CN205607866U - From maring continuous on -line measuring device of formula nitrogen dioxide - Google Patents

From maring continuous on -line measuring device of formula nitrogen dioxide Download PDF

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Publication number
CN205607866U
CN205607866U CN201620423113.7U CN201620423113U CN205607866U CN 205607866 U CN205607866 U CN 205607866U CN 201620423113 U CN201620423113 U CN 201620423113U CN 205607866 U CN205607866 U CN 205607866U
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liquid
gas
nitrogen dioxide
detection
unit
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CN201620423113.7U
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王竹青
付大友
袁东
潘传江
张洪
卢令
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Sichuan University of Science and Engineering
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Sichuan University of Science and Engineering
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Abstract

The utility model discloses a from maring continuous on -line measuring device of formula nitrogen dioxide, the device is including liquid way module, detection module and gas circuit module, detection module includes the reactor, covers the bare hull body, optical window and photoelectric sensor unit, liquid way module includes stock solution unit, the switching of liquid way solenoid valve, liquid pump and drawing liquid pump, the gas circuit module includes sample thief, sampling gas circuit, marks gas circuit and exhaust -gas treatment gas circuit. The utility model discloses carry out the automatic calibration to nitrogen dioxide detection device in real time with the aid of gaseous emergence technique of the nitrogen dioxide of high reliability and generating device on line, accomplish the detection to nitrogen dioxide concentration among the environmental atmosphere simultaneously, avoided the influence of factors such as the change of detect reagent composition, ambient temperature pressure variation to detecting system stability and sensitivity.

Description

Self-calibration formula nitrogen dioxide continuous on-line detection device
Technical field
This utility model relates to the technical field of gas detecting, more particularly, relates to a kind of self-calibration formula nitrogen dioxide continuous on-line detection device.
Background technology
Nitrogen dioxide is one of major pollutants in air, and the nitrogen dioxide in Accurate Determining ambient air is for understanding atmospheric pollution mechanism, judging atmospheric pollution level, determine pollution source, carry out air quality early warning and to help to formulate rational urban planning and construction etc. the most significant.
For the detection of nitrogen dioxide in air; current commonly used gas phase chemiluminescence method; i.e. by molybdenum catalyst, nitrogen dioxide is reduced to nitric oxide (Environmental Protection Agency USA's standard method), is then reacted the concentration measuring nitrogen dioxide by the gas phase chemiluminescence between nitric oxide with ozone.But, in its transformation process, some other nitrogenous gas (HNO3, PAN, organic nitrogen etc.) be also converted simultaneously as NO, this produces the biggest interference to measurement result.
Another method is liquid phase chemoluminescence method, and nitrogen dioxide can directly be measured by the method, and selectivity is preferably and sensitivity is far above gas phase chemiluminescence method.But the method needs to use detectable, when ingress of air or light, it becomes branch to change to detectable, and the sensitivity of impact detection and stability, so needing frequently to demarcate.Owing to nitrogen dioxide gas easily produces absorption at the surface of solids, therefore in the generation of low concentration nitrogen dioxide gas and low strength range detection equipment demarcate higher to the requirement of experimental situation and equipment, demarcate difficulty and cost be high.It addition, the fluctuation of ambient temperature and pressure also can produce impact to the sensitivity of detection equipment, the application in nitrogen dioxide monitoring field of the liquid phase chemoluminescence method all can be brought the biggest obstacle by these.
Therefore, it is necessary to design a kind of detection device that can solve the problem that liquid phase chemoluminescence method is applied to the problems such as poor stability existing during Nitrogen dioxide testing field and demarcation difficulty.
Utility model content
In order to solve problems of the prior art, the purpose of this utility model is to provide and a kind of carries out the self-calibration formula nitrogen dioxide continuous on-line detection device of automatic Calibration while nitrogen dioxide is carried out continuous on-line detection and to it.
This utility model provides self-calibration formula nitrogen dioxide continuous on-line detection device, and described device includes liquid circuit module, gas path module and detection module;
Described detection module includes reactor, opacus housing, optical window and photoelectric sensing unit, optical window is arranged between described reactor and opacus housing, forming airtight reaction chamber between described reactor and opacus housing and described reaction chamber is positioned at the side of described optical window, photoelectric sensing unit is arranged on opacus enclosure interior and is positioned at the opposite side of described optical window;Described reactor includes reactor body, reaction bed and temperature sensing unit, the liquid feeding end connected with described reaction chamber it is provided with on described reactor body, liquid outlet, inlet end and outlet side, described reaction bed is fixed on the basal surface of described reactor body and is positioned in described reaction chamber, described temperature sensing unit includes that sensor encapsulates post, holding wire and temperature sensor, described temperature sensor is arranged on the top of sensor encapsulation post, described holding wire is encapsulated in the inside of sensor encapsulation post and electrically connects with described temperature sensor, described temperature sensing unit is removably mounted in reactor body and makes temperature sensor to be positioned at the bottom of reaction bed;
Described liquid circuit module includes liquid storage unit, fluid path switching solenoid valve, liquid feeding pump and drawing liquid pump, described liquid storage unit includes reagent storage bottle and cleanout fluid storage bottle, described reagent storage bottle is connected with fluid path switching solenoid valve respectively with cleanout fluid storage bottle, described fluid path switching solenoid valve is connected with the liquid feeding end of detection module by liquid feeding pump, and described drawing liquid pump is connected with the liquid outlet of detection module;
Described gas path module includes sampler, sampling gas circuit, demarcate gas circuit and exhaust-gas treatment gas circuit, described sampling gas circuit is arranged in parallel with demarcating gas circuit and is connected with the inlet end of detection module by sampler respectively, described exhaust-gas treatment gas circuit includes exhaust gas treatment unit and air pump, described exhaust gas treatment unit is connected with the outlet side of detection module by air pump, described demarcation gas circuit includes zero gas generating unit, first gas circuit switching solenoid valve, nitrogen dioxide gas generating unit, second gas circuit switching solenoid valve and gas processing unit, described zero gas generating unit is connected with nitrogen dioxide gas generating unit by the first gas circuit switching solenoid valve, described nitrogen dioxide gas generating unit is connected with sampler and gas processing unit respectively by the second gas circuit switching solenoid valve.
