N2O analysis device and analysis method
10156517 ยท 2018-12-18
Assignee
Inventors
- Osamu Tadanaga (Tokyo, JP)
- Akio Tokura (Tokyo, JP)
- Kenji Muta (Tokyo, JP)
- Shuuji FUJII (Tokyo, JP)
- Yoichiro Tsumura (Tokyo, JP)
- Tatsuyuki Nishimiya (Tokyo, JP)
Cpc classification
International classification
Abstract
This N.sub.2O analysis device is provided with: a light source (11) which radiates laser light onto an exhaust gas (5) containing N.sub.2O, H.sub.2O and CO.sub.2; a light receiver (13) which receives the laser light that has been radiated onto the exhaust gas (5); a light source control unit (14a) of a control device (14), which controls the wavelength of the laser light radiated by the light source (11) to between 3.84 m and 4.00 m; and a signal analyzing unit (14b) of the control device (14), which calculates the N.sub.2O concentration by means of infrared spectroscopy, using the laser light received by the light receiver (13) and the laser light controlled by the light source control unit (14a) of the control device (14).
Claims
1. An N.sub.2O analysis device comprising: light emission means for emitting laser light to flue gas containing N.sub.2O, H.sub.2O, and CO.sub.2, the flue gas being at normal pressures and being not treated with any one of a dust removal and a dehumidification and a pressure reduction; light reception means for receiving the laser light emitted to the flue gas; wavelength control means for performing control such that a wavelength of the laser light emitted by the light emission means is in a 3.84 to 4.00 m band; and N.sub.2O concentration calculation means for calculating a concentration of N.sub.2O by means of infrared spectroscopy, using the laser light received by the light reception means and the laser light controlled by the wavelength control means.
2. The N.sub.2O analysis device according to claim 1, wherein the wavelength control means performs control such that the wavelength of the laser light is 3.9034 to 3.9060 m, 3.9090 to 3.9116 m, or 3.9122 to 3.9148 m.
3. The N.sub.2O analysis device according to claim 1, wherein the wavelength control means performs control such that the wavelength of the laser light is 3.9047 m, 3.9103 m, or 3.9135 m.
4. The N.sub.2O analysis device according to claim 1, wherein the light emission means includes a nonlinear optical crystal, generates, by means of difference frequency generation using inputs of laser light with a wavelength of .sub.1 and laser light with a wavelength of .sub.2, laser light with a wavelength of .sub.3 satisfying 1/.sub.3=1/.sub.11/.sub.2, and outputs the laser light with the wavelength of .sub.3.
5. The N.sub.2O analysis device according to claim 1, further comprising temperature measurement means for measuring a temperature of the flue gas, wherein the N.sub.2O concentration calculation means calculates the concentration of N.sub.2O by means of the infrared spectroscopy, using also the temperature of the flue gas measured by the temperature measurement means.
6. The N.sub.2O analysis device according to claim 1, further comprising sampling means for sampling the flue gas, wherein the light emission means emits the laser light to the flue gas sampled by the sampling means.
7. The N.sub.2O analysis device according to claim 6, further comprising heating means for heating the flue gas sampled by the sampling means.
8. An N.sub.2O analysis method comprising: emitting, by light emission means, laser light with a wavelength of 3.84 to 4.00 m to flue gas containing N.sub.2O, H.sub.2O, and CO.sub.2, the flue gas being at normal pressures and being not treated with any one of a dust removal and a dehumidification and a pressure reduction; receiving the laser light emitted to the flue gas; and calculating a concentration of N.sub.2O by means of infrared spectroscopy, using the received laser light and the laser light which is controlled to be 3.84 to 4.00 m.
9. The N.sub.2O analysis method according to claim 8, wherein the wavelength of the laser light emitted by the light emission means is controlled to be 3.9034 to 3.9060 m, 3.9090 to 3.9116 m, or 3.9122 to 3.9148 m.
10. The N.sub.2O analysis method according to claim 8, wherein the wavelength of the laser light emitted by the light emission means is controlled to be 3.9047 m, 3.9103 m, 3.9135 m.
11. The N.sub.2O analysis method according to claim 8, wherein equipment including a nonlinear optical crystal is used for the light emission means, the equipment generating, by means of difference frequency generation using inputs of laser light with a wavelength of .sub.1 and laser light with a wavelength of .sub.2, laser light with a wavelength of .sub.3 satisfying 1/.sub.3=1/.sub.11/.sub.2, and outputting the laser light with the wavelength of .sub.3.
12. The N.sub.2O analysis method according to claim 8, further comprising: measuring a temperature of the flue gas; and calculating the concentration of N.sub.2O by means of the infrared spectroscopy, using also the measured temperature of the flue gas.
13. The N.sub.2O analysis method according to claim 8, wherein the flue gas to which the laser light is emitted is sampled.
