CN101231241A - Device and method for real time on-line detecting flue gas pollutant - Google Patents
Device and method for real time on-line detecting flue gas pollutant Download PDFInfo
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- CN101231241A CN101231241A CNA2008100469127A CN200810046912A CN101231241A CN 101231241 A CN101231241 A CN 101231241A CN A2008100469127 A CNA2008100469127 A CN A2008100469127A CN 200810046912 A CN200810046912 A CN 200810046912A CN 101231241 A CN101231241 A CN 101231241A
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Abstract
The invention discloses a real-time on-line detecting apparatus of smoke pollutant and the test method thereof, and relates to the atmospheric environmental monitoring. The apparatus comprises a pulse generator (1), a pulse laser (2), a time delayer (3), a reflector (4), a long-focus focusing lens (5), a light receiving device (6), optical fibre (7), a spectrometer (8), an A/D converter (10), and a computer (11). The invention utilizes a focused high energy laser beam to motivate the substance in the smoke gas to be the high energy state, various substances radiate respective characteristic spectrums during the process of the high energy state returning the base state, the composition of the pollutant such as magnesium, iron, copper, aluminum, lead, chrome, hydrargyrum, arsenic, etc. in the tested smoke gas and the concentration thereof can be obtained by analyzing the characteristic spectrums. The invention has the advantages of simple structure, reliable method and convenient operation, and is suitable for performing the real-time and on-line continuous detection of the pipeline smoke gas during the combustion process of coal.
Description
Technical field
The present invention relates to atmosphere environment supervision, be mainly used in the real-time online of multiple pollutant detection in the tunnel gas in the coal combustion process.
Background technology
Along with the raising of the needs and the environmental protection consciousness of sustainable development, the harm of human beginning common concern atmospheric pollution.Up-to-date scientific research shows: the flue gas that coal combustion produces is the primary pollution source of atmospheric pollution, has become the main object of environmental improvement.How effectively to control the discharging of combustion process and Air thing, become the focus that government department and scientific research institution pay close attention to further gradually.The prerequisite of pollutant emission is to know the composition and the content of pollutant in the control flue gas, and the measurement of real-time online, and its testing result can in time be found the problem that occurs in the combustion process, so that in time take measures, to reduce the generation of major pollution incident.
The method of pollutant is off-line mostly in the detection flue gas at present commonly used, and representational have inductively coupled plasma emission spectrography (ICP-AES) and a flame photometric analysis method.These two kinds of methods have improved the accuracy of detection to polluter significantly, but all must in the laboratory, finish, and all needing before detection sample to be carried out early stage handles, therefore strict to testing environment, test period is long, need expend the great amount of manpower and material resources resource, thereby can't in the process of burning, carry out in real time, effectively control.Rarely seen single-element analysis of the device of present online detection of contamination composition and vehicle exhaust detection etc.For example: a kind of online atmospheric mercury analyzer (application number: 200510123603.1) can only analyze to single-element mercury.And for example: vehicle exhaust is detected the infrared laser detection system of usefulness and method (application number: 01141682.3) can whether exceed standard to vehicle exhaust and monitor in real time, but can't judge the composition of its pollutant in real time.These devices all are not suitable for the real time on-line monitoring of various pollutants of fume in the coal combustion process.
In view of above reality, consider the complicacy of exhaust gas components, and its on-line monitoring is in the hot environment, at present, find as yet can to multiple pollutant in the flue gas carry out the scene, in real time, the device of continuous detecting.
Summary of the invention
The objective of the invention is: the real time on-line detection device that flue gas pollutant is provided.This device adopts the Laser-induced Breakdown Spectroscopy technology, utilize the high energy laser beam that focuses on that the material in the tested flue gas is energized into high-energy state, they will give off characteristic spectrum separately in getting back to the process of ground state, analyze the wavelength and the intensity of these spectrum, can obtain the composition and the concentration thereof of pollutant in the tested flue gas.This apparatus structure is simple, and is easy to operate, can carry out real-time, online, continuous detection to the multiple pollutant in the flue gas.Another object of the present invention is: the method that detects flue gas pollutant with said apparatus is provided.