An embodiment according to self-calibration formula nitrogen dioxide continuous on-line detection device of the present utility model, rhombus groove is offered on the basal surface of described reactor body, airtight rhombus reaction chamber is formed between described rhombus groove and opacus housing, it is provided with bar shaped reactive tank in the middle part of the basal surface of described rhombus groove, described reaction bed is arranged in described bar shaped reactive tank, wherein, described liquid feeding end, liquid outlet, inlet end and outlet side lay respectively at four apex of described rhombus groove, liquid feeding end is positioned at the upper end of rhombus groove and is positioned at the upper end of bar shaped reactive tank, liquid outlet is positioned at the lower end of rhombus groove and is positioned at the lower end of bar shaped reactive tank, inlet end and outlet side lay respectively at the two ends, left and right of rhombus groove.
An embodiment according to self-calibration formula nitrogen dioxide continuous on-line detection device of the present utility model, described liquid feeding end includes liquid inlet joint and is arranged on the first strongly hydrophilic superfine fibre implant of liquid inlet joint end, and described first strongly hydrophilic superfine fibre implant is close to described reaction bed and is arranged;Described liquid outlet includes liquid joint and liquid outlet channel, the bottom of described bar shaped reactive tank is provided with poly-liquid pool, described poly-liquid pool is by being arranged on liquid outlet channel bottom poly-liquid pool and going out liquid fittings, wherein, being provided with the second strongly hydrophilic superfine fibre implant in described poly-liquid pool, described second strongly hydrophilic superfine fibre implant is close to described reaction bed and is arranged.
An embodiment according to self-calibration formula nitrogen dioxide continuous on-line detection device of the present utility model, described liquid outlet channel includes vertical section and traversing section, described vertical section is connected with poly-liquid pool, and described traversing section is connected with going out liquid joint, and described vertical section is connected with using arc between traversing section.
An embodiment according to self-calibration formula nitrogen dioxide continuous on-line detection device of the present utility model, described temperature sensor is the miniature platinum resistance of ceramic package, and described temperature sensor is positioned at the side of close reaction bed in the middle part of poly-liquid pool and is embedded in the inside of described second strongly hydrophilic superfine fibre implant;The upper surface of described reaction bed is slightly below the upper surface of described rhombus groove.
According to an embodiment of self-calibration formula nitrogen dioxide continuous on-line detection device of the present utility model, described reagent storage bottle includes luminol, Na built with hybrid detection reagent and described hybrid detection reagent2SO3, KI and surfactant, described cleanout fluid storage bottle is built with deionized water;Described liquid storage unit also includes waste collection bottle, and described waste collection bottle is connected with the liquid outlet of detection module by drawing liquid pump, and wherein, described reagent storage bottle, cleanout fluid storage bottle and waste collection bottle are made up of black PP material.
According to an embodiment of self-calibration formula nitrogen dioxide continuous on-line detection device of the present utility model, described liquid circuit module also includes level detection unit and the constant temperature unit being connected with described liquid storage unit.
An embodiment according to self-calibration formula nitrogen dioxide continuous on-line detection device of the present utility model, described zero gas generating unit includes the first Filter column, membrane pump and effusion meter, described nitrogen dioxide gas generating unit includes that first is dried post and nitrogen dioxide calibrating gas generator, described gas processing unit includes that second is dried post and the second Filter column, and described exhaust gas treatment unit includes the 3rd Filter column;Described nitrogen dioxide calibrating gas generator is nitrogen dioxide standard gas generating apparatus based on osmos tube technology, and described first is dried post and second is dried post and is separately positioned on the front-end and back-end of described nitrogen dioxide calibrating gas generator;Described first is dried in post and second is dried post and is filled with blue silica gel, being filled with chemistry filtrate mixture in described first Filter column, the second Filter column and the 3rd Filter column, described chemistry filtrate mixture includes potassium permanganate activated alumina column, alkalization activated carbon and normal activated carbon.
