated, dried and blown away with water, and then enters the second evacuation pipeline 212 from the 3 rd interface of the second six-way valve 205, the 4 th interface of the second six-way valve 205 and the first three-way valve 211 to be discharged outside; the second evacuation line 212 is provided with a first activated carbon tube 213 for adsorbing the contaminants to prevent the contaminants from being directly discharged into the air;

when the first six-way valve 203 is in the B state, the second six-way valve 205 is in the a state, and the first three-way switching valve 301 also switches the inlet of the ventilation; at this time, the standard gas or the sample gas from the gas source pipeline module 100 enters the 1 st interface of the first six-way valve 203 through the first four-way valve 201, and then enters the first-stage enrichment release module 300 from the 2 nd interface of the first six-way valve 203, and then is blocked, so that the channel is closed, and the gas cannot circulate; the standard gas or the sample gas from the gas source pipeline module 100 enters the 1 st interface of the second six-way valve 205 through the first four-way 201, and then enters the second dewatering trap 206 from the 6 th interface of the second six-way valve 205 to perform dewatering operation, the second dewatering trap 206 is in a low-temperature state and freezes for dewatering, and the water is frozen into liquid or condensed; the dehydrated standard gas or sample gas enters the 3 rd interface of the second six-way valve 205 and enters the first-stage enrichment and release module 300 from the 2 nd interface of the second six-way valve 205;

meanwhile, the carrier gas in the carrier gas source 210 passes through the second tee joint 209, the first carrier gas pipeline 207 and the first tee joint 208, and part of the carrier gas passes through the 5 th interface of the first six-way valve 203 and the 6 th interface of the first six-way valve 203 and then comes to the first dewatering trap 204, is heated, dried and blown away with moisture, and then enters the second emptying pipeline 212 from the 3 rd interface of the first six-way valve 203, the 4 th interface of the first six-way valve 203 and the first tee joint 211 and is discharged outside; part of the carrier gas passes through the 5 th port and the 4 th port of the second six-way valve 205 and then enters the first three-way valve 211 to be blocked.

The first stage target enrichment of the first sampling well 303 in steps S3 and S4 includes the steps of:

when the eight-way valve 302 is in the state a, the standard gas or the sample gas transmitted by the water removal module 200 enters the first-stage target object of the first sampling trap 303 through the 2 nd interface and the 8 th interface of the eight-way valve 302 to be adsorbed, and the rest of the standard gas or the sample gas enters the third evacuation pipeline 308 from the 7 th interface and the 1 st interface of the eight-way valve 302 to be discharged.

Meanwhile, the carrier gas in the second carrier gas pipeline 306 enters the second sampling trap 304 through the 5 th interface and the 3 rd interface of the eight-way valve 302, carries out the enriched concentrated gas in the second sampling trap 304, and then enters the second three-way switching valve 305 through the 4 th interface and the 6 th interface of the eight-way valve 302;

when the eight-way valve 302 is switched to the state B, the standard gas or the sample gas transmitted by the water removal module 200 enters the second sampling trap 304 through the 2 nd interface and the 4 th interface of the eight-way valve 302, the first-stage target object is adsorbed, and the rest of the standard gas or the sample gas enters the third evacuation pipeline 308 from the 3 rd interface and the 1 st interface of the eight-way valve 302 and is discharged outside;

meanwhile, the carrier gas in the second carrier gas pipeline 306 enters the first sampling trap 303 through the 5 th interface and the 7 th interface of the eight-way valve 302, carries out the concentrated gas enriched in the first sampling trap 303, and then enters the second three-way switching valve 305 through the 8 th interface and the 6 th interface of the eight-way valve 302;

the second three-way switching valve 305 is provided with 3 interfaces, which are respectively connected with the 6 th interface of the eight-way valve 302, the second-stage enrichment and release module 400 and the fourth emptying pipeline 311; the second three-way switching valve 305 delivers the carrier gas enriched in the first stage targets to the second stage enrichment and release module 400.

