CN101819140B - Continuous monitoring device and method of gaseous elemental mercury concentration - Google Patents
Continuous monitoring device and method of gaseous elemental mercury concentration Download PDFInfo
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- CN101819140B CN101819140B CN2010101714180A CN201010171418A CN101819140B CN 101819140 B CN101819140 B CN 101819140B CN 2010101714180 A CN2010101714180 A CN 2010101714180A CN 201010171418 A CN201010171418 A CN 201010171418A CN 101819140 B CN101819140 B CN 101819140B
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Abstract
The invention provides a continuous monitoring device and a method of gaseous elemental mercury concentration, relating to the gas concentration measurement field and solving the problems of low sensitivity, complex system and overhigh cost of the existing gaseous elemental mercury monitoring technology. To the monitoring device in the invention, a mercury element lamp is arranged in a magnetic field of a magnet, the output light is subjected to transmission to obtain parallel light via a collimation lens, the parallel light enters into a spectroscope via a sample pool, the transmission light enters into a first convex lens via a reference pool and is focused on a first detector, the reflecting light enters into a second convex lens and is focused on a second detector, and the first detector and the second detector are connected with a data collection analyzer. The method is implemented as follows: 1) determining a constant A corresponding to the light intensity contrast ratio M when being zero; 2) drawing a correspondence curve of the light intensity contrast ratio M and gaseous elemental mercury medium concentration; and 3) measuring the light intensity contrast ratio M of the gaseous elemental mercury medium to be measured, and comparing with the correspondence curve to obtain the concentration of the gaseous elemental mercury medium. The invention is used for monitoring the gaseous mercury concentration.
Description
Technical field
The present invention relates to the field of measurement of gas concentration, what be specifically related to is a kind of apparatus and method that are used for the continuous monitoring gaseous elemental mercury concentration.
Background technology
Mercury in the combustion product gases has three kinds of existence forms: gaseous elemental mercury, gaseous state divalence oxidation state mercury and particle mercury.Wherein gaseous mercury is a principal mode.The content of total mercury is that the mode through thermocatalysis or chemical conversion is converted into gaseous elemental mercury with the mercury of other form and records.In the mercury emissions continuous monitor system of existing application at present, the most normal adopted gaseous elemental mercury measuring technique is based on cold steam atomic absorption spectrum (CVAAS) and cold steam atomic fluorescence spectrophotometry (CVAFS) technology that spectroscopy detects principle.The former can implement directly measurement and as the latter, need need not carrier gas the gaseous elemental mercury concentration in the flue gas, thereby is adopted by the overwhelming majority's mercury emissions continuous monitor system.In the system of major part based on CVAAS; Mercury in the flue gas stream needs to improve measurement sensitivity and remove interference gas through preenrichment and two steps of desorption before introducing the optical detection systematic analysis; These two steps greatly reduce the real-time of mercury emissions monitoring, make the mercury monitoring can only be in semicontinuous state.
The technology that can accomplish the gaseous elemental mercury continuous monitoring at present mainly contains two kinds: ultraviolet difference absorption spectrum (UV-DOAS) and Zeeman AAS (ZAAS) technology.These two kinds of technology all are based on the absorption spectroscopy principle, and to testing amount in fact, response speed can reach second-time, accomplishes real-time measurement truly at 253.7nm place that mercury has the absorption maximum cross section.What the former adopted is to cover the broadband emission light source of ultraviolet to visible waveband, but because mercury is monoatomic molecules, and its line-width is very narrow, absorbs ratio even adopt optical filter also to be difficult to obtain big light intensity, thereby be difficult to obtain higher measurement sensitivity.The latter is a special case among the CVAAS; The Mercury element lamp that adopts narrow emission is as light source; Get rid of preenrichment and the desorption of disturbing and need not to carry out mercury through using Zeeman background correction technology; But its requirement to the analyzing system is very high, has increased complicacy and the cost of system and can not get using widely.
Summary of the invention
The present invention is that the sensitivity of existing gaseous elemental mercury monitoring technology is low in order to solve, system complex and the too high problem of cost, thereby a kind of continuous monitoring device and method of gaseous elemental mercury concentration are provided.