Compared with prior art, this utility model provide self-calibration formula nitrogen dioxide continuous on-line detection device preferably solve liquid phase surface chemistry luminescence method Nitrogen dioxide testing field application present in poor stability, demarcate difficulty problem, greatly improve stability and the accuracy of detection, have highly sensitive, selectivity good, stability is high, accuracy high, demarcate and automaticity height without artificial, may be used for the continuous real time on-line monitoring of nitrogen dioxide gas concentration in ambient air.
Accompanying drawing explanation
Fig. 1 shows the structure principle chart of the self-calibration formula nitrogen dioxide continuous on-line detection device according to this utility model exemplary embodiment.
Fig. 2 shows the left view structural representation of detection module in the self-calibration formula nitrogen dioxide continuous on-line detection device according to this utility model exemplary embodiment.
Fig. 3 shows the sectional structure schematic diagram of detection module in the self-calibration formula nitrogen dioxide continuous on-line detection device according to this utility model exemplary embodiment.
Fig. 4 shows the right TV structure schematic diagram of the reactor body of detection module in the self-calibration formula nitrogen dioxide continuous on-line detection device according to this utility model exemplary embodiment.
Description of reference numerals:
10-liquid circuit module, 11-detecting liquid level unit, 12-constant temperature unit, 13-liquid storage unit, 131-reagent storage bottle, 132-cleanout fluid storage bottle, 133-waste collection bottle, 14-fluid path switching solenoid valve, 15-liquid feeding pump, 16-drawing liquid pump;
20-detection module, 21-reactor, 211-reactor body, 212-liquid feeding end, 2121-liquid inlet joint, 2122-the first strongly hydrophilic superfine fibre implant, 213-liquid outlet, 2131-goes out liquid joint, 2132-liquid outlet channel, the poly-liquid pool of 2133-, 2134-the second strongly hydrophilic superfine fibre implant, 214-inlet end, 215-outlet side, 216-temperature sensing unit, 2161-sensor encapsulation post, 2162-holding wire, 2163-temperature sensor, 217-reaction bed, 218-rhombus groove, 219-bar shaped reactive tank, the opacus housing of 22-, 23-optical window, 24-photoelectric sensing unit, 25-reaction chamber, 26-O RunddichtringO;
30-gas path module, 301-samples gas circuit, 302-demarcates gas circuit, 303-exhaust-gas treatment gas circuit, 31-zero gas generating unit, 311-the first Filter column, 312-membrane pump, 313-effusion meter, 32-the first gas circuit switching solenoid valve, 33-nitrogen dioxide gas generating unit, 331-first is dried post, 332-nitrogen dioxide calibrating gas generator, 34-the second gas circuit switching solenoid valve, 35-gas processing unit, 351-second is dried post, 352-the second Filter column, 36-sampler, 37-air pump, 38-exhaust gas treatment unit.
Detailed description of the invention
All features disclosed in this specification, or disclosed all methods or during step, in addition to mutually exclusive feature and/or step, all can combine by any way.
Any feature disclosed in this specification (including any accessory claim, summary and accompanying drawing), unless specifically stated otherwise, all can be by other equivalences or there is the alternative features of similar purpose replaced.I.e., unless specifically stated otherwise, an example during each feature is a series of equivalence or similar characteristics.
Structure and the principle of this utility model self-calibration formula nitrogen dioxide continuous on-line detection device will be described in detail below.
Fig. 1 shows the structure principle chart of the self-calibration formula nitrogen dioxide continuous on-line detection device according to this utility model exemplary embodiment.
As it is shown in figure 1, according to exemplary embodiment of the present utility model, described self-calibration formula nitrogen dioxide continuous on-line detection device includes liquid circuit module 10, gas path module 30 and detection module 20.Wherein, liquid circuit module 10 is for being passed through the liquid such as Nitrogen dioxide testing reagent, cleanout fluid constantly and realizing the renewal of liquid in detection module 20, detection module 10 is the key component realizing nitrogen dioxide continuous on-line detection, and gas path module 30 is for being passed through gas to be measured and carrying out the automatic on-line demarcation of detection system in detection module 20.
Fig. 2 shows the left view structural representation of detection module in the self-calibration formula nitrogen dioxide continuous on-line detection device according to this utility model exemplary embodiment, Fig. 3 shows the sectional structure schematic diagram of detection module in the self-calibration formula nitrogen dioxide continuous on-line detection device according to this utility model exemplary embodiment, and Fig. 4 shows the right TV structure schematic diagram of the reactor body of detection module in the self-calibration formula nitrogen dioxide continuous on-line detection device according to this utility model exemplary embodiment.
According to this utility model, the liquid phase surface chemistry luminous detection sensor that detection module 20 is actually based between luminol and nitrogen dioxide is high to the detection sensitivity of nitrogen dioxide gas, selectivity is good and has the fastest response speed.As shown in Figures 2 to 4, detection module 20 includes reactor 21, opacus housing 22, optical window 23 and photoelectric sensing unit 24, optical window 23 is arranged between reactor 21 and opacus housing 22, form airtight reaction chamber 25 between reactor 21 and opacus housing 22 and reaction chamber 25 is positioned at the side of optical window 23, it is internal and be positioned at the opposite side of optical window 23 that photoelectric sensing unit 24 is arranged on opacus housing 22, thus photoelectric sensing unit 24 can detect the intensity of chemiluminescence signal in reaction chamber 25 by optical window 14 and carry out the measurement of content of nitrogen dioxide.Preferably, O RunddichtringO 26 is used to be sealingly mounted between reactor 21 and opacus housing 22 by optical window 23.