The water removing trap, the sampling trap and the focusing trap are arranged in the low-temperature range (-20-30 ℃), the temperature control precision is 1 ℃, and the low temperature is refrigerated through a semiconductor. The temperature control precision of the high temperature range (30-380 ℃) is 1 ℃, the high temperature is heated by a ceramic heating pipe, the heating rate is higher than 40 ℃/s, and the temperature is rapidly increased, so that adsorbed substances are released instantly when the cold trap is analyzed.

This device, the toxicity equivalent that cooperates dioxin on-line measuring system to measure dioxin in the flue gas includes following step:

the invention realizes the alternate enrichment and release of organic matters in flue gas on line, and the measurement of the toxicity equivalent of dioxin in the flue gas by matching with a dioxin on-line detection system comprises three steps: firstly, calibrating a target substance (standard gas) and establishing a standard fitting working curve. And secondly, actually detecting target substances in the flue gas, and thirdly, converting the toxicity equivalent of the dioxin through a correlation model.

Heating a gas source and a sampling module pipeline:

in order to avoid the loss of target detection substances caused by condensation and adsorption in the process of flowing through a pipeline and influence the accuracy of a detection result, a gas source, the pipeline through which a gas circuit flows in the sampling process and a valve body need to be heated. When the calibration is carried out, the heating process of each part is as follows:

1. and (3) starting a standard gas storage tank (a Suma tank) and a blank (high-purity nitrogen) storage tank for heating, heating through a six-way valve 1 and a six-way valve 2 from the tank body of the Suma tank to the smoke organic matter alternate enrichment and release device, wherein the heating temperature reaches 180 ℃ of the specification, and a heating pipeline is wrapped by a heat tracing band.

2. The water removal module 200 is started to perform a refrigeration function, and the semiconductor refrigeration device is used for cooling the water removal module to-10 ℃.

3. Starting a first-stage enrichment and release module 300 for samples in the smoke organic matter alternative enrichment and release device; all of the piping and valve body in the gas sampling flow path of the sample second stage enrichment release module 400 are heated.

4. The gas chromatography module 404 is turned on and the carrier gas flow rate is turned on to adjust the carrier gas flow rate to 2 mL/min. And starting an online dioxin detection system.

Calibrating a target substance standard gas, and establishing a standard fitting working curve, wherein the steps are as follows:

1. the valve of the standard gas storage tank is opened, the sample introduction switching valve 110 is adjusted to communicate the standard gas pipeline 103 with the water removal module 200, the first MFC202a is opened to control the flow rate of the gas entering the main pipeline, and the first evacuation pump 202b is opened to provide the pumping force. The main circuit first MFC202a flow rate is adjusted to 50 mL/min. The purpose of designing this way main road is in order to switch different sampling sources and under the condition in sampling clearance, guarantee that the interior gas of sampling pipeline circulates all the time, prevent to produce the dead volume, prevent to produce static volume promptly.

2. The standard gas passing through the gas source pipeline module 100 enters the water removal module 200. The water removal module 200 sets the freezing low-temperature of the water removal trap to-10 ℃, and the first water removal trap 204 and the second water removal trap 206 work alternately. The first water removal trap 204 corresponds to the first sampling trap 303, and the second water removal trap 206 corresponds to the second sampling trap 304.

3. The marker gas enters the first sampling well 303.

When the standard gas passes through the water removal module 200 and then enters the first sampling trap 303, the temperature of the first sampling trap 303 is set to be 30 ℃, and the target substance is adsorbed by the filler filled in the first sampling trap 303. The sample flow rate is controlled by a second MFC309, and a second evacuation pump 310 is powered. The sampling flow rate is 10ml/Min, and the sampling time is 15 Min.

4. The first sampling well 303 is blown back.

The back-flushing flow rate is controlled by the third MFC307, the carrier gas (Ar) in the gas storage tank is used as back-flushing gas, and the substances (gas, liquid and solid) which are not adsorbed in the back-flushing pipeline and the first sampling trap 303 are back-flushed. The way blowback aims at improving the purity of the collected substances and reducing the interference of other substances. The back flushing flow rate is 50ml/Min, and the back flushing time is 2 Min.