The continuous monitoring device of gaseous elemental mercury concentration; It is made up of Mercury element lamp, magnet, collimation lens, sample cell, spectroscope, reference cell, first convex lens, first detector, second convex lens, second detector, data collection and analysis device, and Mercury element lamp places the magnetic field of magnet, and is arranged on the along of collimation lens; The test surface of first detector overlaps with the focal plane of first convex lens; The test surface of second detector overlaps with the focal plane of second convex lens, and the output light of Mercury element lamp is incident to collimation lens, obtains directional light through the collimation lens transmission; Said directional light is incident to spectroscope through behind the sample cell; Said directional light is divided into reflected light and transmitted light through spectroscope, and wherein transmitted light is incident to first convex lens through behind the reference cell, again through first convex lens focus to the first detector; Reflected light is incident to second convex lens; Through second convex lens focus to the second detector, the output terminal of the output terminal of said first detector and second detector is connected two incoming ends of data collection and analysis device respectively again, and the medium in the reference cell is the elemental mercury body of saturation concentration.
The continuous monitoring method of gaseous elemental mercury concentration, detailed process is following:
When step 1, sample cell were full of gaseous elemental mercury medium to be measured, the data collection and analysis device was measured the transmitted light intensity that first detector is surveyed
I R Reflective light intensity with the detection of second detector
I S
Wherein,
AIt is light intensity contrast ratio when only containing air in the sample cell
MIt is zero pairing constant;
The present invention utilizes Zeeman associated light spectral technology to realize the continuous effective monitoring to elemental mercury concentration, has realized the selectivity of gaseous elemental mercury is surveyed with the spectral information of reference gas itself, has got rid of the interference that gases such as sulphuric dioxide and nitrogen dioxide bring.System forms simple, need not to use the spectrometer isochrome to be casually arranged with the analyzing equipment that is equipped with complicated, and cost is lower.The LDL that the present invention can reach is lower than 1 μ g/m
3, fully satisfied the requirement of mercury content monitoring in the industrial gas emission.Be applicable to the highly sensitive gaseous elemental mercury concentration monitoring field that requires.
Description of drawings
Fig. 1 is the structural representation of the continuous monitoring device of gaseous elemental mercury concentration.Fig. 2 is the process flow diagram of the continuous monitoring method of gaseous elemental mercury concentration.Fig. 3 is the corresponding relation figure of light intensity contrast ratio and gas concentration to be measured in the embodiment ten.
Embodiment
Embodiment one,In conjunction with Fig. 1 this embodiment is described; The continuous monitoring device of gaseous elemental mercury concentration; It is made up of Mercury element lamp 1, magnet 2, collimation lens 3, sample cell 4, spectroscope 5, reference cell 6, first convex lens 7, first detector 8, second convex lens 9, second detector 10, data collection and analysis device 11, and Mercury element lamp 1 places the magnetic field of magnet 2, and is arranged on the along of collimation lens 3; The test surface of first detector 8 overlaps with the focal plane of first convex lens 7; The test surface of second detector 10 overlaps with the focal plane of second convex lens 9, and the output light of Mercury element lamp 1 is incident to collimation lens 3, obtains directional light through collimation lens 3 transmissions; Said directional light is incident to spectroscope 5 through behind the sample cell 4; Said directional light is divided into reflected light and transmitted light through spectroscope 5, and wherein transmitted light is incident to first convex lens 7 through behind the reference cell 6, focuses to first detector 8 through first convex lens 7 again; Reflected light is incident to second convex lens 9; Focus to second detector 10 through second convex lens 9 again, the output terminal of the output terminal of said first detector 8 and second detector 10 is connected two incoming ends of data collection and analysis device 11 respectively, and the medium in the reference cell 6 is the elemental mercury body of saturation concentration.
Medium in the sample cell 4 is a gaseous elemental mercury medium to be measured.The elemental mercury body of saturated concentration can make that to be in wavelength be that near the 253.7nm light is farthest absorbed in the reference cell 6.
