WO2001033200A1 - Procede permettant de surveiller de maniere continue des especes chimiques et une temperature dans des gaz de processus chauds - Google Patents

Procede permettant de surveiller de maniere continue des especes chimiques et une temperature dans des gaz de processus chauds Download PDF

Info

Publication number
WO2001033200A1
WO2001033200A1 PCT/US2000/028869 US0028869W WO0133200A1 WO 2001033200 A1 WO2001033200 A1 WO 2001033200A1 US 0028869 W US0028869 W US 0028869W WO 0133200 A1 WO0133200 A1 WO 0133200A1
Authority
WO
WIPO (PCT)
Prior art keywords
line
monitoring
flow rate
species
absoφtion
Prior art date
Application number
PCT/US2000/028869
Other languages
English (en)
Inventor
William Anthony Von Drasek
Olivier Charon
David M. Sonnenfroh
Phillip A. Mulhall
Mark G. Allen
Eric Wetjen
Original Assignee
L'air Liquide, Societe Anonyme À Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude
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 L'air Liquide, Societe Anonyme À Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude filed Critical L'air Liquide, Societe Anonyme À Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude
Priority to AU17517/01A priority Critical patent/AU1751701A/en
Priority to JP2001535035A priority patent/JP2003513272A/ja
Priority to EP00980224A priority patent/EP1230535A1/fr
Publication of WO2001033200A1 publication Critical patent/WO2001033200A1/fr

Links

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
    • G01N21/39—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using tunable lasers
    • 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
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/85—Investigating moving fluids or granular solids
    • 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
    • G01N2021/396—Type of laser source
    • G01N2021/399—Diode laser
    • 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
    • G01N21/84—Systems specially adapted for particular applications
    • G01N2021/8411—Application to online plant, process monitoring
    • G01N2021/8416—Application to online plant, process monitoring and process controlling, not otherwise provided for

Definitions

  • This invention relates to the field of combustion.
  • the invention relates to continuously monitoring the concentration of reactants, intermediates, or products from or in high temperature combustion processes.
  • measurements on the process gas temperature, particulate concentration level and air entrainment rates can be obtained.
  • diagnostic instrumentation is useful for analysis of key combustion species such as O 2 , CO 2 , CO, NOx, etc. and using the measurement information for optimizing and controlling the process to improve energy efficiency, product quality, and minimize pollutants.
  • key combustion species such as O 2 , CO 2 , CO, NOx, etc.
  • high temperature and high particulate densities typically found in industrial processes limits the available monitoring methods to extractive sampling techniques.
  • in-situ techniques are available for limited operating conditions and a specific set of chemical species.
  • a temperature resistant probe e.g., water-cooled, a water removal system, a particle filter, and a suction pump to withdraw the sample from the process.
  • a temperature resistant probe e.g., water-cooled, a water removal system, a particle filter, and a suction pump to withdraw the sample from the process.
  • sampling lines from the process to the analyzer can be 10's to 100's of feet in length.
  • the use of long sample lines introduce a delay that can be 10's tolOO's of seconds before reaching the analyzer.
  • the choice of analysis instrumentation is dependent on the chemical species of interest. For example, to monitor the O 2 concentration in the process or stack a paramagnetic resonance technique or electrochemical cell is often used. To monitor CO, CO 2 or NO nondispersive infrared detectors can be used. All of these commercially available analyzers also exhibit a characteristic response time that will add to the measurement delay.
  • GC instruments gas chromatographs (GC), mass spectrometers (MS) or the combination GC/MS.
  • GC instruments have an advantage of monitoring an array of chemical species such as, O 2 , N 2 , CO 2 , CO, and H 2 that are important in combustion processes.
  • these instruments sample the gas in a batch mode with a slow response time ranging from approximately 30 seconds to several minutes depending on the GC operating conditions.
  • Discrete sampling and slow instrument response time hinders the ability to use the acquired information in a process control loop, particularly for processes with dynamic behavior.
