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WO1997025609A1 - Sonde optique permettant de detecter in situ des concentrations d'hydrocarbures - Google Patents

Sonde optique permettant de detecter in situ des concentrations d'hydrocarbures Download PDF

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Publication number
WO1997025609A1
WO1997025609A1 PCT/US1997/000389 US9700389W WO9725609A1 WO 1997025609 A1 WO1997025609 A1 WO 1997025609A1 US 9700389 W US9700389 W US 9700389W WO 9725609 A1 WO9725609 A1 WO 9725609A1
Authority
WO
WIPO (PCT)
Prior art keywords
light
light beam
probe
hydrocarbon
prisms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1997/000389
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English (en)
Inventor
Robert W. Dibble
Rajiv K. Mongia
Quang-Viet Nguyen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of California Berkeley
University of California San Diego UCSD
Original Assignee
University of California Berkeley
University of California San Diego UCSD
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of California Berkeley, University of California San Diego UCSD filed Critical University of California Berkeley
Priority to AU18257/97A priority Critical patent/AU1825797A/en
Publication of WO1997025609A1 publication Critical patent/WO1997025609A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis

Definitions

  • the present invention relates to the detection of the hydrocarbon vapors, and, more particularly, to optical probes to detect the absorption of infrared radiation and measure the concentration of hydrocarbon vapors in a combustion environment.
  • hydrocarbon fuel into an oxygen-containing atmosphere to form a mixture of air and fuel .
  • the hydrocarbon fuel is traditionally stored in a liquid state, and may be evaporated to form a gaseous fuel vapor or sprayed into the oxygen-containing atmosphere as a fine mist of liquid fuel droplets.
  • the mixture of air and fuel (whether droplets or vapor) is then ignited.
  • Knowledge of the fuel vapor distribution, i.e., the concentration, as a function of time, of gaseous hydrocarbon fuel at various locations in the engine, is essential to model the fuel efficiency, performance, and pollutant emissions of an engine.
  • the mixing of the fuel with the oxygen-containing atmosphere is a turbulent process, and the concentration of any fuel vapor may be spatially and temporally non-uniform. Therefore, there is a need for a detector which can measure the fluctuating concentration of hydrocarbon vapors in an engine environment .
  • One method of measuring the fuel vapor concentration is to insert a hypodermic or hollow needle into a portion of the engine, e.g., a fuel line, and suction off a sample of the gas.
  • the gas sample is fed into a gas chromatograph, mass spectrometer, or some similar instrument, and the hydrocarbon concentration is measured.
  • the needle may be manipulated, e.g., pushed or pulled through the fuel line, in order to measure the fuel concentration at different locations. It takes about one second to draw a sufficient amount of gas through the needle to form a sample. Because most engines fire more than twenty times per second, the single sample represents the average concentration, over at least twenty cycles, of fuel at the tip of the needle.
  • Another method of measuring the concentration of fuel vapor is to detect the absorption of light by the hydrocarbon gas.
  • hydrocarbon molecules that can be used as fuel such as methane, ethane, propane, n- pentane, n-hexane, n-heptane, n-octane, methanol, ethanol, butanol, acetone, and iso-octane, have absorption lines in the infrared range. The peak and width of an absorption line depends upon the type of hydrocarbon molecule, but most hydrocarbon molecules have a strong absorption line around 3.39 microns. This absorption line is due to the vibrational transition (v 3 P7 for methane) of the carbon-hydrogen bond in the hydrocarbon molecule.
  • a helium-neon laser emits light at a wavelength almost exactly equal to the peak of the hydrocarbon absorption line, i.e., at about 3.39 microns.
  • 2947.909 cm “1 is a working value for the wavenumber (the inverse of the wavelength) of the peak of the helium-neon laser emission
  • 2947.912 cm 1 is a working value for the wavenumber of the peak of the methane absorption.
  • the emission line for the helium- neon laser is very narrow compared to the absorption line of the hydrocarbon molecules; the broad absorption line overlaps the narrow emission line.
  • the concentration of hydrocarbon gas can be measured by firing a helium-neon laser through the mixture of air and fuel and detecting the absorption of laser light.
  • a combustor such as a furnace, incinerator or engine.
  • an device which can measure the concentration of hydrocarbon vapors in a combustion environment.
  • Such a device should detect the absorption by hydrocarbon molecules of light having a wavelength around 3.39 microns.