Principle of work: Mercury element lamp 1 sends ultraviolet light; The spectral line of emission splitting at its 253.7nm place is a series of Zeeman components with different wave length under the action of a magnetic field that magnet 2 produces; Ultraviolet light after the wavelength splitting becomes directional light behind collimation lens 3; Be divided into transmitted light and reflected light through sample cell 4 backs that gas to be measured is housed by spectroscope 5; Transmitted light is through after being equipped with the reference cell 6 of saturation concentration gaseous elemental mercury, and near the Zeeman component that is in the 253.7nm is farthest absorbed, remaining Zeeman component as a reference light again after first convex lens 7 focus on by 8 receptions of first detector; Reflected light is a sample light; Reflected light is directly received by second detector 10 after second convex lens 9 focus on, and the signal of the generation of first detector 8 and second detector 10 is input to and carries out mould/number conversion and data analysis, acquisition of transmission light and catoptrical intensity signal in the data collection and analysis device 11.When not having gaseous elemental mercury in the sample cell 4; The light intensity contrast ratio of two-way light is zero; When gaseous elemental mercury occurring in the sample cell 4, the light intensity contrast ratio of two-way light increases along with the increase of mercury content, and light intensity contrast ratio and mercury content are relation one to one.
Reflected light path behind the spectroscope 5 and transmitted light path can be exchanged; Can be incident to first convex lens 7 through behind the reference cell 6 by reflected light; Focus to first detector 8 through first convex lens 7, transmitted light is incident to second convex lens 9, focuses to second detector 10 through second convex lens 9.
Embodiment two,In conjunction with Fig. 1 this embodiment is described, this embodiment is that with the difference of embodiment one spectroscope 5 is the beam splitter of half reflection and half transmission.
Embodiment three,In conjunction with Fig. 1 this embodiment is described, this embodiment is that with the difference of embodiment one every meter saturation concentration of elemental mercury body is 0.2 ~ 20mg/m in the reference cell 6
3
Embodiment four,In conjunction with Fig. 1 this embodiment is described, this embodiment is that with the difference of embodiment one magnetic induction density that magnet 2 is produced is 1 ~ 3T.
Embodiment five,In conjunction with Fig. 2 this embodiment is described, the continuous monitoring method of gaseous elemental mercury concentration, detailed process is following:
Step 1, sample cell 4 is full of gaseous elemental mercury medium to be measured, data collection and analysis device 11 is measured the transmitted light intensity that first detector 8 is surveyed
I R Reflective light intensity with 10 detections of second detector
I S
Wherein,
AIt is light intensity contrast ratio when only containing air in the sample cell 4
MIt is zero pairing constant;
Embodiment six,This embodiment is that embodiment five further specified light intensity contrast ratio when only containing air in the sample cell 4 in the step 2
MIt is zero pairing constant
AObtain through following method:
When only containing air in step 2 M, the sample cell 4, data collection and analysis device 11 is measured the transmitted light intensity that first detector 8 is surveyed
I R0 Reflective light intensity with 10 detections of second detector
I S0
Step 2 N, try to achieve described transmitted light of step 2 M and catoptrical light intensity contrast ratio
MIt is zero pairing constant
A
Wherein, light intensity contrast ratio
MTry to achieve through following formula:
Embodiment seven,This embodiment is that embodiment five further specified the described light intensity contrast ratio of step 3
MObtain through following method with the corresponding relation curve of gaseous elemental mercury concentration of medium:
Step 3 M, sample cell 4 is full of the gaseous elemental mercury medium of concentration known, data collection and analysis device 11 is measured the transmitted light intensity that first detector 8 is surveyed
I R Reflective light intensity with 10 detections of second detector
I S
Step 3 N, the following described transmitted light of formula calculation procedure three M of basis and catoptrical light intensity contrast ratio
M
Wherein,
ABe that contrast is not zero pairing constant when not containing gas to be measured in the sample cell 4;
Step 3 P, repeated execution of steps three N are up to the light intensity contrast ratio that obtains n group gaseous elemental mercury concentration of medium
M, and be transverse axis with the gaseous elemental mercury concentration of medium, light intensity contrast ratio
MFor the longitudinal axis is described light intensity contrast ratio
MCorresponding relation curve with the gaseous elemental mercury concentration of medium.