Specifically, reactor 21 includes reactor body 211, reaction bed 217 and temperature sensing unit 216, being provided with liquid feeding end 212, liquid outlet 213, inlet end 214 and the outlet side 215 connected with reaction chamber 25 on reactor body 211, reaction bed 217 is fixed on the basal surface of reactor body 211 and is positioned in reaction chamber 25.Temperature sensing unit 216 includes sensor encapsulation post 2161, holding wire 2162 and temperature sensor 2163, temperature sensor 2163 is arranged on the top of sensor encapsulation post 2161, holding wire 2162 is encapsulated in the inside of sensor encapsulation post 2161 and electrically connects with temperature sensor 2163, temperature sensing unit 216 is removably mounted in reactor body 211 and makes temperature sensor 2163 to be positioned at the bottom of reaction bed 217, such as, screw fixation method can be used to be arranged in reactor body 211.Wherein, reaction bed 217 has stronger liquid adsorption ability and can adsorb detectable, and gas to be detected can be with the detectable generation liquid phase chemiluminescence reaction of reaction bed 217 absorption;Temperature sensing unit 216 for reaction temperature measurement and can Real-time Feedback reaction temperature.
In order to ensure the precision of detection, the structure of reactor in detection module is also improved by this utility model, but this utility model is not limited to this, it would however also be possible to employ the reactor of other structure or detection module, as long as it is capable of the effect of Nitrogen dioxide testing.But, the reactor of following structure can reach superior technique effect the accuracy ensureing continuous on-line detection and stability.
As shown in Figure 4, according to this utility model, the basal surface of reactor body 211 offers rhombus groove 218, between rhombus groove 218 and opacus housing 22, form airtight rhombus reaction chamber, being provided with bar shaped reactive tank 219 in the middle part of the basal surface of rhombus groove 218, reaction bed 217 is arranged in bar shaped reactive tank 219.Specifically, bar shaped reactive tank 219 is vertically arranged, and reaction bed 217 preferably has the shape matched with bar shaped reactive tank 219 and can be fixed in bar shaped reactive tank 219.Wherein, liquid feeding end 212, liquid outlet 213, inlet end 214 and outlet side 215 lay respectively at four apex of rhombus groove 218, liquid feeding end 212 is positioned at the upper end of rhombus groove 218 and is positioned at the upper end of bar shaped reactive tank 219, liquid outlet 213 is positioned at the lower end of rhombus groove 218 and is positioned at the lower end of bar shaped reactive tank 219, is thus easy to detectable flowing from the top down;Inlet end 214 and outlet side 215 lay respectively at the two ends, left and right of rhombus groove 218, so that the flow direction of gas to be detected is vertical with the flow direction of detectable to ensure contacting efficiency and reaction efficiency, the most preferably the gas flow path between inlet end 214 and outlet side 215 is used airflow design and without dead volume, it is simple to upgrading in time of reaction chamber 25 reaction gases.
In addition, the upper surface of bottom and reaction bed 217 that reaction bed 217 is positioned at bar shaped reactive tank 219 is preferably slightly below the upper surface of rhombus groove 218, this set-up mode both can ensure that being fully contacted of detectable and gas to be detected, can farthest weaken the impact that distribution and the flowing of detectable are produced by gas flowing, it is ensured that the concordance of the detection state during measuring continuously also ensure that stability and the accuracy of testing result simultaneously.
According to this utility model, liquid feeding end 212 includes liquid inlet joint 2121 and is arranged on the first strongly hydrophilic superfine fibre implant 2122 of liquid inlet joint 2121 end, and the first strongly hydrophilic superfine fibre implant 2122 is close to reaction bed 217 and is arranged.Owing to the end of liquid feeding end 212 is provided with the strongly hydrophilic superfine fibre implant being in close contact with reaction bed 217, therefore detectable enters from liquid feeding end 212 and can initially enter the first strongly hydrophilic superfine fibre implant 2122 after detection module, arrive reaction bed 217 again, this can reduce the pulsation effect of feed liquor peristaltic pump feed liquor and weaken the feed liquor impact to reaction bed 217, the beneficially detectable the most uniformly diffusion on reaction bed 217.Wherein, the first strongly hydrophilic superfine fibre implant can use the materials such as superfine polypropylene fiber, absorbent cotton;Reaction bed can use the materials such as polyester fiber cloth, silk, pure cotton cloth, non-woven fabrics.