  • such a device should have a probe which measures the hydrocarbon concentration in situ.
  • such a device should have a high spatial resolution, e.g., a few millimeters, and a high temporal resolution, e.g., less than fifty milliseconds, and be cost-effective and reliable.
  • An apparatus for detecting the concentration of hydrocarbon vapor uses a first light source to generate a first light beam having a wavelength of in the infrared range.
  • a second light source generates a second light beam having a wavelength in the visible range.
  • the first and second light beams are combined into a third light beam by a beam combiner.
  • a beam splitter splits the third light beam into fourth and fifth light beams.
  • An infrared light detector is positioned in the path of the fourth light beam, and a visible light detector is positioned in the path of the fifth light beam.
  • a probe which includes a two substantially parallel and adjacent light pipes, and two prisms attached to the ends of the light pipes, is positioned in the optical path of the third light beam. The two prisms have substantially parallel opposing faces which are separated by a gap.
  • a first optical fiber couples one light pipe to the first beam splitter, and a second optical fiber couples another light pipe to the second beam splitter.
  • Each light pipe may comprise a sapphire rod, and each prism may comprise a polished end of the sapphire rod.
  • Each light pipe may comprise a metal tube with one of the optical fibers inserted into the tube, and each prism may comprise a sapphire prism attached to an end of the metal tube.
  • FIG. 1 is a schematic cross-sectional view of an optical probe inserted into an inlet of a combustion device.
  • FIG. 2 is a schematic graph of the emission spectrum of a laser and the absorption spectrum of a hydrocarbon molecules a function of the wavenumber.
  • FIG. 3 is a schematic diagram of a hydrocarbon detector according to the present invention.
  • FIG. 4 is a schematic perspective view of the detector of FIG. 3 in which the probe includes optical fibers inserted into metal tubes.
  • FIG. 5 is a schematic perspective view of the detector of FIG. 3 in which the probe includes sapphire rods.
  • a detector 20 is provided to measure the concentration of hydrocarbon vapor in a fuel injection system 10 for a combustion device.
  • an oxygen-containing atmosphere e.g., air
  • a port 12 flows from a port 12 through a line 14 and into a combustion chamber 18 having an exhaust line 19.
  • Some means for distributing liquid or gaseous fuel projects into line 14.
  • a pipe 16 may project across the diameter of the line, and fuel may flow out of a plurality of holes in the inward facing side of the pipe. If the fuel is in a liquid state, then it may be sprayed as a mist of droplets into line 14. In addition, liquid fuel will begin evaporating as it flows through the line.
  • the air from port 12 and fuel from pipe 16 mix turbulently as they are drawn through line 14 toward combustion chamber 18. Due to this turbulent mixture, the concentration of hydrocarbon vapor in line 14 will vary.
  • a probe 22 of detector 20 is inserted into line 14 so that the air and fuel mixture pass through a probe volume 24 located at the tip of the probe.
  • the detector 20 may measure the concentration of hydrocarbon vapor in probe volume 24 in real time, with a sampling rate of at least one hundred hertz, and more preferably about five to ten kilohertz.
  • the probe can be moved across the diameter of the line in order to measure the spatial distribution of the hydrocarbon vapor.
  • the detector 20 operates by measuring the absorption of infrared light, preferably at a wavelength of approximately 3.39 microns.
  • a helium-neon laser emits light, also at a wavelength of approximately 3.39 microns.
  • the graph shows the absorption or emission constant, in units of k, the Boltzmann constant, on the y-axis, and the wavenumber (the inverse of the wavelength) on the y-axis.
  • the absorption of light by methane is shown by the curve A.
  • Absorption spectrum A shows the absorption of methane with a peak at 2947.912 cm 1 .
  • the relative emission of light by a helium neon laser as a function of wavenumber is shown by the curve E.
  • the emission spectrum E has a peak at about 2947.909 cm 1 , but is much narrower than the absorption line A.
  • Other hydrocarbon molecules such as ethane, propane, n- pentane, n-hexane, n-heptane, n-octane, methanol, ethanol, butanol , acetone, and iso-octane, have similar absorption spectra with maxima which overlap the helium neon laser emission line.
  • Oxygen, nitrogen and water do not appreciably absorb light at a wavelength of 3.39 microns; in most combustion devices the only absorptive gas will be the hydrocarbon vapor.
  • I/I 0 e ! - ⁇ 'L Pl (1)
  • I 0 is the original intensity of the light
  • a is the absorption coefficient of the hydrocarbon molecule which is being measured