  • Continuous gas sampling with an MS instrument can be conducted with a fast response time ⁇ l-sec.
  • MS instruments need to operate under vacuum conditions. Variations in the sampling flow rate, e.g., due to plugging or pressure fluctuations in the process itself, will change the response of the detector resulting in a measurement error.
  • ZrO 2 In-situ zirconium oxide (ZrO 2 ) probes developed in the late 1960s by NASA have been used on many industrial applications for O 2 monitoring.
  • the sensor uses a sealed ZrO 2 tube which when heated becomes an electrolytic conductor because of the mobility of O 2 ions which requires a minimum operating temperature of -600 °C for permeation of the ions.
  • the sensor can operate at moderate to very high temperatures > 1600 °C with response times reported to be approximately seconds.
  • These devices work well in relatively clean environments where low levels (few percent) of excess O 2 are present such as steel slab reheat furnaces.
  • plugging of the probe surface results in measurement degradation.
  • thermal shock of the ceramic probe can occur resulting in permanent damage.
  • optical measurement techniques viz., absorption
  • optical measurement techniques provide a means for conducting in-situ measurements on combustion processes. Since optical measurements are non-intrusive, measurements can be conducted on the harshest of environments containing high particle density atmospheres that can be either reducing or oxidizing. Temperature limits are not a concern since the measurements are optical and conducted in-situ. Additionally, optical measurements in corrosive atmospheres that are acidic or basic are handled without the difficulties typically experienced with extractive sampling.
  • CO and O 2 are key species in defining the local or global process stoichiometry.
  • Optical measurement techniques provide a means for conducting in-situ measurements on harsh process environments that avoid issues such as long delay times, thermal cycling, and atmosphere effects such as reducing or oxidizing.
  • O 2 and CO can be simultaneously monitored by a number of optical techniques using lasers such as Raman, REMPI(resonance enhanced multiphoton ionization), or absorption in the UV region.
  • lasers such as Raman, REMPI(resonance enhanced multiphoton ionization), or absorption in the UV region.
  • these techniques suffer due to the complexity of the optical equipment needed and to date have been restricted to well controlled environments.
  • solid state diode lasers the devices offer the simplicity necessary for conducting absorption measurements in industrial harsh environments.
  • Solid state lasers are compact robust devices that provide a spectrally pure narrow line width tunable source of radiation (typically 1MHz) with wavelength accessibility ranging from 600nm to 25 ⁇ m.
  • diode lasers operating in the near infrared spectral region offer a tunable source of radiation from a device that operates near room temperature and is compatible with standard optical fiber components, where standard refers to common materials used in the telecommunication industry, e.g., silica.
  • Diode lasers operating at longer wavelengths require special cooling.
  • Mid-infrared diode lasers 2.5-25 ⁇ m require cryogenic cooling and are not easily coupled to fiber optic components, making the devices cumbersome for industrial applications.
  • the transitions observed in the near infrared are not from the fundamental bands, but rather overtones or combination band systems.
  • the methods presented herein provide means for conducting in-situ real-time measurements on important combustion process parameters such as product, intermediate or reactant species concentrations, gas temperature, and particulate loading density using diode laser light source to conduct absorption measurements. This information can then be related to the global or zone process stoichiometry, air entrainment rates, particulate density levels, and gas temperature. Use of the measured values in process control strategies can lead to improvements in energy efficiency, product quality, and pollutant reduction. Since the methods use a line-of- sight optical measurement, no gas extraction is required. This reduces the system cost and associated maintenance issues due to probe plugging. A unique feature of the methods is the fast-time response that allows real-time monitoring of the combustion atmosphere.
  • a primary objective of the present invention is to provide a method to monitor and, preferably, control the performance of an industrial combustion space, where performance may refer to global stoichiometry, or zone stoichiometry of the process, gas temperature, particulate density, or air entrainment level.