Embodiment eight,This embodiment is that embodiment five further specified the light intensity contrast ratio in the step 4
MWith the corresponding relation curve of gaseous elemental mercury concentration of medium be straight line.
Embodiment nine,This embodiment is that embodiment five further specified light intensity contrast ratio during the measurement n in the step 4 gaseous elemental mercury concentration of medium
MFor measuring 5-12 value.
Embodiment ten,In conjunction with Fig. 3 this embodiment is described, this embodiment adopts embodiment one described device and embodiment five described methods to measure the instantiation of gaseous elemental mercury concentration to be measured, selected following parameter:
The magnetic field intensity that magnet 2 is produced is 1T, and every meter saturation concentration of the elemental mercury body in the reference cell 6 is 1mg/m
3
Calculate two light intensity contrast ratio through formula, confirm the gaseous elemental mercury concentration of sample cell according to the different light intensity contrast that obtains, the result is as shown in Figure 3, and transverse axis is the gaseous elemental mercury concentration of medium; The longitudinal axis is a light intensity contrast ratio.
Claims (9)
1. the continuous monitoring device of gaseous elemental mercury concentration; It is characterized in that it is made up of Mercury element lamp (1), magnet (2), collimation lens (3), sample cell (4), spectroscope (5), reference cell (6), first convex lens (7), first detector (8), second convex lens (9), second detector (10), data collection and analysis device (11); Mercury element lamp (1) places the magnetic field of magnet (2); And be arranged on the along of collimation lens (3), the test surface of first detector (8) overlaps with the focal plane of first convex lens (7), and the test surface of second detector (10) overlaps with the focal plane of second convex lens (9); The output light of Mercury element lamp (1) is incident to collimation lens (3); Obtain directional light through collimation lens (3) transmission, be incident to spectroscope (5) behind the said directional light process sample cell (4), said directional light is divided into reflected light and transmitted light through spectroscope (5); Wherein be incident to first convex lens (7) behind the transmitted light process reference cell (6); Focus to first detector (8) through first convex lens (7) again, reflected light is incident to second convex lens (9), focuses to second detector (10) through second convex lens (9) again; The output terminal of the output terminal of said first detector (8) and second detector (10) is connected two incoming ends of data collection and analysis device (11) respectively, and the medium in the reference cell (6) is the elemental mercury body of saturation concentration.
2. the continuous monitoring device of gaseous elemental mercury concentration according to claim 1 is characterized in that spectroscope (5) is the beam splitter of half reflection and half transmission.
3. the continuous monitoring device of gaseous elemental mercury concentration according to claim 1 is characterized in that every cubic metre of saturation concentration of elemental mercury body in the reference cell (6) is 0.2～20mg/m
3
4. the continuous monitoring device of gaseous elemental mercury concentration according to claim 1 is characterized in that the magnetic induction density that magnet (2) is produced is 1～3T.
5. utilize the continuous monitoring method of the continuous monitoring device of the described gaseous elemental mercury concentration of claim 1, it is characterized in that detailed process is following:
Step 1, sample cell (4) is full of gaseous elemental mercury medium to be measured, data collection and analysis device (11) is measured the transmitted light intensity I that first detector (8) is surveyed
RReflective light intensity I with second detector (10) detection
S
Step 2, the following formula calculation procedure one described transmitted light of basis and catoptrical light intensity contrast ratio M;
Wherein, A is that light intensity contrast ratio M is zero pairing constant when only containing air in the sample cell (4);
The corresponding relation curve contrast of step 3, the light intensity contrast ratio M that step 2 is obtained and light intensity contrast ratio M and gaseous elemental mercury concentration of medium obtains the concentration of gaseous elemental mercury medium to be measured.