  • L is the path length of the light through the hydrocarbon-containing atmosphere
  • P is the partial pressure of the hydrocarbon gas.
  • the absorption coefficient of methane is about 10-20 atm "1 cm 1 . Therefore, if the partial pressure of methane is 0.5 atm and the path length is on the order of two millimeters, there will be a 22% reduction from the original intensity I 0 .
  • a detector 20 includes a probe 22 for optically detecting the concentration of hydrocarbon vapor in a probe volume 24.
  • Probe 22 is optically coupled to an infrared light source 26.
  • the infrared light source 26 which may be a helium-neon (HeNe) laser, generates a light beam 28 having a wavelength in the infrared range, i.e., above 0.7 microns, and preferably a wavelength of 3.39 microns.
  • HeNe helium-neon
  • a commercially available HeNe laser was utilized for infrared light source 26, but a diode laser or a light emitting diode (LED) having an emission line at 3.39 microns could be used instead.
  • Probe 22 is also optically coupled to a visible light source 30, which may be a commercially available gas or diode laser.
  • Visible light source 30 generates a light beam 32 having a wavelength in the visible range, i.e., 0.3 to 0.7 microns, preferably at a wavelength of 0.633 microns.
  • Infrared light source 26 and visible light source 30 are carefully aligned so that a beam combiner 34, e.g., an ordinary partial reflector, may combine light beams 28 and 32 into a single multi- wavelength light beam 36.
  • An LED could be used instead of a laser as visible light source 30.
  • a light source could be designed to emit light in both the infrared and visible ranges. If the light source emits light both the infrared and visible ranges, beam combiner 34 is unnecessary.
  • Optical fiber 42 guides multi-wavelength light beam 36 from beam combiner 34 to probe 22, whereas optical fiber 44 guides the light beam from the probe to a set of detectors.
  • Optical fibers 42 and 44 may be composed of fluoride glass, zinc selenide, or sapphire.
  • Multi-wavelength light beam 36 is focused by reflection off an optical element 40, such as a parabolic mirror, into optical fiber 42.
  • light beam 36 could be focused by transmission through an optical element, such as a lens.
  • the optical element is preferably a mirror because its optical characteristics are independent of the wavelength of the incident light.
  • Probe 22 includes two substantially parallel, and preferably relatively inflexible, light pipes 46 and 48.
  • the optical fibers 42 and 44 may be coupled to light pipes 46 and 48, respectively, by an optical coupler 50.
  • Each light pipe may be about two inches long.
  • Two prisms 52 and 54 are positioned at the ends of light pipes 46 and 48, respectively.
  • the prisms may be composed of sapphire, and each prism has an angled outer face 56 and a flat inner face 58.
  • the light beam 36 is projected from optical fiber 42 into the base of probe 22.
  • the multi-wavelength light beam is bent by a prism through a ninety degree angle to travel along a path perpendicular to the length of the light pipe.
  • the light beam may be bent by internally reflecting off angled outer face 56 of prism 52.
  • the light beam exits prism 52 through inner face 58, traverses probe volume or gap 24, and enters prism 54 through flat inner face 58.
  • the light beam 36 is again reflected through a ninety degree angle, this time by angled outer face 56 of prism 52, to pass through light pipe 48.
  • the probe volume 24 comprises the space between the opposing and substantially parallel inner faces of the prisms.
  • the probe volume has a gap of width w : .
  • the path length L through the hydrocarbon vapor (used in Equation 1 above) is equal to w x .
  • the width w x of probe volume 24 is selected to be sufficiently large that a change in concentration results in a measurable change in light intensity, but sufficiently small that detector 20 has a high spatial resolution. Width x may be about one to two millimeters.
  • each light pipe comprises a portion of an optical fiber which has been inserted into a metal tube 60.
  • the metal tube 60 has a thickness of about one-half millimeter and an inner diameter which substantially matches the diameter of the optical fiber to ensure a tight fit of the fiber inside the tube.
  • Light pipes 46 and 48 are separated by a spacer body 62 and are held rigidly in position so that the gap width w x does not change.
  • Light pipes 46 and 48 may be attached to spacer body 62 by a glue or an adhesive tape, or some other mechanical means may be provided to hold the light pipes stationary relative to each other.
  • the width of spacer body 62 may be adjusted by a screw 63 to vary the width w 1 of the probe volume.
  • Sapphire prisms 52 and 54 are affixed to the ends of metal tubes 60 by, for example, a commercially available transparent glue. The optical fibers are inserted into the tubes so that the ends of the fibers abut the prisms.
