WO2003069316A1 - Method for the rapid spectroscopic analysis of the concentration, temperature, and pressure of gaseous water - Google Patents
Method for the rapid spectroscopic analysis of the concentration, temperature, and pressure of gaseous water Download PDFInfo
- Publication number
- WO2003069316A1 WO2003069316A1 PCT/AT2003/000040 AT0300040W WO03069316A1 WO 2003069316 A1 WO2003069316 A1 WO 2003069316A1 AT 0300040 W AT0300040 W AT 0300040W WO 03069316 A1 WO03069316 A1 WO 03069316A1
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- WO
- WIPO (PCT)
- Prior art keywords
- spectroscopic measurement
- carried out
- gas
- temperature
- pressure
- Prior art date
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/39—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using tunable lasers
Definitions
- the exact water concentration in a hot, multi-phase measuring volume is often required for process optimization and control.
- Spectroscopic methods are successfully used for the contactless, selective and sensitive concentration measurement of certain species.
- Absorption spectroscopy using a tunable diode laser is a successfully used technique. Because of the tuning of the wavelength over a complete absorption feature, for example a single rotation line in the infrared spectral range, it is able to distinguish the absorption caused by the analyte from unspecific light attenuation (such as scattering). This gives a great advantage over methods that measure concentrations at a fixed wavelength (cf. Manfred Hesse, Herbert Meier, Bernd Zeeh: Spectroscopic Methods in Organic Chemistry, 4th Edition, Thieme, 1991, and Wolfgang Demtröder: Laser Spectroscopy. Basics and techniques, 4th edition, Springer, 2000).
- the present invention has for its object to overcome the disadvantages of the prior art. This object is achieved with the inventive method according to claim 1. Preferred embodiments of the method according to the invention are specified in the subclaims.
- the method presented solves in particular the illustrated problem of pressure limitation.
- VCSEL Surface-emitting lasers
- Detected, selective wavelengths for the detection of water in the range from 1.8 ⁇ m to 2.5 ⁇ m are approximately 1.80 ⁇ m, 1.87 ⁇ m, 1.97 ⁇ m, 1.98 ⁇ m, 1.99 ⁇ m, 2, 0 ⁇ m, 2.1 ⁇ m, 2.2 ⁇ m, 2.47 ⁇ m, 2.48 ⁇ m, and 2.50 ⁇ m.
- Figure 1 is a schematic representation of a device for performing the method according to the invention
- Figure 2 shows the basic scheme of a data evaluation
- FIG. 3 shows the tuning behavior of a VCSEL (tuning range versus tuning frequency)
- Figure 4 is a plot of the absorbance of the measurement signal for water
- Figure 5 and Figure 6 absorption spectra of water at a pressure of 50 bar
- Figure 7 Spectra of water at different pressure.
- Surface-emitting lasers vertical cavity surface emitting lasers, VCSELs
- VCSELs vertical cavity surface emitting lasers
- edge emitters diode lasers of conventional design
- the frequency with which the emission wavelength can be changed by varying the current is far above the bandwidth of the frequencies customary for absorption spectroscopy (a few hundred Hz to kHz).
- Edge emitters can usually be tuned continuously over 1 cm "1 (ie a dominant mode, no mode jumps). In order to distinguish the absorption caused by the analyte from unspecific light attenuation, one has to tune the emission frequency of the laser to such an extent that a complete absorption characteristic is measured can.
- the invention shown uses VCSEL for the spectroscopy of gases, in particular water, as shown for example in FIG. 1.
- a suitable VCSEL (1) which is located in a block (2), is bundled by appropriate optics (3), mirrors (4), (5) through the measuring medium (13) and further directed via mirrors (6) and (7) to a detector (8) and to an evaluation device (12).
- Diode lasers can be tuned with the current and the temperature. On the other hand, this means that the temperature at which the laser is located must be kept constant. This condition is not as strict for the VCSELs used in this procedure as for diode lasers of conventional construction (edge emitter). It is therefore not essential to control the temperature precisely.