The present invention adopts following technical scheme in order to achieve the above object:
The real time on-line detection device of flue gas pollutant is made up of pulse producer, pulsed laser, time delays device, saturating anti-mirror, long-focus condenser lens, light receiving device, optical fiber, spectrometer, photoelectric detector, A/D converter and computing machine.Pulse producer connects the external trigger end of pulsed laser and the input end of time delays device respectively; Laser emission direction saturating anti-mirror of the coaxial arrangement of order and long condenser lens at pulsed laser, the receiving end of light receiving device is placed in the coaxial position of anti-specular reflection direction, the output terminal of light receiving device is connected with the input end of spectrometer by optical fiber, and the output terminal of spectrometer is connected to the input end of photoelectric detector; The output terminal of time delays device is connected to another input end of photoelectric detector, and the output terminal of photoelectric detector is connected to the input end of A/D converter, and the output terminal of A/D converter is connected to computing machine.
Principle of work of the present invention is: adopt this elemental analysis method of Laser-induced Breakdown Spectroscopy (LIBS) technology, this method comes from " the Laser-induced Breakdown Spectroscopy handbook (Handbook of Laser-InducedBreakdown Spectroscopy) that U.S. David A.Cremers and Leon J.Radziemski write.It is to utilize the high energy laser beam that focuses on that tested flue gas is punctured to form high-temperature plasma, various materials in the flue gas all are excited to high-energy state, get back to various materials in the process of ground state at high-energy state and will give off separately characteristic spectrum, by wavelength and the intensity of analyzing these spectrum, can obtain the composition and the concentration thereof of pollutant in the tested flue gas.Definite the atomic spectrum standard and the technical data library of element spectral line with reference to American National Standard and Institute for Research and Technology (NIST).According to our a large amount of simulation tunnel gas experiments of measuring, the characteristic spectral line of getting the pollutant element is as follows: magnesium-279.6 nanometer, iron-404.6 nanometer, copper-324.8 nanometer, aluminium-309.3 nanometer, lead-405.8 nanometer, chromium-520.8 nanometer, mercury-253.7 nanometer, arsenic-228.8 nanometer.
Utilize Laser-induced Breakdown Spectroscopy (LIBS) technology, the result who obtains the flue gas pollutant discharging that can real-time online, whether reasonably whether the discharging that these results can be used as flue gas pollutant conformance with standard, and whether comburant meets the demands, and combustion process foundation.
The present invention is used for flue gas and detects pollutants such as magnesium, iron, copper, aluminium, lead, chromium, mercury, arsenic.
Compared with prior art, the present invention has the following advantages:
1, can detect pollutant and concentration thereof such as magnesium in the flue gas, iron, copper, aluminium, lead, chromium, mercury, arsenic simultaneously;
2, can carry out real-time, online continuous detecting to pollutants such as the magnesium in the flue gas, iron, copper, aluminium, lead, chromium, mercury, arsenic;
3, do not need that before detection testing sample is carried out early stage and handle, can in time obtain analysis result;
4, transmit and receive the coaxial design of device, spectral signal that can easier test sample;
5, simple in structure, easy to operate, be adapted at using in the coal combustion flue gas pipeline.
Description of drawings
Fig. 1 is a structural representation of the present invention.
Fig. 2 is with the curve map of lead element 405.8 nanofeature spectral lines " spectral intensity-concentration " in the detected flue gas of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further illustrated.
As shown in Figure 1, the real time on-line detection device of flue gas pollutant is made up of pulse producer 1, pulsed laser 2, time delays device 3, saturating anti-mirror 4, long-focus condenser lens 5, light receiving device 6, optical fiber 7, spectrometer 8, photoelectric detector 9, A/D converter 10 and computing machine 11.Pulse producer 1 connects the external trigger end of pulsed laser 2 and the input end of time delays device 3 respectively; Saturating anti-mirror 4 of the coaxial arrangement of Laser emission direction order and long condenser lens 5 at pulsed laser 2, the receiving end of light receiving device 6 is placed in the coaxial position of anti-mirror 4 reflection directions, the output terminal of light receiving device 6 is connected with the input end of spectrometer 8 by optical fiber 7, and the output terminal of spectrometer 8 is connected to the input end of photoelectric detector 9; The output terminal of time delays device 3 is connected to another input end of photoelectric detector 9, and the output terminal of photoelectric detector 9 is connected to the input end of A/D converter 10, and the output terminal of A/D converter 10 is connected to computing machine 11.