  • a first aspect of the invention is a method of monitoring or controlling the global or local stoichiometry of a process (preferably an oxy-fuel combustion process) operating at lean conditions, i.e., excess O 2 present, the method comprising the steps of: a) launching an initial collimated beam of radiation emitted by tunable diode laser along a line-of-sight path through the process; (For O 2 monitoring a selected rotational line near the B-X (0,0) band of O 2 is preferred.
  • the detector is preferably a silicon photo-diode, photomultiplier tube, or similar photo detector with sensitivity in the O 2 spectral region.
  • the filter element is preferably be either a narrow band reflector or transmitting optic and/or a dispersing element for use in suppressing background radiation.) c) processing the optical signal by observing the amount of attenuation observed from the initial beam as the laser is tuned over a resonance absorption line of O 2 ; (The integrated area of the absorption line is directly proportional to the O 2 number density for a given temperature.) and d) producing an electrical signal based on the O 2 number density for use in controlling one or more of the following variables: process pressure, fuel inlet flow rate, and oxidant inlet flow rate.
  • the electrical signal produced preferably alerts an operator of the process operating condition, allowing manual adjustment of the process by adjusting oxidant, fuel or process pressure or any combination of these three variables.
  • One preferred method is to use the electrical signal to control the operation of one or more actuators, which in turn allows manipulation of one or more of the process variables.
  • the furnace pressure may be increased by reducing the stack area thereby decreasing air infiltration, which will decrease the measured O 2 concentration.
  • the oxidant input flow rate which preferably comprises air, oxygen enriched air or oxygen, can be adjusted to reach the desired amount for the process.
  • the input fuel flow rate can be adjusted, however, this will also influence the energy input to the process.
  • a second aspect of the invention is a method of monitoring or controlling the global or local stoichiometry of a process (preferably an oxy-fuel combustion process) operating at fuel rich conditions, i.e., excess CO present, (processes that produce a reducing atmosphere of CO), the method comprising the steps of: a) launching an initial collimated beam of radiation emitted by tunable diode laser along a line-of-sight path through the process; (For CO, monitoring a selected rotational line is preferably used from the CO overtone band near 1.56 ⁇ m, which can be accessed using commercially available InGaAsP/InP diode lasers that can be fiber optically coupled.) b) opposite the launch position the transmitted radiation is collected and transported to photo detector having a filter element; (The detector is preferably InGaAs photo-diode, photomultiplier tube, or similar photo detector with sensitivity in the CO spectral region.
  • the filter element is preferably either a narrow band reflector or transmitting optic and/or a dispersing element for use in suppressing background radiation from hot walls and/or particles.) c) processing the optical signal by observing the amount of attenuation observed from the initial beam as the laser is tuned over a resonance absorption line of CO; (The integrated area of the absorption line divided by the line strength and pathlength is directly proportional to the CO number density for a given temperature.) and d) producing an electrical signal based on the CO number density for use in controlling one or more of the following variables: process pressure, fuel inlet flow rate, and oxidant inlet flow rate.
  • the electrical signal produced preferably alerts an operator of the process operating condition, allowing manual adjustment of the process by adjusting oxidant, fuel or process pressure or any combination of these three variables.
  • One preferred method is to use the electrical signal to control the operation of one or more actuators, which in turn allows manipulation of one or more of the process variables. For example, if the process is a furnace, the furnace pressure may be decreased by increasing the stack damper area thereby increasing air infiltration, which will decrease the measured CO concentration due to combustion with air.
  • the oxidant input flow rate which preferably comprises air, oxygen enriched air or oxygen can be adjusted to reach the desired CO concentration for the process.
  • the input fuel flow rate can be adjusted.