- the fastening of the VCSEL in a block (2), in an advantageous embodiment made of metal, is therefore sufficient in some cases.
- the laser holder can also be thermostatted by water cooling or a thermoelectric cooler.
- the detector (8) must be matched to the wavelength of the VCSEL, its bandwidth must be adapted to the desired tuning rate (see Nyquist sampling theorem, according to which the sampling frequency for signal reconstruction must be at least twice as high as the frequency of the signal itself).
- the VCSEL (1) is operated either in series with an ohmic resistor (10) via a conventional laser driver (11) or via a function generator (9).
- the laser driver (11) generates a current curve of any shape (symmetrical or asymmetrical triangle, sine, step, ...) typically of the order of magnitude 0-10 mA. It is not necessary to let the ramp start from 0 mA or from the current I th . It is possible and sometimes sensible to apply a current ramp to the laser, which begins at I> I t h.
- Commercially available laser drivers have bandwidths up to a few 100 kHz.
- a function generator (9) is used to generate a saving curve of any shape (symmetrical or asymmetrical triangle, sine, step, ...), typically of about 0-10V , to create.
- a series resistor (10) of approximately 2000 ohms must be connected in series with the VCSEL in order to limit the current that is passed through (VCSELs are sensitive to voltage and current peaks).
- the current is typically 0 to 5 mA in a current-controlled manner. This makes it possible to tune the VCSEL very quickly (up to MHz).
- a current curve corresponding to the economy curve now ensures the change in the laser emission frequency. It has been found that the tuning range of a VCSEL decreases with the tuning frequency. This results in a limit for the method at about 20 MHz.
- a single measurement is possible during each ramp.
- the signal is evaluated according to the Lambert Beer law (see below for the theory).
- A ln (In / ⁇ )
- the absorbance A gives one of the concentration of the water directly proportional size.
- I 0 is the intensity of the incident laser light (depending on the wavelength), I that of the transmitted light, also depending on the wavelength.
- the intensity IQ the baseline to a certain extent, can be determined by measuring the laser intensity as a function of the wavelength without absorbing water in the beam path. It is also possible to determine this mathematically.
- FIG. 2 shows the basic diagram of the data evaluation.
- a current ramp is shown with which the VCSEL is operated.
- the second field shows the corresponding detector signal.
- the laser output power increases linearly in the first approximation.
- the wavelength changes, also approximately linear. If there is an absorbing molecule (e.g. water) in the beam path, the signal is weakened at the correct wavelength. This is illustrated by the indentation of the curve in the third drawing.
- the partial picture on the right shows the absorbance, calculated from ln (output intensity / transmitted intensity) as a function of the wavelength. The absorbance is directly proportional to the concentration of the absorbing molecule.
- the measured absorbance depends on the temperature. For a constant concentration of the absorbing water, the temperature of the water can therefore be determined in situ from the value of the absorbance.
- 4 shows a plot of the absorbance (standardized) of the measurement signal for water with a partial pressure of 5 bar at a total pressure of 50 bar over a path length of 1 cm depending on the temperature for two absorption lines (1.92 and 2.02 ⁇ m). The range examined extends from 300K to 1500K.
- the method presented allows the temperature of the absorbing gas (here: water) to be determined by comparing the signal strength for two lines.
- one of the lines is strong at low temperature, while the other is more pronounced at high temperature. This is advantageously done by evaluating the Quotients of the absorbances with two absorption lines. One of these should be strong at a higher temperature, the other at a lower temperature.
- multiplexing can be used.
- time division multiplexing is used. This means that two VCSELs are used, each of which measures one of the two lines.
- the laser beams run in parallel and hit the same detector.
- the lasers are now controlled alternately, making quasi-simultaneous measurement possible.
- Multiplexing is not just limited to temperature measurements. This principle can also be used for concentration measurement.