14. The N.sub.2O analysis method according to claim 13, wherein the sampled flue gas is heated.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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MODE FOR CARRYING OUT THE INVENTION
(14) Descriptions will be provided for embodiments of an N.sub.2O concentration analysis device and analysis method according to the present invention based on the drawings. However, the present invention is not limited only to the following embodiments described based on the drawings.
(15) [First Embodiment]
(16) Descriptions will be provided using
(17) As illustrated in
(18) The sludge incinerator 100A includes an N.sub.2O concentration analysis device 10A for analyzing the concentration of N.sub.2O in the flue gas 5 passing through the flue 105.
(19) As illustrated in
(20) Here, descriptions will be provided for an example of the light source 11 and the light source control unit 14a, using
(21) As illustrated in
(22) In addition, to utilize the nonlinear constant efficiently, the phases of the wavelengths .sub.1, .sub.2, and .sub.3 of the incident and outgoing laser lights need to be matched, and the angle matching method or the quasi phase matching method are used for it. For example, as shown in Non-Patent Document 1, LN is used as a nonlinear optical crystal, a periodic polarization reversal structure is adopted to achieve the quasi phase matching, and a waveguiding structure is further adopted to generate a mid-infrared light in a 3 m band with high efficiency. Although in Non-Patent Document 1, light of a 3 m band is generated, for example, it is possible to generate a short-wavelength mid-infrared light with a desired wavelength .sub.3 in a 2 to 5 m range, by appropriately selecting the wavelength .sub.1 and the wavelength .sub.2, which are in the near-infrared range.
(23) In this case, the stability/robustness of the device is guaranteed by using NIR-LD light sources, which have been used for many applications for communication or the like, for the original light sources. In addition, in a QCL that oscillates and generates a long-wavelength mid-infrared light, since the wavelength line width of the generated laser light is wide, the measurement tends to be affected by coexisting gases. On the other hand, since in this embodiment, the NIR-LDs, the wavelength line widths of which are extremely narrow, are used as origins, the wavelength line width of the generated short-wavelength mid-infrared laser light is as narrow as the NIR-LDs, and this embodiment has a characteristic of being hardly affected by coexisting gases.
(24) Note that although the incident lights from the two NIR-LDs 11a and 11b enter the nonlinear optical crystal 11e through the spatial optical system in
(25) The light source 11 is controlled by the light source control unit 14a , which performs temperature control for the two NIR-LDs 11a and 11b and the nonlinear optical crystal 11e, and electric current control for the two NIR-LDs 11a and 11b. Appropriate setting of the temperature allows for precise control of the oscillation wavelengths at the NIR-LDs 11a and 11b, and precise control of combinations of wavelengths that can be efficiently generated by the difference frequency generation, at the nonlinear optical crystal 11e.
(26) Further, in this embodiment, utilizing short-wavelength mid-infrared (around 4 m) for the measurement wavelength allows sapphire window plates having high strength/corrosion resistance to be utilized for the windows 12a and 12b. On the other hand, since, in a QCL utilizing long-wavelength mid-infrared (8 m), only CaF.sub.2, MgF.sub.2, or the like having a high deliquescent property can be used for window material, it is impossible to directly measure combustion flue gas containing a large amount of H.sub.2O.
(27) Meanwhile, strong basic absorption of N.sub.2O exists at a wavelength of 4.50 m (absorption intensity 110.sup.18 cm/molecule), and typically, N.sub.2O is observed as a target in a wavelength region where such strong absorption exists. However, in the application described above, for example, where gases such as 50% of water and 12% of carbon dioxide coexist, for example, even though a strong absorption of N.sub.2O exists, it is impossible to measure the absorption line accurately because the absorption of N.sub.2O is small compared to the coexisting gases and the coexisting gases obstruct (interfere) the measurement.
(28) After diligent studies in this respect, it was found that absorption of N.sub.2O can be observed at around 3.9 m while avoiding influence of the coexisting gases, even though the absorption intensity is 2.510.sup.20 cm/molecule, which is a small absorbance compared to the basic absorption. The situation will be described using
(29)
(30) Meanwhile,
(31) From this result, the light source 11 is a mid-infrared semiconductor laser capable of emitting laser light with, for example, a vibrational-rotational absorption wavelength of N.sub.2O in a wavelength band of 3.84 to 4.00 m, preferably a wavelength region A1 (wavelengths of 3.9034 to 3.9060 m), a wavelength region A2 (wavelengths of 3.9090 to 3.9116 m), or a wavelength region A3 (wavelengths of 3.9122 to 3.9148 m), or more preferably a wavelength of 3.9047 m, a wavelength of 3.9103 m, or a wavelength of 3.9135 m.