  • each light pipe comprises a sapphire rod.
  • the optical fibers 42 and 44 are coupled to light pipes 46 and 48 by an optical coupler 50.
  • the light pipes may be held stationary relative to each other by the optical coupler or by some other mechanism.
  • Prisms 52' and 54' are formed by polishing or cutting angled outer faces 56 into the sapphire rods. Although shown with a rectangular cross-section, the sapphire rods could also have a circular cross-section.
  • optical fiber 44 guides light beam 36 from probe 22 to a beam splitter 64, such as an ordinary partial reflector.
  • Beam splitter 64 splits the light beam into two separate light beams.
  • One light beam is directed through a filter 70 which filters out non- infrared wavelengths to generate an infrared light beam 66.
  • the other light beam is directed through a filter 72 which filters out non-visible wavelengths to generate a visible light beam 68.
  • An infrared light detector 74 is positioned in the path of infrared light beam 66, and a visible light detector 76 is positioned in the path visible light beam 68.
  • Light detectors 74 and 76 may be indium-tin (InSb) photodetectors.
  • the detectors 74 and 76 were commercially available liquid-nitrogen cooled InSb photodetectors. However, thermo-electrically cooled InSb detectors, or pyroelectric detectors could also be used. As light beam 36 passes through probe volume 24, the infrared light, but not the visible light, will be absorbed by the hydrocarbon vapor. The higher the concentration of hydrocarbon vapor in the probe volume, the more light will be absorbed. By comparing the intensity I measured by infrared light detector 74 to the original intensity I 0 , the partial pressure P of the hydrocarbon gas in probe volume 24 may be calculated from the equation:
  • the air and fuel mixture passing through probe volume 24 may contain liquid hydrocarbon droplets.
  • both the infrared light and the visible light will be scattered by the liquid hydrocarbon droplets, resulting in a reduction in the light intensity measured by both infrared light detector 74 and visible light detector 76.
  • the detector 20 may isolate the reduction in light intensity due to the hydrocarbon vapor in order to accurately measure the hydrocarbon vapor pressure.
  • a correction factor can be determined by comparing fluctuations in the intensity of the visible light to fluctuations in the intensity of the infrared light.
  • the partial pressure may be calculated from the equation: where I' is the current intensity measured by the visible light detector and I' 0 is the original intensity, and R is an empirically determined constant.
  • probe 22 is inserted into an environment containing a flame or heated material, e.g., an incinerator, the materials in or near the probe volume may emit light.
  • a flame or heated material e.g., an incinerator
  • the materials in or near the probe volume may emit light.
  • hot soot particles in an exhaust flume may radiate light in the infrared range.
  • the light emitted in or near the probe volume may pass through inner face 58 of prism 54 and be measured by infrared detector, resulting in an underestimation of the hydrocarbon vapor density.
  • an optical element 80 such as a beam splitter, may be placed in the path of multi-wavelength light beam 36 between beam combiner 34 and optical element 40. Some of the light emitted in or near the probe volume may pass through flat inner face 58 of prism 52 and return along the optical path of light pipe 46 and optical fiber 42.
  • Optical element 80 reflects a portion of light that is returned along the optical train into a light beam 82, and a pyroelectric or infrared optical detector 84 may be placed in the path of light beam 82. The intensity measured by detector 84 may be subtracted from the intensity measured by infrared light detector 74 to generate a corrected intensity measurement.
  • the detection apparatus of the present invention includes a probe with two parallel light pipes and two prisms affixed at the ends of the light pipes.
  • the detection apparatus directs the combined beam through a probe volume between the parallel faces of the prisms to detect the concentration of hydrocarbon vapor.
  • detector 20 has been described with reference to an inlet port of a combustion device, detector 20 is adaptable to a variety of applications, such as measuring the fuel distribution in the inlet port of a reciprocating engine, in the premixing section of a premixed gas turbine, or in the afterburner of a gas turbine engine.
  • the detection system may be used to measure the concentration of hydrocarbons in the exhaust of an incinerator system, furnace, or other processing chamber.
  • the detection system may be used in various non-combustion environments, such as a building or tunnel, to detect leaks of hydrocarbon vapor.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