Liquid outlet 213 includes liquid joint 2131 and liquid outlet channel 2132, the bottom of bar shaped reactive tank 219 is provided with poly-liquid pool 2133, poly-liquid pool 2133 connects with going out liquid joint 2131 by being arranged on the liquid outlet channel 2132 bottom poly-liquid pool 2133, wherein, being provided with the second strongly hydrophilic superfine fibre implant 2134 in poly-liquid pool 2133, the second strongly hydrophilic superfine fibre implant 2134 is close to reaction bed 217 and is arranged.Preferably, the inner surface of poly-liquid pool 2133 is Curve Design and in inverted cone, it is simple to detectable converges to bottom poly-liquid pool.Due to the inside of poly-liquid pool 2133 be filled with strongly hydrophilic and with reaction bed 217 be in close contact the second strongly hydrophilic superfine fibre implant 2134, thus under the effect of the drawing liquid peristaltic pump of liquid outlet rear end, draft will be produced at liquid outlet channel mouth, and uniform suction will be produced under the capillarity of the internal superfine fibre of implant, this detectable being easy to be collected to reaction bed 217 bottom overcomes reaction bed suction and the effect of surface tension of liquid to depart from bottom reaction bed, ensure the detectable timely continuous updating on reaction bed 217 surface and ensure the stability of detection.Wherein, above-mentioned liquid inlet joint 2121 and go out liquid joint 2131 and all can install in the way of being threadably secured.
Wherein, one end of liquid outlet channel 2132 with go out liquid joint and be connected and the port of the other end is positioned at the bottommost of poly-liquid pool 2133.Preferably, liquid outlet channel 2132 of the present utility model includes vertical section and traversing section, and vertical section is connected with poly-liquid pool 2133, and traversing section is connected with going out liquid joint 2131, and vertical section is connected with using arc between traversing section.Wherein, discharge opeing is easy in the design of vertical section, the design of traversing section is easily installed and safeguards, the mode using arc to connect can be easy to dredging in the case of liquid outlet channel blocks, and be more beneficial for the flowing of liquid during discharge opeing and reduce gas resistance around the corner during discharging gas-liquid mixture.
Preferably, temperature sensor 2163 is the miniature platinum resistance of ceramic package, and temperature sensor 2163 is preferably located in the side of close reaction bed 217 in the middle part of poly-liquid pool 2133 and is embedded in the inside of the second strongly hydrophilic superfine fibre implant 2134, so that temperature sensor 2163 does not contacts with reactor body 211 and can be fully contacted with detectable, and then the impact on measurement result of reactor body 211 surface temperature can be reduced, measure reaction temperature more accurately.
According to this utility model, liquid circuit module 10 includes liquid storage unit 13, fluid path switching solenoid valve 14, liquid feeding pump 15 and drawing liquid pump 16.Wherein, liquid storage unit 13 includes reagent storage bottle 131 and cleanout fluid storage bottle 132, reagent storage bottle 131 is connected with fluid path switching solenoid valve 14 respectively with cleanout fluid storage bottle 132, fluid path switching solenoid valve 14 is connected with the liquid feeding end 212 of detection module 20 by liquid feeding pump 15, and drawing liquid pump 16 is connected with the liquid outlet 213 of detection module 20.
Wherein, reagent storage bottle 131 includes luminol, potassium hydroxide, Na built with hybrid detection reagent and this hybrid detection reagent2SO3, KI and surfactant.nullAccording to an embodiment of the present utility model,Described hybrid detection reagent includes luminol 0.001~0.005mol/L、Potassium hydroxide 0.1~0.5mol/L、Sodium sulfite 0.1~0.5mol/L、Potassium iodide 0.1~0.5mol/L and surfactant triton X-100 0.1~0.5vol.%,This hybrid detection reagent can be with nitrogen dioxide generation gas-liquid chemiluminescence reaction the detection realizing content of nitrogen dioxide,And this hybrid detection reagent can effectively eliminate ozone in ambient air、The minor way of two kinds of gases of PAN,Further increase the accuracy of detection,Its response to nitrogen dioxide gas concentration in wider scope simultaneously has fabulous linear dependence,Which ensure that the reliability of single-point calibration method used in this utility model,Make calibration process simpler、Practical;Cleanout fluid storage bottle 132 is built with deionized water, and the cleaning of reactor in can being passed into completing detection module in detection module by fluid path switching after detection terminates, prevention detectable residual forms crystallization and affects detection next time.In addition, liquid storage unit 131 can also include waste collection bottle 133, waste collection bottle 133 is connected with the liquid outlet 213 of detection module 20 by drawing liquid pump 16, and the water after the most reacted detectable and cleaning all can be collected by waste collection bottle 133, it is to avoid pollutes.Preferably, reagent storage bottle 131, cleanout fluid storage bottle 132 and waste collection bottle 133 are made by black PP material, both can effectively prevent reagent contact light from composition transfer occurring, can avoid again reagent and bottle material generation chemical action.
It is highly preferred that liquid circuit module 10 can also include level detection unit 11 and the constant temperature unit 12 being connected with liquid storage unit 13.Wherein, the liquid level of the detectable in liquid storage unit, cleanout fluid and waste liquid can be monitored and be checked without artificial by level detection unit 11 in real time, and prevention occurs that liquid is under-supply or the problem of waste liquid bottle discharge, improves the automaticity of device;Specifically, detecting liquid level unit 11 detects liquid level in bottle by being located at the pressure transducer institute pressure measurement force value at the bottom of liquid storage unit bottle.And, constant temperature unit 12 can carry out temperature holding (prevent temperature of reagent too high or too low) to the detectable in liquid storage unit, prevent the harmful effect that reagent is produced by ambient temperature or reduction or device interior thermal source, eliminate the ambient temperature impact on detecting system stability, improve detection sensitivity and stability.