- Fig. 7 shows spectra of water (100%) at 800K and different pressure (5 bar, 50 bar, 100 atm). It can be seen that at higher pressures, individual lines merge into a broad peak shape. Conventional diode lasers cannot be fully tuned across such wide formations. The procedure presented here is able to do this.
- the method according to the invention is also suitable for use in a two-beam experiment.
- the output beam is split; one of the two partial beams passes through the measuring volume and experiences specific absorption, the other, called the reference beam, is guided past it.
- the reference beam can be called I 0 in analogy to the previous one, the measuring beam I.
- the measuring beam passing through the measuring volume and the reference beam are of the same size.
- Two detectors record the signals.
- the reference beam is used to obtain a baseline for calculating the absorption.
- the combination with an auto balancing technique allows significant noise suppression if the quotient of I 0 / I is formed before the signal amplification of the individual signals I and I 0 . If both signals are first amplified and then divided and logarithmized, they contain uncorrelated noise.
- Wavelength modulation or frequency modulation enable an improved detection limit compared to simple absorption.
- the method is therefore also suitable for determining the concentration of the gas to be detected (in particular water) only in order to infer the concentration of other species.
- Fiber coupling is particularly useful when using the described method in sensors and measuring systems.
- the optical fibers enable easier handling of a system constructed according to the method for field measurements.
- the fibers can be made of quartz, for example.
- the very fast tuning capability enables quick measurements or high time resolution
- the very wide tunability also allows the investigation at high pressures.
- the process is inexpensive.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03706109A EP1476741A1 (en) | 2002-02-11 | 2003-02-11 | Method for the rapid spectroscopic analysis of the concentration, temperature, and pressure of gaseous water |
AU2003208157A AU2003208157A1 (en) | 2002-02-11 | 2003-02-11 | Method for the rapid spectroscopic analysis of the concentration, temperature, and pressure of gaseous water |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT2102002A AT500543B1 (en) | 2002-02-11 | 2002-02-11 | METHOD FOR RASKING SPECTROSCOPIC CONCENTRATION, TEMPERATURE AND PRESSURE MEASUREMENT OF GASEOUS WATER |
ATA210/2002 | 2002-02-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003069316A1 true WO2003069316A1 (en) | 2003-08-21 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AT2003/000040 WO2003069316A1 (en) | 2002-02-11 | 2003-02-11 | Method for the rapid spectroscopic analysis of the concentration, temperature, and pressure of gaseous water |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1476741A1 (en) |
AT (1) | AT500543B1 (en) |
AU (1) | AU2003208157A1 (en) |
WO (1) | WO2003069316A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008079032A3 (en) * | 2006-12-22 | 2008-08-28 | Photonic Innovations Ltd | Gas detector |
CN101504367B (en) * | 2009-03-10 | 2011-07-20 | 哈尔滨工业大学 | Apparatus for simultaneously monitoring concentration of carbon monoxide and carbon dioxide |
CN102269698A (en) * | 2011-07-04 | 2011-12-07 | 中国科学院合肥物质科学研究院 | Device for detecting nitrous oxide based on infrared absorption spectrum |
CN102269699A (en) * | 2011-07-25 | 2011-12-07 | 北京农业智能装备技术研究中心 | System and method for detecting concentration of hydrogen sulfide gas in poultry house |
CN102967580A (en) * | 2012-11-09 | 2013-03-13 | 山东微感光电子有限公司 | VCSEL (vertical cavity surface emitting laser)-based low-power-consumption gas detection method and device |