The output wavelength of pulsed laser 2 is 1064 nanometers, and range of laser energy is that 100～500 millis are burnt.
Detect the method for flue gas pollutant with the real time on-line detection device of flue gas pollutant, this method follows these steps to carry out:
A, the real time on-line detection device of flue gas pollutant is placed near the flue gas that needs to detect, makes the focus of the long condenser lens 5 of this device be positioned at the sampling spot place of flue gas;
B, open the real time on-line detection device of flue gas pollutant, at this moment, the pulse producer 1 of this device sends pulse signal for simultaneously pulsed laser 2 and time delays device 3, the external trigger end of pulsed laser 2 receives that a pulse signal just sends a pulse laser, pulse laser focuses on the flue gas behind saturating anti-mirror 4 and long condenser lens 5;
C, after high energy laser beam that flue gas is focused punctures, can form high-temperature plasma, various materials in the flue gas will be excited to high-energy state, before next pulse laser arrives, the various materials of high-energy state will be got back to ground state, in this process, various materials can give off characteristic spectrum separately;
D, characteristic spectrum can reflex to the long condenser lens 5 of the real time on-line detection device of flue gas pollutant, through saturating anti-mirror 4 reflections, enter light receiving device 6, are transmitted to spectrometer 8 through optical fiber 7 again;
Import photoelectric detector 9 into after the light signal beam split that e, 8 pairs of spectrometers receive, at this moment, pulse producer 1 excites another pulse signal that this pulse laser sends simultaneously just in time to trigger photoelectric detector 9 collection of opening the door through time delays device 3, and convert the light signal that collects to electric signal, electric signal transfers simulating signal to digital signal through A/D converter 10, and imports computing machine 11;
Which kind of material f, computing machine 11 belong to the flue gas sample Laser-induced Breakdown Spectroscopy that obtains according to pollutant in the following method judgement sample, and the contained concentration of this material;
The determination methods of f1, contaminant species is:
When characteristic spectral line was 279.6 nanometers, the pollutant element was a magnesium;
When characteristic spectral line was 404.6 nanometers, the pollutant element was an iron;
When characteristic spectral line was 324.8 nanometers, the pollutant element was a copper;
When characteristic spectral line was 309.3 nanometers, the pollutant element was an aluminium;
When characteristic spectral line was 405.8 nanometers, the pollutant element was plumbous;
When characteristic spectral line was 520.8 nanometers, the pollutant element was a chromium;
When characteristic spectral line was 253.7 nanometers, the pollutant element was a mercury;
When characteristic spectral line was 228.8 nanometers, the pollutant element was an arsenic;
F2, the contained concentration of all contaminations are calculated by following formula respectively:
lgI＝blgC+lga (1.1)
I is line strength in the formula, and a is a constant, b by the self absorption factor of survey material, C is the concentration of element;
Formula (1.1) is by the fundamental formular Lomakin-Scheibe formula I=aC of emission spectrum quantitative test
bTake the logarithm and obtain;
F21, get contained magnesium, iron, copper, aluminium, lead, chromium, mercury, gas that arsenic concentration is known respectively, detect line strength I separately respectively, calculate the constant a of magnesium, iron, copper, aluminium, lead, chromium, mercury, arsenic by formula (1.1) respectively;