According to this utility model, gas path module 30 includes sampler 36, sampling gas circuit 301, demarcates gas circuit 302 and exhaust-gas treatment gas circuit 303, sampling gas circuit 301 is arranged in parallel with demarcating gas circuit 302 and is connected with the inlet end 214 of detection module 20 by sampler 36 respectively, namely sampling gas circuit 301 is for being passed through gas to be detected in detection module, and demarcate gas circuit for detecting system being carried out automatic on-line demarcation, exhaust-gas treatment gas circuit 303 is discharged after processing the waste gas after detection.
Exhaust-gas treatment gas circuit 303 includes that exhaust gas treatment unit 38 and air pump 37, exhaust gas treatment unit 38 are connected with the outlet side 215 of detection module 20 by air pump 37.Demarcate gas circuit 302 and include zero gas generating unit the 31, first gas circuit switching solenoid valve 32, nitrogen dioxide gas generating unit the 33, second gas circuit switching solenoid valve 34 and gas processing unit 35, zero gas generating unit 31 is connected with nitrogen dioxide gas generating unit 33 by the first gas circuit switching solenoid valve 32, and nitrogen dioxide gas generating unit 33 is connected with sampler 36 and gas processing unit 35 respectively by the second gas circuit switching solenoid valve 34.
As shown in Figure 1, zero gas generating unit 31 includes the first Filter column 311, membrane pump 312 and effusion meter 313, nitrogen dioxide gas generating unit 332 includes that first is dried post 331 and nitrogen dioxide calibrating gas generator 332, gas processing unit 35 includes that second is dried post 351 and the second Filter column 352, and exhaust gas treatment unit 38 includes the 3rd Filter column.
Wherein, nitrogen dioxide calibrating gas generator 332 is nitrogen dioxide standard gas generating apparatus based on osmos tube technology, and nitrogen dioxide calibrating gas needed for can accurately and reliably producing automatic Calibration also improves the accuracy of testing result.Specifically, this utility model can use the nitrogen dioxide standard gas generating apparatus disclosed in the utility application of Application No. 201410774120.7, but this utility model is not limited to this.
First is dried post 331 and second is dried post 351 and is separately positioned on the front-end and back-end of nitrogen dioxide calibrating gas generator 332, and is filled with blue silica gel in first is dried post 331 and second is dried post 351.Chemistry filtrate mixture it is filled with in first Filter column the 311, second Filter column 352 and the 3rd Filter column, specifically, this chemistry filtrate mixture includes potassium permanganate activated alumina column, alkalization activated carbon and normal activated carbon, can the effective dusty gas such as nitrogen oxides, ozone, sulfur dioxide in filtered atmospheric, improve precision and the purity producing gas.
In the case of being not powered on, the front-end and back-end gas circuit of nitrogen dioxide calibrating gas generator 332 is respectively connected with silica dehydrator post, the diffusion of moisture that is possible to prevent in air enters to react with nitrogen dioxide gas in the osmos tube of nitrogen dioxide calibrating gas generator 332 and generates nitrous acid and corrosion contamination pipeline, improve the reproducibility and reliability of produced calibrating gas, thus the beneficially stability of detection equipment and accuracy;Rear end gas circuit is connected with outside air also by a gas filtration post, prevent from constantly accumulating at nitrogen dioxide gas produced by device storage stage osmos tube and in pipeline, producing more absorption, and effectively reduce generation and the corrosion of piping risk of nitrous acid;Simultaneously, the nitrogen dioxide gas that Filter column is also prevented from producing outwards discharges, other dusty gas being simultaneously possible to prevent again in environment reversely diffuses into nitrogen dioxide calibrating gas generator and destroys osmos tube, it is ensured that the repeatability of nitrogen dioxide gas and reliability.
When using self-calibration formula nitrogen dioxide continuous on-line detection device of the present utility model to detect, may comprise steps of:
Step 1: detection module is energized and makes temperature sensor complete preheating, liquid circuit module is energized and makes fluid path switching solenoid valve connect, the detectable in reagent storage bottle is made to enter detection module under the effect of liquid feeding pump and extract detection module under the effect of drawing liquid pump out, it is achieved the circulation of detectable.
Step 2: gas path module is energized and opens the first gas circuit switching solenoid valve, air is made to enter in nitrogen dioxide gas generating unit as carrier gas after zero gas generating unit, completing the nitrogen dioxide calibrating gas generator internal cavity in nitrogen dioxide gas generating unit and the purging of pipeline, purging gas empties after gas processing unit purifies.Specifically, under the effect of membrane pump and effusion meter, air enters first after the first Filter column filtration, purification and is dried post except water, then enters in nitrogen dioxide calibrating gas generator as carrier gas and completes purging.
Step 3: open the second gas circuit switching solenoid valve, control described nitrogen dioxide calibrating gas generator under temperature constant state, produce nitrogen dioxide gas with constant productivity and make the carrier gas of firm discharge bring in sampler by nitrogen dioxide gas, quantitative gas enter detection module and with the detectable generation liquid phase chemiluminescence reaction within detection module, the demarcation of the concentration completion system of nitrogen dioxide in the signal detected by photoelectric sensing unit and gas, the record current mean temperature detected by temperature sensor.