  • a third and preferred aspect of the invention is a method for monitoring both
  • a preferred method is adaptable to a range of process operating conditions with CO and O 2 ranging from 100% to .01%, the method comprising the steps of: a) launching a plurality of collimated beams of radiation emitted by a plurality of tunable diode lasers along a line-of-sight path through the process; (The collimated beam comprising a plurality of wavelengths, e.g., 763 nm and 1.5 ⁇ m radiation for O 2 and CO monitoring respectively.) b) simultaneously launching a plurality of tunable beams by spatially introducing the radiation through a fiber optic network; (Alternatively, near simultaneous beam introduction by temporally separating the multiple input beams, i.e., tune the lasers at different times.) c) simultaneous transmission of multiple frequencies separated using dispersion elements and/or narrowband filters and detector combination allowing discrimination between the different wavelengths; (
  • a fourth aspect of the invention is a method for monitoring temperature of gas phase of a process, preferably an oxy-fuel combustion process, comprising the steps of: a) launching an initial collimated beam of radiation emitted by tunable diode laser along a line-of-sight path through the combustion process; b) tuning the diode laser over two or more rotational lines of the selected species; (CO and or O 2 can be used for temperature monitoring however the preferred species is H 2 O or another detectable process gas that may be present, e.g., HC1. Whichever species is chosen it is preferred that the dependence on process stoichiometry is minimal.
  • H 2 O is present in the vast majority of combustion processes and others where H 2 O is known to be present.
  • a photo detector sensitive at the wavelength of interest
  • the filter element is preferably either a narrow band reflector or transmitting optic and/or a dispersing element for use in suppressing background radiation from hot walls and/or particles.
  • processing the optical signal by observing the amount of attenuation observed from the initial beam as the laser is tuned over two or more resonance abso ⁇ tion lines; (The temperature is obtained by applying the following expression hcAE f x exp
  • R is the ratio of the integrated absorbance of each transition at the unknown temperature T.
  • T is the ratio of the linestrength values at some reference temperature
  • T 0 is the ratio of the linestrength values at some reference temperature
  • ⁇ E is the energy separation of the absorbing states
  • h is Planck's constant
  • k is Boltzmann's constant
  • c is the speed of light.
  • Measurement of gas phase temperature provides additional information that is preferably used in process mass and energy balances, provide information on linestrengths used in determining the number density from abso ⁇ tion measurements, useful in unit conversion, and beneficial for process optimization.
  • temperature is used to convert number density values obtained from abso ⁇ tion measurements to the more industrial acceptable percent concentration values typically used in industrial plant environments.
  • Process optimization is preferably practiced for temperature measurements at defined process locations. For example, one objective of a reheat furnace is to achieve a uniform temperature of a billet and hold the temperature for a predetermined time. Measurement of the gas phase temperature near the surface of the billet provides feedback information on the temperature level and stability, providing a means to control an undesired temperature or fluctuations in temperature.
  • a fifth aspect of the invention is a method for monitoring particulate concentration level in a monitored gas phase region of a process comprising the steps of: a) launching an initial collimated beam of radiation emitted by tunable diode laser along a line-of-sight path through the gas phase; b) opposite the launch position the transmitted radiation is collected and transported to photo detector (sensitive at the wavelength of interest) having a filter element; (The filter element can be either a narrow band reflector or transmitting optic and/or a dispersing element for use in suppressing background radiation.) c) tuning the laser off any resonance absorbing species and monitor the attenuated radiation detected; d) processing the optical signal by observing the amount of attenuation observed from the initial beam as the laser is tuned away from all resonance abso ⁇ tion lines; (The observed attenuation is related to the particle density along the line-of-sight optical path by the following expression
  • I 0 is the beam initial intensity and I is the measured intensity after the beam propagates a distance 1 through the process.
  • the measured attenuation can be related to the particle number density if the extinction coefficient,a ext , is known.
  • e) producing an electrical signal based on the particle number density is preferably used in regulation of one or more of the following variables: process pressure, fuel inlet flow rate, and oxidant inlet flow rate.