F22,279.6 nanometer line strength I that will from flue gas, measure, and the self absorption factor b of magnesium, the constant a of the magnesium that obtains by step f21, substitution step f2 formula (1.1) just can obtain the concentration C of contained magnesium in the gas;
404.6 nanometer line strength I that will from flue gas, measure, and the self absorption factor b of iron, the constant a of the iron that obtains by step f21, substitution step f2 formula (1.1) just can obtain the concentration C of institute's iron content in the flue gas;
324.8 nanometer line strength I that will from flue gas, measure, and the self absorption factor b of copper, the constant a of the copper that obtains by step f21, substitution step f2 formula (1.1) just can obtain the concentration C of institute's cupric in the flue gas;
309.3 nanometer line strength I that will from flue gas, measure, and the self absorption factor b of aluminium, the constant a of the aluminium that obtains by step f21, substitution step f2 formula (1.1) just can obtain the concentration C of contained aluminium in the flue gas;
405.8 nanometer line strength I that will from flue gas, measure, and plumbous self absorption factor b, the constant a of the lead that obtains by step f21, substitution step f2 formula (1.1), just can obtain in the flue gas leaded concentration C;
520.8 nanometer line strength I that will from flue gas, measure, and the self absorption factor b of chromium, the constant a of the chromium that obtains by step f21, substitution step f2 formula (1.1) just can obtain the concentration C of contained chromium in the flue gas;
253.7 nanometer line strength I that will from flue gas, measure, and the self absorption factor b of mercury, the constant a of the mercury that obtains by step f21, substitution step f2 formula (1.1), just can obtain in the flue gas mercurous concentration C;
228.8 nanometer line strength I that will from flue gas, measure, and the self absorption factor b of arsenic, the constant a of the arsenic that obtains by step f21, substitution step f2 formula (1.1) just can obtain the concentration C of contained arsenic in the flue gas.
Fig. 2 is with the curve map of lead element 405.8 nanofeature spectral lines " spectral intensity-concentration " in the detected flue gas of the present invention.Wherein, horizontal ordinate is the logarithm lgC of constituent content, and ordinate is line strength logarithm lgI, the linearity 0.99, and slope 0.41, promptly self absorption factor is 0.41.
Claims (3)
1. the real time on-line detection device of flue gas pollutant, it is characterized in that this device is made up of pulse producer (1), pulsed laser (2), time delays device (3), saturating anti-mirror (4), long-focus condenser lens (5), light receiving device (6), optical fiber (7), spectrometer (8), photoelectric detector (9), A/D converter (10) and computing machine (11); Pulse producer (1) connects the external trigger end of pulsed laser (2) and the input end of time delays device (3) respectively; Laser emission direction order saturating anti-mirror of coaxial arrangement (4) and long condenser lens (5) at pulsed laser (2), the receiving end of light receiving device (6) is placed in the coaxial position of anti-mirror (4) reflection direction, the output terminal of light receiving device (6) is connected with the input end of spectrometer (8) by optical fiber (7), and the output terminal of spectrometer (8) is connected to the input end of photoelectric detector (9); The output terminal of time delays device (3) is connected to another input end of photoelectric detector (9), and the output terminal of photoelectric detector (9) is connected to the input end of A/D converter (10), and the output terminal of A/D converter (10) is connected to computing machine (11).
2. the real time on-line detection device of flue gas pollutant according to claim 1 is characterized in that, the output wavelength of described pulsed laser (2) is 1064 nanometers, and laser energy is that 100～500 millis are burnt.