6. the continuous monitoring method of gaseous elemental mercury concentration according to claim 5, light intensity contrast ratio M is that zero pairing constant A obtains through following method when it is characterized in that only containing air in the sample cell in the step 2 (4):
When only containing air in step 2 M, the sample cell (4), data collection and analysis device (11) is measured the transmitted light intensity I that first detector (8) is surveyed
R0Reflective light intensity I with second detector (10) detection
S0
Step 2 N, to try to achieve the described transmitted light of step 2 M and catoptrical light intensity contrast ratio M be zero pairing constant A; Wherein, light intensity contrast ratio M is tried to achieve through following formula:
7. the continuous monitoring method of gaseous elemental mercury concentration according to claim 5 is characterized in that the corresponding relation curve of described light intensity contrast ratio M of step 3 and gaseous elemental mercury concentration of medium obtains through following method:
Step 3 M, sample cell (4) is full of the gaseous elemental mercury medium of concentration known, data collection and analysis device (11) is measured the transmitted light intensity I that first detector (8) is surveyed
RReflective light intensity I with second detector (10) detection
S
Step 3 N, the following described transmitted light of formula calculation procedure three M of basis and catoptrical light intensity contrast ratio M;
Wherein, A is that light intensity contrast ratio M is not zero pairing constant when not containing gas to be measured in the sample cell (4);
Step 3 P, repeat execution in step three M～step 3 N successively; Up to the light intensity contrast ratio M that obtains n group gaseous elemental mercury concentration of medium; And be transverse axis with the gaseous elemental mercury concentration of medium, light intensity contrast ratio M is the corresponding relation curve that the longitudinal axis is described light intensity contrast ratio M and gaseous elemental mercury concentration of medium.
8. according to the continuous monitoring method of claim 5 or 7 described gaseous elemental mercury concentrations, the corresponding relation curve that it is characterized in that light intensity contrast ratio M and gaseous elemental mercury concentration of medium is a straight line.
9. the continuous monitoring method of gaseous elemental mercury concentration according to claim 7 is characterized in that the light intensity contrast ratio M of the acquisition n group gaseous elemental mercury concentration of medium among the step 3 P is organized light intensity contrast ratio M numerical value for obtaining 5-12.
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| EP2482057B1 (en) * | 2011-01-27 | 2013-03-20 | Sick Ag | Gas analyser for measuring the mercury content of a gas and calibration method |
| CN102495010B (en) * | 2011-11-18 | 2013-04-24 | 南京国电环保设备有限公司 | High sensitivity optical system of DOAS analyzer |
| CN102564986B (en) * | 2011-12-30 | 2014-08-27 | 北京雪迪龙科技股份有限公司 | Smoke mercury emission monitoring system and method |
| CN102590097B (en) * | 2012-03-05 | 2013-09-25 | 哈尔滨工业大学 | Mercury vapor continuous monitoring method based on diode laser |
| CN102698657B (en) * | 2012-06-19 | 2015-04-01 | 北京雪迪龙科技股份有限公司 | Catalytic reaction device of mercury |
| CN103163100B (en) * | 2013-03-01 | 2015-06-03 | 华北电力大学（保定） | Gaseous element mercury detection method |
| CN103528970A (en) * | 2013-10-22 | 2014-01-22 | 长春长光思博光谱技术有限公司 | Light path system in portable near-infrared analyzer |
| CN105987877B (en) * | 2015-02-11 | 2019-08-13 | 苏州瑞蓝环保科技有限公司 | Trace Hg concentration detection method and device based on optical fiber-coupled laser and frequency technology |
| CN105372191A (en) * | 2015-10-22 | 2016-03-02 | 燕山大学 | Gaseous elemental mercury spectrum monitoring method and monitoring device thereof |
| CN106370621A (en) * | 2016-08-16 | 2017-02-01 | 苏州瑞蓝环保科技有限公司 | Frequency-doubled semiconductor laser-based detection apparatus and method for concentration of gaseous elemental mercury |
| CN107884372A (en) * | 2017-09-30 | 2018-04-06 | 维科托（北京）科技有限公司 | For the incidence system of atomic fluorescence detection device and the mounting bracket of excitation source |
| CN113029956A (en) * | 2021-03-31 | 2021-06-25 | 中国科学院长春光学精密机械与物理研究所 | Gas concentration detection device and method |
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| CN101498665A (en) * | 2009-02-27 | 2009-08-05 | 哈尔滨工业大学 | Sulphur dioxide gas concentration detection apparatus based on associated spectrum technology |
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| CN101498665A (en) * | 2009-02-27 | 2009-08-05 | 哈尔滨工业大学 | Sulphur dioxide gas concentration detection apparatus based on associated spectrum technology |
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