(32) The windows 12a and 12b are arranged to face each other at the flue 105 and can be passed through by the laser light. It is preferable that the windows 12a and 12b are made of, for example, sapphire. This is because that sapphire does not have a deliquescent property and eliminates the need of maintenance such as replacing the windows.
(33) The light receiver 13 receives the laser light emitted by the light source 11 and having passed through the window 12a, the flue 105, and the window 12b. A light intensity signal (light reception signal) obtained by the light receiver 13 is outputted to the signal analyzing unit 14b to be described in detail later of the control device 14.
(34) The temperature measurement instrument 15a is disposed so as to measure the temperature at generally the same position as the laser measurement position in the flue 105, and capable of measuring the temperature of the flue gas 5 flowing inside the flue 105. The temperature measurement instrument 15a measures the temperature of the flue gas 5, and the temperature signal generated by the signal generator 15b is outputted to the signal analyzing unit 14b.
(35) The light source control unit 14a transmits a control signal to the light source 11 to control the wavelength of the laser light emitted by the light source 11, and transmits the reference signal to the signal analyzing unit 14b. The reference signal is a signal having the wavelength information of the laser light emitted by the light source 11 based on the control signal.
(36) The signal analyzing unit 14b calculates the concentration of N.sub.2O and outputs a signal corresponding to this concentration of N.sub.2O. The signal analyzing unit 14b calculates the concentration of N.sub.2O by means of infrared spectroscopy based on the reference signal transmitted from the light source control unit 14a, the light reception signal obtained at the light receiver 13, and the temperature signal transmitted from the temperature measurement instrument 15a via the signal generator 15b.
(37) The measurement time of the N.sub.2O concentration analysis device 10A described above and the measurement result of the concentration of N.sub.2O will be described using
(38) As illustrated in
(39) Thus, the N.sub.2O concentration analysis device 10A according to this embodiment, having the equipment described above, can directly measure the concentration of N.sub.2O in the flue gas 5 without pretreatment of removing dust and coexisting gases other than N.sub.2O in the flue gas 5, which makes it possible to measure the concentration of N.sub.2O in the flue gas 5 promptly and accurately.
(40) In addition, changing the attachment positions of the windows 12a and 12b allows for the measurement at an upstream portion such as the inside of the freeboard 103 where the concentration of particles is high, or a position directly above the fluidized bed where flames cross and the concentration of N.sub.2O is high. Moreover, in the measurement at a downstream portion, the concentration of N.sub.2O measured by the N.sub.2O concentration analysis device 10A according to this embodiment shows an average value on the laser light path. For this reason, although conventional sampling measurement requires traverse measurement or the like to find a representative value when the concentration is not constant inside the flue, the N.sub.2O concentration analysis method in accordance with the N.sub.2O concentration analysis device 10A according to this embodiment makes it possible to always measure the average concentration of N.sub.2O in the flue 105.
(41) [Second Embodiment]
(42) Descriptions will be provided for an application of the measurement of N.sub.2O in a sludge incinerator in accordance with a N.sub.2O concentration analysis device according to a second embodiment of the present invention using
(43) In this embodiment, a sampling device is added to the N.sub.2O concentration analysis device according to the first embodiment described above, and except for it, this embodiment is generally the same as the first embodiment.
(44) As illustrated in
(45) The N.sub.2O concentration analysis device 10B includes the same equipment as in the N.sub.2O concentration analysis device 10A according to the above first embodiment, and further includes a sampling device 16. The sampling device 16 includes a sampling pipe 16a, a delivery pipe 16b, a sampling cell 16c, a discharge pipe 16d, and a blower 16e.
(46) The sampling pipe 16a is disposed with its distal end side protruded into the flue 105, and samples the flue gas 5 flowing through the flue 105.
(47) The proximal end side of the delivery pipe 16b is connected to the proximal end side of the sampling pipe 16a, and the distal end side of the delivery pipe 16b is connected to the proximal end side (the end side connected to the light receiver 13) of the sampling cell 16c.
(48) The distal end of the sampling cell 16c is coupled to the light source 11 through a window 12c, and the proximal end of the sampling cell 16c is coupled to the light receiver 13 through a window 12d. Note that it is preferable that the windows 12c and 12d be made of, for example, sapphire in the same way as in the windows 12a and 12b.
(49) The proximal end of the discharge pipe 16d is connected to the distal end side (the end side connected to the light source 11) of the sampling cell 16c, and the distal end of the discharge pipe 16d is connected to the flue 105 downstream of the sampling pipe 16a in the flowing direction of the flue gas. The blower 16e is disposed in the middle of the discharge pipe 16d. With the operation of this blower 16e, a part of the flue gas 5 flowing through the flue 105 will be introduced through the sampling pipe 16a and the delivery pipe 16b into the sampling cell 16c, and the flue gas 5 having flowed through the sampling cell 16c will be returned through the discharge pipe 16d to the flue 105.