DE202013103647U1 (en) | 2013-08-12 | 2013-09-02 | Aspect Imaging Ltd. | A system for online measurement and control of O2 fraction, CO fraction and CO2 fraction |
US8945936B2 (en) | 2011-04-06 | 2015-02-03 | Fresenius Medical Care Holdings, Inc. | Measuring chemical properties of a sample fluid in dialysis systems |
CN107884427A (en) * | 2017-11-09 | 2018-04-06 | 北京理工大学 | Gas content measuring system in a kind of bubbling crystallzation bubble based on circulating water tunnel |
Families Citing this family (1)
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CN108732113B (en) * | 2018-01-22 | 2021-03-23 | 复旦大学 | System and method for measuring NO in water body |
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EP0692222A1 (en) * | 1994-07-15 | 1996-01-17 | Vixel Corporation | Sensor for analyzing molecular species |
US6091504A (en) * | 1998-05-21 | 2000-07-18 | Square One Technology, Inc. | Method and apparatus for measuring gas concentration using a semiconductor laser |
US6274879B1 (en) * | 1998-09-04 | 2001-08-14 | DRäGER MEDIZINTECHNIK GMBH | Process and device for the quantitative detection of a given gas |
-
2002
- 2002-02-11 AT AT2102002A patent/AT500543B1/en not_active IP Right Cessation
-
2003
- 2003-02-11 WO PCT/AT2003/000040 patent/WO2003069316A1/en not_active Application Discontinuation
- 2003-02-11 EP EP03706109A patent/EP1476741A1/en not_active Withdrawn
- 2003-02-11 AU AU2003208157A patent/AU2003208157A1/en not_active Abandoned
Patent Citations (3)
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EP0692222A1 (en) * | 1994-07-15 | 1996-01-17 | Vixel Corporation | Sensor for analyzing molecular species |
US6091504A (en) * | 1998-05-21 | 2000-07-18 | Square One Technology, Inc. | Method and apparatus for measuring gas concentration using a semiconductor laser |
US6274879B1 (en) * | 1998-09-04 | 2001-08-14 | DRäGER MEDIZINTECHNIK GMBH | Process and device for the quantitative detection of a given gas |
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008079032A3 (en) * | 2006-12-22 | 2008-08-28 | Photonic Innovations Ltd | Gas detector |
US7999232B2 (en) | 2006-12-22 | 2011-08-16 | Photonic Innovations Limited | Gas detector |
AU2007338957B2 (en) * | 2006-12-22 | 2014-05-22 | Photonic Innovations Limited | Gas detector |
CN101504367B (en) * | 2009-03-10 | 2011-07-20 | 哈尔滨工业大学 | Apparatus for simultaneously monitoring concentration of carbon monoxide and carbon dioxide |
US8945936B2 (en) | 2011-04-06 | 2015-02-03 | Fresenius Medical Care Holdings, Inc. | Measuring chemical properties of a sample fluid in dialysis systems |
US9599599B2 (en) | 2011-04-06 | 2017-03-21 | Fresenius Medical Care Holdings, Inc. | Measuring chemical properties of a sample fluid in dialysis systems |
CN102269698A (en) * | 2011-07-04 | 2011-12-07 | 中国科学院合肥物质科学研究院 | Device for detecting nitrous oxide based on infrared absorption spectrum |
CN102269699A (en) * | 2011-07-25 | 2011-12-07 | 北京农业智能装备技术研究中心 | System and method for detecting concentration of hydrogen sulfide gas in poultry house |
CN102967580A (en) * | 2012-11-09 | 2013-03-13 | 山东微感光电子有限公司 | VCSEL (vertical cavity surface emitting laser)-based low-power-consumption gas detection method and device |
EP2918994A4 (en) * | 2012-11-09 | 2016-08-24 | Shandong Micro Photographic Electronic Co Ltd | Vcsel-based low-power-consumption gas detection method and device |
DE202013103647U1 (en) | 2013-08-12 | 2013-09-02 | Aspect Imaging Ltd. | A system for online measurement and control of O2 fraction, CO fraction and CO2 fraction |
CN107884427A (en) * | 2017-11-09 | 2018-04-06 | 北京理工大学 | Gas content measuring system in a kind of bubbling crystallzation bubble based on circulating water tunnel |
Also Published As
Publication number | Publication date |
---|---|
EP1476741A1 (en) | 2004-11-17 |
AT500543B1 (en) | 2006-11-15 |
AT500543A1 (en) | 2006-01-15 |
AU2003208157A1 (en) | 2003-09-04 |
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