Step 4: close the second gas circuit switching solenoid valve, by sampling gas circuit by ambient air with identical speed by sampler suction in detection module and with the detectable generation liquid phase chemiluminescence reaction within detection module, calibrating parameters that the signal detected by photoelectric sensing unit and step 3 are obtained also combines the current mean temperature detected by temperature sensor and step 3 measured temperature carries out temperature correction, converses the content of nitrogen dioxide in current environment air.Wherein, ambient air is gas to be detected.
Step 5: repeat step 3 and step 4 with fixing frequency, it is achieved the self-calibration formula real-time online of the nitrogen dioxide gas concentration in ambient air is measured continuously.
Wherein, in step 3, the concentration of nitrogen dioxide calibrating gas produced by nitrogen dioxide calibrating gas generator is for it is known that be designated as C1;Within this detection cycle, the meansigma methods of the luminous signal that photoelectric sensing unit detects is V1, the meansigma methods of the reaction temperature that temperature sensing unit detects is T1;In step 4, the meansigma methods of detected chemiluminescence signal is V2And the meansigma methods of reaction temperature is T2;Further, by photomultiplier tube dark current reasons for its use noise V during device detection0For it is known that computer thus can be utilized and uses following formula to be calculated current content of nitrogen dioxide C in real time2:
C2=C1*(V2-V0)/(V1-V0)*ek*(T2-T1),
Wherein, k is temperature correction factor, and value is 0.1~0.5.
Further, it is also possible to close the fluid path switching solenoid valve in liquid circuit module after measurement terminates and make the cleanout fluid entrance detection module in cleanout fluid storage bottle is carried out.Preferably, control 1.5~2 times that go out that liquid speed is feed liquor speed of detection module, to prevent detectable from producing hydrops at inside reactor and farthest reducing the impact on gas circuit.
In sum, the self-calibration formula nitrogen dioxide continuous on-line detection device that this utility model provides utilizes liquid phase surface chemistry principle of luminosity, it is achieved high sensitivity, the high selective quickly measurement to nitrogen dioxide gas;Utilize the detectable formula optimized, eliminate ozone and the impact of PAN in ambient air, and ensure that detection system is to the linear response of content of nitrogen dioxide in atmospheric concentration horizontal extent, it is ensured that the reliability of single-point calibration method.
This utility model is not limited to aforesaid detailed description of the invention.This utility model expands to any new feature disclosed in this manual or any new combination, and the arbitrary new method that discloses or the step of process or any new combination.

Claims (8)

1. a self-calibration formula nitrogen dioxide continuous on-line detection device, it is characterised in that described device bag Include liquid circuit module, gas path module and detection module;
Described detection module includes reactor, opacus housing, optical window and photoelectric sensing unit, and optical window is arranged on Between described reactor and opacus housing, between described reactor and opacus housing, form airtight reaction chamber also And described reaction chamber is positioned at the side of described optical window, photoelectric sensing unit is arranged on opacus enclosure interior and position Opposite side in described optical window;Described reactor includes reactor body, reaction bed and temperature sensing unit, It is provided with liquid feeding end, liquid outlet, the inlet end connected with described reaction chamber on described reactor body and gives vent to anger End, described reaction bed is fixed on the basal surface of described reactor body and is positioned in described reaction chamber, institute Stating temperature sensing unit and include sensor encapsulation post, holding wire and temperature sensor, described temperature sensor sets Put sensor encapsulation post top, described holding wire be encapsulated in sensor encapsulation post inside and with described temperature Degree sensor electrical connection, described temperature sensing unit is removably mounted in reactor body and makes temperature pass Sensor is positioned at the bottom of reaction bed;
Described liquid circuit module includes liquid storage unit, fluid path switching solenoid valve, liquid feeding pump and drawing liquid pump, described storage Liquid unit includes that reagent storage bottle and cleanout fluid storage bottle, described reagent storage bottle and cleanout fluid storage bottle are respectively Being connected with fluid path switching solenoid valve, described fluid path switching solenoid valve is by the liquid feeding end of liquid feeding pump with detection module Being connected, described drawing liquid pump is connected with the liquid outlet of detection module;
Described gas path module includes sampler, sampling gas circuit, demarcates gas circuit and exhaust-gas treatment gas circuit, described in adopt Sample gas road is arranged in parallel with demarcating gas circuit and is connected with the inlet end of detection module by sampler respectively, institute State exhaust-gas treatment gas circuit and include exhaust gas treatment unit and air pump, described exhaust gas treatment unit by air pump with The outlet side of detection module is connected, and described demarcation gas circuit includes zero gas generating unit, the first gas circuit switching electromagnetism Valve, nitrogen dioxide gas generating unit, the second gas circuit switching solenoid valve and gas processing unit, described zero gas Generating unit is connected with nitrogen dioxide gas generating unit by the first gas circuit switching solenoid valve, described titanium dioxide Nitrogen gas generating unit is connected with sampler and gas processing unit respectively by the second gas circuit switching solenoid valve.