5. The first sampling well 303 is heated to desorb from the adsorbed substance into the focusing well 403.

Heating the first sampling trap 303 to 300 ℃ (within 20 s), simultaneously opening the third MFC307, adjusting the flow rate to make the back-flushing gas 50ml/Min for 5Min, and taking the adsorbed substances into the focusing trap 403 through the first sampling trap 303. The focus well 403 is at a temperature of 30 deg.c.

6. Focused well 403 heating desorption

Heating the focusing trap 403 to 300 deg.C (within 5 s), switching the third six-way valve 401, introducing carrier gas (Ar)2ml/min for 5min, flowing through the focusing trap 403, and carrying adsorbed substances into the capillary chromatographic column of the gas chromatographic module 404. The transmission line 405 connecting the focusing trap 403 and the capillary column is connected through an 1/16 inch inner diameter transition 1/32 inch (0.25 mm inner diameter) empty column for focusing function (from thick inner diameter to thin inner diameter).

The device comprises a first water removal trap 204, a second water removal trap 206, a first sampling trap 303, a second sampling trap 304 and a focusing trap 403, wherein sampling, water removal, dry blowing and analysis are alternately performed, so that blank-free, full-coverage and real-time sampling are realized.

7. Gas chromatography separation

The substances released through the focusing trap 403 are separated through the chromatographic column of the gas chromatography module 404 into a subsequent detection system.

And standard gas storage tanks with different concentration gradients (0.5 ppb,2ppb,4ppb,6ppb,8ppb and 10 ppb) are connected to a sampling pipeline module, and sampling valves are switched for sample injection. The flow rate was 10mL/min, time 15min, and a total volume of 150mL was collected. And (3) performing 6 times of repeated measurement on the target object standard gas with each volume concentration, and inputting the detected result into the data acquisition device through the signal input end of the data acquisition device to display data.

According to the steps, a working curve is drawn according to each volume concentration and the detection result corresponding to each concentration, then fitting is carried out according to a least square method to obtain a regression equation Y = ax + b of the standard working curve, and the working curve is obtained through fitting calculation: a =0.0011, b =0.0012, R²=0.9675, i.e. standard fit operating curve y =0.0011x +0.0012

Detection limit

Standard gas concentration (ppb)	Signal (mv)	Concentration (ppb)
			0.2	0.00128	0.07
0.2	0.00130	0.09
			0.2	0.00126	0.06
0.2	0.00124	0.03
			0.2	0.00123	0.03
0.2	0.00128	0.07
			0.2	0.00121	0.01

Formula (II)

The calculation method detects the limit MDL. Method detection limit of 0.11ppb

Concentration ratio

The smoke organic matter alternate enrichment and release device is used for collecting target substances and directly introducing the target substances into the dioxin online detection device. The ratio of the two is the concentration ratio of the smoke organic matter alternating enrichment and release device.

Drawing a working curve according to detection results corresponding to different sampling volumes, fitting according to a least square method to obtain a regression equation Y = ax + b of the standard working curve, and calculating through fitting to obtain: a =0.01446, b = -0.1685, R²=0.9988, i.e. standard fit working curve y =0.1446x-0.1685

Accuracy of

Standard gas concentration (ppb)	Signal (mv)	Concentration (ppb)
			5	0.00715	5.41
5	0.00728	5.52
			5	0.00697	5.25
5	0.00709	5.36
			5	0.00714	5.40
5	0.00728	5.53
			5	0.00739	5.62

Accuracy: 8.8 percent

Precision (relative standard deviation): 2.3 percent of

24 hours concentration drift

And (3) introducing 10ppb standard gas under the normal working state of the instrument, calculating the average value of the concentration of the instrument to be measured for 6 times continuously, repeating the operation after the aeration is finished and the analytical instrument to be measured continuously runs for 24h (no maintenance or calibration is allowed during the period), and calculating the average value of the concentration of the instrument to be measured for 3 times after 24 h.

The concentration drifts by 0.4ppb in 24h under the standard gas concentration of 10 ppb.

And (4) water removal performance of the drying pipe.