(50) The sampling device 16 further includes a heater 16f that heats the sampling cell 16c to keep the temperature of the flue gas 5 inside the sampling cell 16c at a desired temperature. This allows the inside of the sampling cell 16c to be kept at a predetermined constant temperature, and makes it possible to measure the concentration of N.sub.2O in the flue gas 5 without measuring the temperature.
(51) Here, the main operation of the above N.sub.2O concentration analysis device 10B will be described. Note that the main operation of the sludge incinerator 100B is the same as that of the above sludge incinerator 100A, and descriptions thereof are omitted.
(52) First, the heater 16f is activated to heat the sampling cell 16c. This keeps the inside of the sampling cell 16c at a constant temperature, making it possible to keep a temperature correction constant when directly measuring the concentration of N.sub.2O in the flue gas 5 flowing through the flue 105, and thereby eliminating the need for a temperature measurement instrument and its signal generator.
(53) Then, the blower 16e is activated. This will cause a part of the flue gas 5 flowing through the flue 105 to flow into the sampling cell 16c through the sampling pipe 16a and the delivery pipe 16b.
(54) Next, the light source 11 emits laser light with a wavelength of a predetermined range (for example, 3.84 to 4.00 m) based on a control signal from the light source control unit 14a of the control device 14. The laser light is received by the light receiver 13 through the window 12c, the flue gas 5 inside the sampling cell 16c, and the window 12d. The light receiver 13 transmits the light reception signal corresponding to the received laser light to the signal analyzing unit 14b of the control device 14. The signal analyzing unit 14b also receives the reference signal from the light source control unit 14a.
(55) The signal analyzing unit 14b calculates the concentration of N.sub.2O in the flue gas by means of infrared spectroscopy based on the light reception signal and the reference signal.
(56) Thus, even in the case where the flue gas 5 is sampled, the N.sub.2O concentration analysis device 10B according to this embodiment including the above equipment makes it possible to directly measure the concentration of N.sub.2O in the flue gas without removing dust and coexisting gasses other than N.sub.2O in the flue gas 5, which makes it possible to measure the concentration of N.sub.2O in the flue gas 5 promptly and accurately.
(57) Moreover, the N.sub.2O concentration analysis device 10B allows for the installment without a large-scale modification work such as attaching measurement windows to a furnace.
(58) [Other Embodiments]
(59) In the above, descriptions have been provided for the case where the concentration of N.sub.2O in the flue gas containing 100 ppm of N.sub.2O, 50% of H.sub.2O, and 12% of CO.sub.2is measured. However, the concentration of N.sub.2O in the flue gas is not limited to 100 ppm. When the concentration of N.sub.2O is higher than 100 ppm, the absorbance of laser is high, and accordingly, it is possible to obtain the same operation effect as described above.
(60) In addition, although in the above, descriptions have been provided for the case where the concentration of N.sub.2O in the flue gas containing 100 ppm of N.sub.2O, 50% of H.sub.2O, and 12% of CO.sub.2 is measured, the concentration of H.sub.2O in the flue gas is not limited to 50%. When the concentration of H.sub.2O is lower than 50%, the absorbance of laser is lower than in the case where the concentration of H.sub.2O is 50%, and the influence on the measurement of the concentration of N.sub.2O is small. Accordingly, it is possible to obtain the same operation effect as described above.
(61) Moreover, although in the above, descriptions have been provided for the case where the concentration of N.sub.2O in the flue gas containing 100 ppm of N.sub.2O, 50% of H.sub.2O, and 12% of CO.sub.2 is measured, the concentration of CO.sub.2 in the flue gas is not limited to 12%. When the concentration of CO.sub.2 is lower than 12%, the absorbance of laser is lower than in the case where the concentration of CO.sub.2 is 12%, and the influence on the measurement of the concentration of N.sub.2O is small. Accordingly, it is possible to obtain the same operation effect as described above.
INDUSTRIAL APPLICABILITY
(62) Since the N.sub.2O analysis device and analysis method according to the present invention can measure the concentration of N.sub.2O in the flue gas accurately and promptly without pretreatment, it can be utilized extremely usefully in industrial applications.
REFERENCE SIGNS LIST
(63) 1 sludge (fuel) 2 combustion air 3 auxiliary fuel 4 secondary air 5 flue gas 10A, 10B N.sub.2O concentration analysis device 11 light source (light emission means) 12a, 12b window 13 light receiver (light reception means) 14 control device 14a light source control unit (wavelength control means) 14b signal analyzing unit (N.sub.2O concentration calculation means) 15a temperature measurement instrument (temperature measurement means) 100A, 100B sludge incinerator 101 incinerator main body 102 fluidized bed 103 freeboard 105 flue