Self-calibration formula nitrogen dioxide continuous on-line detection device the most according to claim 1, its feature It is, the basal surface of described reactor body offers rhombus groove, between described rhombus groove and opacus housing Form airtight rhombus reaction chamber, in the middle part of the basal surface of described rhombus groove, be provided with bar shaped reactive tank, described reaction Bed is arranged in described bar shaped reactive tank, and wherein, described liquid feeding end, liquid outlet, inlet end and outlet side are divided Not being positioned at four apex of described rhombus groove, liquid feeding end is positioned at the upper end of rhombus groove and is positioned at bar shaped reactive tank Upper end, liquid outlet is positioned at the lower end of rhombus groove and is positioned at the lower end of bar shaped reactive tank, inlet end and outlet side Lay respectively at the two ends, left and right of rhombus groove.
Self-calibration formula nitrogen dioxide continuous on-line detection device the most according to claim 2, its feature Being, described liquid feeding end includes liquid inlet joint and is arranged on the first ultra-fine fibre of strongly hydrophilic of liquid inlet joint end Dimension implant, described first strongly hydrophilic superfine fibre implant is close to described reaction bed and is arranged;Described go out liquid End includes that liquid joint and liquid outlet channel, the bottom of described bar shaped reactive tank are provided with poly-liquid pool, described poly-liquid Pond, by being arranged on liquid outlet channel bottom poly-liquid pool and going out liquid fittings, wherein, sets in described poly-liquid pool Being equipped with the second strongly hydrophilic superfine fibre implant, described second strongly hydrophilic superfine fibre implant is close to institute State reaction bed to arrange.
Self-calibration formula nitrogen dioxide continuous on-line detection device the most according to claim 3, its feature Being, described liquid outlet channel includes vertical section and traversing section, and described vertical section is connected with poly-liquid pool, described horizontal stroke Being connected with going out liquid joint to section, described vertical section is connected with using arc between traversing section.
Self-calibration formula nitrogen dioxide continuous on-line detection device the most according to claim 3, its feature Being, described temperature sensor is the miniature platinum resistance of ceramic package, and described temperature sensor is positioned at poly-liquid pool Middle part is near the side of reaction bed and is embedded in the inside of described second strongly hydrophilic superfine fibre implant; The upper surface of described reaction bed is slightly below the upper surface of described rhombus groove.
Self-calibration formula nitrogen dioxide continuous on-line detection device the most according to claim 1, its feature Being, described reagent storage bottle includes Rumi built with hybrid detection reagent and described hybrid detection reagent Promise, potassium hydroxide, Na2SO3, KI and surfactant, described cleanout fluid storage bottle is built with deionization Water;Described liquid storage unit also includes waste collection bottle, and described waste collection bottle passes through drawing liquid pump and detection module Liquid outlet be connected, wherein, described reagent storage bottle, cleanout fluid storage bottle and waste collection bottle are by black PP material is made.
Self-calibration formula nitrogen dioxide continuous on-line detection device the most according to claim 1, its feature Being, described liquid circuit module also includes level detection unit and the constant temperature unit being connected with described liquid storage unit.
Self-calibration formula nitrogen dioxide continuous on-line detection device the most according to claim 1, its feature Being, described zero gas generating unit includes the first Filter column, membrane pump and effusion meter, described nitrogen dioxide mark Gas generating unit includes that first is dried post and nitrogen dioxide calibrating gas generator, described gas processing unit bag Including second and be dried post and the second Filter column, described exhaust gas treatment unit includes the 3rd Filter column;Described titanium dioxide Nitrogen calibrating gas generator is nitrogen dioxide standard gas generating apparatus based on osmos tube technology, described first Dry post and second is dried post and is separately positioned on the front-end and back-end of described nitrogen dioxide calibrating gas generator; Described first is dried in post and second is dried post and is filled with blue silica gel, described first Filter column, second filters Being filled with chemistry filtrate mixture in post and the 3rd Filter column, described chemistry filtrate mixture includes potassium permanganate Activated alumina column, alkalization activated carbon and normal activated carbon.
CN201620423113.7U 2016-05-11 2016-05-11 From maring continuous on -line measuring device of formula nitrogen dioxide Active CN205607866U (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107064117A (en) * 2017-04-27 2017-08-18 四川理工学院 Nitrogen oxides and peroxyacetyl nitrate joint on-line measuring device and method
CN109187456A (en) * 2018-08-17 2019-01-11 南京科略环境科技有限责任公司 A kind of atmosphere total oxidant photochemistry generating rate monitoring system

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107064117A (en) * 2017-04-27 2017-08-18 四川理工学院 Nitrogen oxides and peroxyacetyl nitrate joint on-line measuring device and method
CN107064117B (en) * 2017-04-27 2019-05-14 四川理工学院 Nitrogen oxides and peroxyacetyl nitrate joint on-line measuring device and method
CN109187456A (en) * 2018-08-17 2019-01-11 南京科略环境科技有限责任公司 A kind of atmosphere total oxidant photochemistry generating rate monitoring system
CN109187456B (en) * 2018-08-17 2020-10-20 南京科略环境科技有限责任公司 System for monitoring photochemical generation rate of total atmospheric oxidant

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