10ppb, the moisture content in the smoke at 180 ℃ is 22%, and the mixing test of the Suma tank and the standard gas which are configured at different moisture contents at 180 ℃ is carried out.

The water content is 30% or less, the loss of standard gas in the water removing device is less than 15%, but the loss of standard gas in the water removing device is 61% under the condition of 10% of water content. The water removal device is very necessary for the high-humidity flue gas test.

In this embodiment, the technical scheme is described by using dioxin detection, and it is worth pointing out that the technical scheme is not limited to dioxin detection, but is also applicable to detection of other gases.

The eight-way valve 302 is a two-position eight-way valve commercially available, for example, the two-position eight-way valve disclosed in chinese patent application publication No. CN105938130A may be used.

This technical scheme through the reasonable setting of pipeline for the direction of admitting air of dewatering trap and sampling trap is opposite with the direction of blowback, thereby promotes the effect of blowback.

The present invention has been described in terms of embodiments, and several variations and modifications can be made to the device without departing from the principles of the present invention. It should be noted that all the technical solutions obtained by means of equivalent substitution or equivalent transformation, etc., fall within the protection scope of the present invention.

Claims (3)

1. A processing method for online alternate concentration and release of smoke pollutants is characterized in that a smoke pollutant online alternate concentration and release device is adopted, and the device comprises an air source pipeline module (100), a water removal module (200), a first-stage enrichment and release module (300) and a second-stage enrichment and release module (400) which are sequentially connected;

the air source pipeline module (100) comprises a blank pipeline (101), a standard gas pipeline (103), a sampling pipeline (105), a back-blowing pipeline (107) and a sample introduction switching valve (110); the sample introduction switching valve (110) is provided with a sample outlet, a back flushing port and four sample inlets, and the number of the sample inlets communicated with the sample outlet is always one; a first sample inlet of the sample introduction switching valve (110) is connected with a blank pipeline (101); the blank pipeline (101) is connected with a blank source (102); a second sample inlet of the sample introduction switching valve (110) is connected with a standard gas pipeline (103); the standard gas pipeline (103) is connected with a standard gas source (104); a third sample inlet of the sample introduction switching valve (110) is connected with a sampling pipeline (105); the sampling pipeline (105) is connected with a sampling gun (106), and the sampling pipeline (105) is provided with a heating filter (111);

an eight-way valve (302), a first sampling trap (303) and a second sampling trap (304) are arranged in the first-stage enrichment and release module (300); both ends of the first sampling trap (303) and both ends of the second sampling trap (304) are connected with an eight-way valve (302);

the second-stage enrichment and release module (400) comprises a third six-way valve (401), a fourth activated carbon tube (406), a focusing trap (403), a gas chromatography module (404) and a transmission line (405);

the third six-way valve (401) is provided with 6 interfaces: the 1 st interface is connected with the first-stage enrichment release module (300), the 2 nd interface is connected with a fifth emptying pipeline (402), the 3 rd interface is connected with one end of a focusing trap (403), the 4 th interface is connected with a gas chromatography module (404), the 5 th interface is connected with a transmission line (405), and the 6 th interface is connected with the other end of the focusing trap (403);

the third six-way valve (401) having two states, A and B; when the state is in the A state, the 1 st port and the 6 th port of the third six-way valve (401) are communicated, the 2 nd port and the 3 rd port of the third six-way valve (401) are communicated, and the 4 th port and the 5 th port of the third six-way valve (401) are communicated; when the state is in the B state, the 1 st port and the 2 nd port of the third six-way valve (401) are communicated, the 3 rd port and the 4 th port of the third six-way valve (401) are communicated, and the 5 th port and the 6 th port of the third six-way valve (401) are communicated;

the gas chromatography module (404) is connected with a transmission line (405);

the processing method comprises the following steps:

step 1, debugging the working state: heating the air inlet pipeline and the valve body to 150-210 ℃; starting the refrigeration state of the water removal module (200), and enabling the first water removal trap (204) and the second water removal trap (206) to reach the low temperature of-20-30 ℃;

step 2, removing waste gas in the device pipeline:

communication of blank pipe (101): a blank pipeline (101) of the gas source pipeline module (100) is communicated with the water removal module (200), and blank gas stored in a blank source (102) is discharged outside after flowing through the water removal module (200) and the first sampling trap (303) to replace waste gas in the pipeline;

step 3, measuring standard gas: a standard gas pipeline (103) of the gas source pipeline module (100) is communicated with the water removal module (200), and after the standard gas is subjected to water removal of the water removal module (200) and first-stage target object enrichment of the first sampling trap (303), the rest of the standard gas is discharged outside; after the enriched target object is heated and released, the enriched target object flows into a second-stage enrichment and release module (400) along with carrier gas to carry out enrichment and adsorption on the second-stage target object, and the rest first-stage target object is discharged; finally, after the second-stage target object is heated and released, the second-stage target object enters a gas chromatography module (404) for detection after passing through a transmission line (405);

and 4, determination of a sample: a sampling pipeline (105) of the gas source pipeline module (100) is communicated with the water removal module (200), and after a sample is subjected to water removal of the water removal module (200) and first-stage target enrichment of a first sampling trap (303), the rest of the sample is discharged outside; after the enriched target object is heated and released, the enriched target object flows into a second-stage enrichment and release module (400) along with carrier gas to carry out enrichment and adsorption on the second-stage target object, and the rest first-stage target object is discharged; finally, after the second-stage target object is heated and released, the second-stage target object enters a gas chromatography module (404) for detection after passing through a transmission line (405);

the first stage target enrichment of the first sampling well (303) in steps 3 and 4, comprising the steps of:

the first-stage enrichment and release module (300) further comprises a first three-way switching valve (301), a second three-way switching valve (305), a second carrier pipeline (306) and a third emptying pipeline (308);

the eight-way valve (302) is provided with 8 interfaces, which have two states: when the state is A, the 1 st interface is communicated with the 7 th interface, the 2 nd interface is communicated with the 8 th interface, the 3 rd interface is communicated with the 5 th interface, and the 4 th interface is communicated with the 6 th interface; when the device is in the state B, the 1 st interface is communicated with the 3 rd interface, the 2 nd interface is communicated with the 4 th interface, the 5 th interface is communicated with the 7 th interface, and the 6 th interface is communicated with the 8 th interface;

the 1 st interface of the eight-way valve (302) is connected with a third emptying pipeline (308); the 2 nd interface of the eight-way valve (302) is connected with a first three-way switching valve (301); the 3 rd interface of the eight-way valve (302) is connected with one end of the second sampling trap (304); the 4 th interface of the eight-way valve (302) is connected with the other end of the second sampling trap (304); the 5 th interface of the eight-way valve (302) is connected with a second gas carrying pipeline (306); the 6 th interface of the eight-way valve (302) is connected with a second three-way switching valve (305); the 7 th interface of the eight-way valve (302) is connected with one end of the first sampling trap (303); the 8 th interface of the eight-way valve (302) is connected with the other end of the first sampling trap (303);

when the eight-way valve (302) is in the state A, the standard gas or the sample gas transmitted by the water removal module (200) enters the first-stage target object of the first sampling trap (303) through the 2 nd interface and the 8 th interface of the eight-way valve (302) to be adsorbed, and the rest of the standard gas or the sample gas enters the third evacuation pipeline (308) from the 7 th interface and the 1 st interface of the eight-way valve (302) to be discharged outside;

meanwhile, the carrier gas in the second carrier gas pipeline (306) enters the second sampling trap (304) through the 5 th interface and the 3 rd interface of the eight-way valve (302), carries out the concentrated gas enriched in the second sampling trap (304), and then passes through the 4 th interface and the 6 th interface of the eight-way valve (302) to enter the second three-way switching valve (305);

when the eight-way valve (302) is switched to the state B, the standard gas or the sample gas transmitted by the water removal module (200) enters the second sampling trap (304) through the 2 nd interface and the 4 th interface of the eight-way valve (302) and is adsorbed by the first-stage target object, and the rest of the standard gas or the sample gas enters the third evacuation pipeline (308) from the 3 rd interface and the 1 st interface of the eight-way valve (302) and is discharged outside;

meanwhile, the carrier gas in the second carrier gas pipeline (306) enters the first sampling trap (303) through the 5 th interface and the 7 th interface of the eight-way valve (302), carries out the concentrated gas enriched in the first sampling trap (303), and then passes through the 8 th interface and the 6 th interface of the eight-way valve (302) to enter the second three-way switching valve (305);

and a second three-way switching valve (305) for delivering the carrier gas enriched in the first-stage target to a second-stage enrichment and release module (400).