Cette invention concerne une sonde (22) comprenant deux tubes conducteurs de lumière (46, 48), ainsi que deux prismes (52, 54) qui sont fixés aux extrémités de ces tubes (46, 48). Un faisceau lumineux dont la longueur d'onde se situe dans l'infrarouge, est combiné à un autre faisceau lumineux dont la longueur d'onde se situe dans le spectre visible, ceci afin d'obtenir un faisceau combiné (36). Un appareil de détection va diriger le faisceau combiné (36) à travers un volume (24) de la sonde défini par les parois des prismes (52, 54) de manière à pouvoir détecter une concentration de vapeur d'hydrocarbures.
PCT/US1997/000389 1996-01-12 1997-01-09 Sonde optique permettant de detecter in situ des concentrations d'hydrocarbures Ceased WO1997025609A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU18257/97A AU1825797A (en) 1996-01-12 1997-01-09 Optical probe for in-situ detection of hydrocarbon concentration

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US58731196A 1996-01-12 1996-01-12
US08/587,311 1996-01-12

Publications (1)

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WO1997025609A1 true WO1997025609A1 (fr) 1997-07-17

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PCT/US1997/000389 Ceased WO1997025609A1 (fr) 1996-01-12 1997-01-09 Sonde optique permettant de detecter in situ des concentrations d'hydrocarbures

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19843553A1 (de) * 1998-09-23 2000-04-13 Bayer Ag Meßvorrichtung zur In-Prozeß-Kontrolle
WO2007000166A1 (fr) * 2005-06-27 2007-01-04 Sfk Technology A/S Enregistrement de spectres d’absorption de longueur d’onde spécifiques à la position
GB2538563A (en) * 2015-05-22 2016-11-23 Optosci Ltd Gas sensing apparatus
EP3244195A4 (fr) * 2015-03-31 2018-09-05 Mitsubishi Heavy Industries, Ltd. Système d'analyse de gaz et chaudière
US10189632B2 (en) 2016-09-12 2019-01-29 Altria Client Services Llc Aerosol-generating system

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2580500A (en) * 1949-04-25 1952-01-01 Albert Paul Mch Device for determining turbidity within a body of liquid
SU1103082A1 (ru) * 1982-08-20 1984-07-15 Vigderman Volf Sh Погружной датчик фотоколориметра
US4637729A (en) * 1983-12-14 1987-01-20 Carrier Corporation Fiber optic moisture analysis probe
US5125747A (en) * 1990-10-12 1992-06-30 Tytronics, Inc. Optical analytical instrument and method having improved calibration

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2580500A (en) * 1949-04-25 1952-01-01 Albert Paul Mch Device for determining turbidity within a body of liquid
SU1103082A1 (ru) * 1982-08-20 1984-07-15 Vigderman Volf Sh Погружной датчик фотоколориметра
US4637729A (en) * 1983-12-14 1987-01-20 Carrier Corporation Fiber optic moisture analysis probe
US5125747A (en) * 1990-10-12 1992-06-30 Tytronics, Inc. Optical analytical instrument and method having improved calibration

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19843553A1 (de) * 1998-09-23 2000-04-13 Bayer Ag Meßvorrichtung zur In-Prozeß-Kontrolle
DE19843553C2 (de) * 1998-09-23 2001-09-20 Bayer Ag Meßvorrichtung zur In-Prozeß-Kontrolle
WO2007000166A1 (fr) * 2005-06-27 2007-01-04 Sfk Technology A/S Enregistrement de spectres d’absorption de longueur d’onde spécifiques à la position
US8530844B2 (en) 2005-06-27 2013-09-10 Sfk Technology A/S Recording of position-specific wavelength absorption spectra
EP3244195A4 (fr) * 2015-03-31 2018-09-05 Mitsubishi Heavy Industries, Ltd. Système d'analyse de gaz et chaudière
US10302558B2 (en) 2015-03-31 2019-05-28 Mitsubishi Heavy Industries, Ltd. Gas analysis system and boiler
GB2538563A (en) * 2015-05-22 2016-11-23 Optosci Ltd Gas sensing apparatus
GB2538563B (en) * 2015-05-22 2017-08-02 Optosci Ltd Gas sensing apparatus
US10189632B2 (en) 2016-09-12 2019-01-29 Altria Client Services Llc Aerosol-generating system
US11091314B2 (en) 2016-09-12 2021-08-17 Altria Client Services Llc Aerosol-generating system
US11945644B2 (en) 2016-09-12 2024-04-02 Altria Client Services Llc Aerosol-generating system

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