3. detect the method for flue gas pollutant with the real time on-line detection device of the described flue gas pollutant of claim 1, it is characterized in that this method follows these steps to carry out:
A, the real time on-line detection device of flue gas pollutant is placed near the flue gas that needs to detect, makes the focus of the long condenser lens 5 of this device be positioned at the sampling spot place of flue gas;
B, open the real time on-line detection device of flue gas pollutant, at this moment, the pulse producer of this device (1) sends pulse signal for simultaneously pulsed laser (2) and time delays device (3), the external trigger end of pulsed laser (2) receives that a pulse signal just sends a pulse laser, pulse laser focuses on the flue gas behind saturating anti-mirror (4) and long condenser lens (5);
C, after high energy laser beam that flue gas is focused punctures, can form high-temperature plasma, various materials in the flue gas will be excited to high-energy state, before next pulse laser arrives, the various materials of high-energy state will be got back to ground state, in this process, various materials can give off characteristic spectrum separately;
D, characteristic spectrum can reflex to the long condenser lens (5) of the real time on-line detection device of flue gas pollutant, through saturating anti-mirror (4) reflection, enter light receiving device (6), are transmitted to spectrometer (8) through optical fiber (7) again;
E, spectrometer (8) import photoelectric detector (9) into after to the light signal beam split that receives, at this moment, pulse producer (1) excites another pulse signal that this pulse laser sends simultaneously just in time to trigger photoelectric detector (9) collection of opening the door through time delays device (3), and convert the light signal that collects to electric signal, electric signal transfers simulating signal to digital signal through A/D converter (10), and imports computing machine (11);
Which kind of material f, computing machine (11) belong to the flue gas sample Laser-induced Breakdown Spectroscopy that obtains according to pollutant in the following method judgement sample, and the contained concentration of this material;
The determination methods of f1, contaminant species is:
When characteristic spectral line was 279.6 nanometers, the pollutant element was a magnesium;
When characteristic spectral line was 404.6 nanometers, the pollutant element was an iron;
When characteristic spectral line was 324.8 nanometers, the pollutant element was a copper;
When characteristic spectral line was 309.3 nanometers, the pollutant element was an aluminium;
When characteristic spectral line was 405.8 nanometers, the pollutant element was plumbous;
When characteristic spectral line was 520.8 nanometers, the pollutant element was a chromium;
When characteristic spectral line was 253.7 nanometers, the pollutant element was a mercury;
When characteristic spectral line was 228.8 nanometers, the pollutant element was an arsenic;
F2, the contained concentration of all contaminations are calculated by following formula respectively:
lgI＝blgC+lga (1.1)
I is line strength in the formula, and a is a constant, b by the self absorption factor of survey material, C is the concentration of element;
F21, get contained magnesium, iron, copper, aluminium, lead, chromium, mercury, gas that arsenic concentration is known respectively, detect line strength I separately respectively, calculate the constant a of magnesium, iron, copper, aluminium, lead, chromium, mercury, arsenic by formula (1.1) respectively;
F22,279.6 nanometer line strength I that will from flue gas, measure, and the self absorption factor b of magnesium, the constant a of the magnesium that obtains by step f21, substitution step f2 formula (1.1) just can obtain the concentration C of contained magnesium in the gas;
404.6 nanometer line strength I that will from flue gas, measure, and the self absorption factor b of iron, the constant a of the iron that obtains by step f21, substitution step f2 formula (1.1) just can obtain the concentration C of institute's iron content in the flue gas;
324.8 nanometer line strength I that will from flue gas, measure, and the self absorption factor b of copper, the constant a of the copper that obtains by step f21, substitution step f2 formula (1.1) just can obtain the concentration C of institute's cupric in the flue gas;
309.3 nanometer line strength I that will from flue gas, measure, and the self absorption factor b of aluminium, the constant a of the aluminium that obtains by step f21, substitution step f2 formula (1.1) just can obtain the concentration C of contained aluminium in the flue gas;
405.8 nanometer line strength I that will from flue gas, measure, and plumbous self absorption factor b, the constant a of the lead that obtains by step f21, substitution step f2 formula (1.1), just can obtain in the flue gas leaded concentration C;
520.8 nanometer line strength I that will from flue gas, measure, and the self absorption factor b of chromium, the constant a of the chromium that obtains by step f21, substitution step f2 formula (1.1) just can obtain the concentration C of contained chromium in the flue gas;
253.7 nanometer line strength I that will from flue gas, measure, and the self absorption factor b of mercury, the constant a of the mercury that obtains by step f21, substitution step f2 formula (1.1), just can obtain in the flue gas mercurous concentration C;
228.8 nanometer line strength I that will from flue gas, measure, and the self absorption factor b of arsenic, the constant a of the arsenic that obtains by step f21, substitution step f2 formula (1.1) just can obtain the concentration C of contained arsenic in the flue gas.
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