2. The on-line alternate concentration and release treatment method for the smoke pollutants as claimed in claim 1, wherein the water removal of the water removal module (200) in the steps 3 and 4 comprises the following steps:

the water removal module (200) comprises a first four-way (201), a first emptying pipeline (202), a first six-way valve (203), a first water removal trap (204), a second six-way valve (205), a second water removal trap (206), a first carrier pipeline (207), a first three-way (208), a first three-way valve (211) and a second emptying pipeline (212);

the first four-way joint (201) is provided with four joints which are respectively connected with a sample introduction switching valve (110) of the gas source pipeline module (100), a 1 st interface of the first six-way valve (203), a 1 st interface of the second six-way valve (205) and a first emptying pipeline (202);

the first evacuation line (202) is provided with a first MFC (202 a) and a first evacuation pump (202 b);

the first six-way valve (203) and the second six-way valve (205) are both provided with 6 interfaces, which are respectively a 1 st interface, a 2 nd interface, a 3 rd interface, a 4 th interface, a 5 th interface and a 6 th interface, and have two states: when the device is in the A state, the 1 st interface is communicated with the 6 th interface, the 2 nd interface is communicated with the 3 rd interface, and the 4 th interface is communicated with the 5 th interface; when the device is in the state B, the 1 st interface is communicated with the 2 nd interface, the 3 rd interface is communicated with the 4 th interface, and the 5 th interface is communicated with the 6 th interface; the 2 nd interface of the first six-way valve (203) is connected with a first stage enrichment and release module (300); the 3 rd interface pipeline of the first six-way valve (203) is connected with one end of a first dewatering trap (204), and the other end of the first dewatering trap (204) is connected with the 6 th interface of the first six-way valve (203); the 4 th interface pipeline of the first six-way valve (203) is connected with a first three-way valve (211); the 5 th interface pipeline of the first six-way valve (203) is connected with a first tee joint (208); the 2 nd interface of the second six-way valve (205) is connected with a first stage enrichment and release module (300); a 3 rd interface pipeline of the second six-way valve (205) is connected with one end of a second dewatering trap (206), and the other end of the second dewatering trap (206) is connected with a 6 th interface of the second six-way valve (205); the 4 th interface pipeline of the second six-way valve (205) is connected with a first three-way valve (211); the 5 th interface pipeline of the second six-way valve (205) is connected with a first tee joint (208);

one end of the first gas carrying pipeline (207) is connected with a first tee joint (208), the other end of the first gas carrying pipeline is connected with a second tee joint (209), and the first gas carrying pipeline (207) is provided with a second electromagnetic valve (207 a);

the first tee joint (208) is provided with three joints which are respectively connected with a first gas carrying pipeline (207), a 5 th interface of the first six-way valve (203) and a 5 th interface of the second six-way valve (205);

the second tee joint (209) is provided with three joints which are respectively connected with a load gas source (210), a first gas carrying pipeline (207) and a second gas carrying pipeline (306);

the first three-way valve (211) is connected with a 4 th port of the first six-way valve (203), a 4 th port of the second six-way valve (205) and a second emptying pipeline (212);

the second emptying pipeline (212) is provided with a first activated carbon pipe (213);

the first and second six-way valves (203, 205) are in opposite states:

when the first six-way valve (203) is in the A state, the second six-way valve (205) is in the B state; at the moment, part of the standard gas or the sample gas from the gas source pipeline module (100) enters a 1 st interface of the first six-way valve (203) through the first four-way valve (201), and then enters a first water removal trap (204) from a 6 th interface of the first six-way valve (203) for water removal operation, the first water removal trap (204) is in a low-temperature state and freezes for water removal, and water is frozen into liquid or condensed; the standard gas or the sample gas subjected to the water removal treatment enters a 3 rd interface of the first six-way valve (203) and enters a first-stage enrichment and release module (300) from a 2 nd interface of the first six-way valve (203); part of standard gas or sample gas enters a 1 st interface of the second six-way valve (205) through the first four-way valve (201), and then enters the first-stage enrichment release module (300) from a 2 nd interface of the second six-way valve (205) to be blocked;

meanwhile, the carrier gas in the carrier gas source (210) passes through the second tee joint (209), the first carrier gas pipeline (207) and the first tee joint (208), and part of the carrier gas passes through the 5 th interface of the first six-way valve (203) and the 4 th interface of the first six-way valve (203) to enter the first three-way valve (211); part of the carrier gas passes through a 5 th interface of the second six-way valve (205), a 6 th interface of the second six-way valve (205) and the second water removing trap (206), is heated, blown and used for removing water, and then enters the second evacuation pipeline (212) from a 3 rd interface of the second six-way valve (205), a 4 th interface of the second six-way valve (205) and the first three-way valve (211) and is discharged outside; the second emptying pipeline (212) is provided with a first activated carbon pipe (213) for adsorbing pollutants and preventing the pollutants from being directly discharged into the air;

when the first six-way valve (203) is in the B state, the second six-way valve (205) is in the A state; at the moment, the standard gas or the sample gas from the gas source pipeline module (100) enters a 1 st interface of the first six-way valve (203) through the first four-way joint (201), and then enters the first-stage enrichment release module (300) from a 2 nd interface of the first six-way valve (203) to be blocked; the standard gas or the sample gas from the gas source pipeline module (100) enters a 1 st interface of the second six-way valve (205) through the first four-way joint (201), and then enters a second water removal trap (206) from a 6 th interface of the second six-way valve (205) for water removal, the second water removal trap (206) is in a low-temperature state and is frozen for water removal, and the water is frozen into liquid or condensed; the standard gas or the sample gas subjected to water removal treatment enters a 3 rd interface of the second six-way valve (205) and enters the first-stage enrichment and release module (300) from a 2 nd interface of the second six-way valve (205);

meanwhile, carrier gas in a carrier gas source (210) passes through a second tee joint (209), a first carrier gas pipeline (207) and a first tee joint (208), part of the carrier gas passes through a 5 th interface of a first six-way valve (203) and a 6 th interface of the first six-way valve (203) and then comes to a first dewatering trap (204), is heated and blown to remove moisture, and then enters a second emptying pipeline (212) from a 3 rd interface of the first six-way valve (203), a 4 th interface of the first six-way valve (203) and a first three-way valve (211) and then is discharged outside; and part of the carrier gas passes through a 5 th port and a 4 th port of the second six-way valve (205) and then enters the first three-way valve (211) to be blocked.

3. The on-line alternative concentration and release treatment method for flue gas pollutants as claimed in claim 2, wherein the first-stage enrichment and release module (300) further comprises a fourth emptying pipeline (311) and a third activated carbon pipe (313);

the first three-way switching valve (301) is provided with 3 interfaces, including an interface A connected with the first six-way valve (203), an interface B connected with the second six-way valve (205), and an interface C connected with the eight-way valve (302);

the third emptying pipeline (308) is provided with a second MFC (309), a second activated carbon pipe (312) and a second emptying pump (310);

the second carrier gas line (306) comprises a third MFC (307); one end of the third MFC (307) is connected with the second tee joint (209), and the other end of the third MFC is connected with the 5 th interface of the eight-way valve (302);

the fourth emptying pipeline (311) is provided with a third activated carbon pipe (313);

the second three-way switching valve (305) is provided with 3 interfaces which are respectively connected with the 6 th interface of the eight-way valve (302), the second-stage enrichment and release module (400) and the fourth emptying pipeline (311).

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