  • a sixth aspect of the invention is a method for monitoring the rate of air entrainment into a combustion process comprising the steps of: a) measuring the concentration of the major combustion product species such as CO 2 or H 2 O by launching a collimated beam of radiation emitted by tunable diode laser along a line-of-sight path through the combustion process; b) opposite the launch position the transmitted radiation is collected and transported to a photo detector (sensitive at the wavelength of interest) with a filtering element; (The filter element can be either a narrow band reflector or transmitting optic and/or a dispersing element for use in suppressing background radiation from hot walls and/or particles.) c) processing the optical signal by observing the amount of attenuation observed as the laser is tuned over a resonance abso ⁇ tion line; (The integrated area of the abso ⁇ tion line divided by the line strength and pathlength is
  • a seventh aspect of the invention is an indirect means of monitoring H 2 (which has no infrared abso ⁇ tion transitions) and/or combustible hydrocarbons in a high temperature > 1000 °C gas phase comprising of the steps: a) measuring the concentration of H 2 O by launching an initial collimated beam of radiation by a tunable diode laser along a line-of- sight path through a gaseous phase (preferably flue gas of a combustion process) in the spectral region where H 2 O abso ⁇ tion transitions are found.
  • a gaseous phase preferably flue gas of a combustion process
  • a filter element opposite the launch position the transmitted radiation is collected and transported to a photo detector with a filter element;
  • the filter element preferably comprises a narrow band reflector, narrow bandpass filter, and/or a dispersing element for use in suppressing background radiation.
  • processing the optical signal by observing the amount of attenuation observed from the initial beam as the laser is tuned over a resonance abso ⁇ tion line of H 2 O; (The integrated area of the abso ⁇ tion line is directly proportional to the H 2 O number density for a given temperature.)
  • a second measurement point is used either within the gas phase region or in a diverted stream of gas; (The measurement of H 2 O is conducted in a similar manner as described above but here O 2 is introduced and allowed to mix with the heated gas.
  • the O 2 gas will react with unburned H 2 and /or hydrocarbons that may be present thereby forming H 2 O as a product.
  • This signal is preferably used in controlling one or more of the following variables: fuel inlet flow rate and/or oxidant inlet flow rate, and process pressure.
  • the O 2 content can range from air to pure O 2 .
  • O 2 purity > 90% is preferred.
  • CO in a high temperature gas such as combustion flue gas reacts with injected O 2 forming CO 2 .
  • the CO 2 can then be monitored using a near infrared laser in the 1.5 ⁇ m spectral region. Comparison between the CO 2 observed before O 2 injection and after O 2 , injection provides an indirect means for measuring CO.
  • a further aspect of the invention is a means to monitor pollutant X where X is a pollutant of specific interest to a process.
  • X can be NO or SO in exhaust of a process flue or at a specified location in the process.
  • the method for monitoring comprising the steps: a) launching an initial collimated beam of radiation emitted by tunable diode laser along a line-of-sight path through the combustion process; (For monitoring species X, the preferred method consists of monitoring one of the abso ⁇ tion transitions in the near infrared that is free of interfering background species such as H 2 O.) b) opposite the launch position the transmitted radiation is collected and transported to a photo detector having a filter element; (The detector is preferably a silicon photo-diode, photomultiplier tube, or similar photo detector with sensitivity in the spectral region of species X.
  • the filter element can be either a narrow band reflector or transmitting optic and/or a dispersing element for use in suppressing background radiation.) c) processing the optical signal by observing the amount of attenuation observed from the initial beam as the laser is tuned over a resonance abso ⁇ tion line of species X; (The integrated area of the abso ⁇ tion line is directly proportional to the number density for a given temperature.) and d) producing an electrical signal based on the number density of species
  • the electrical signal may be useful in controlling one or more of the following variables: process pressure, fuel inlet flow rate, and oxidant inlet flow rate.
  • additional combustion species such as NO and /or SO with the main monitoring species set namely O 2 , CO, and H 2 O provides a means to fully characterize the exhaust gas and/or zone of a combustion process. Since diode lasers cover a broad wavelength range the limitations for detecting a specific species is dictated by the physics of the abso ⁇ tion process. For example, some species are not infrared active such as N 2 . While other species that are infrared active have limited use due to weak abso ⁇ tion transitions and/or interference by other species in the measurement volume.
  • the generality of this invention provides unique methods for monitoring operating conditions on high temperature large-scale industrial processes.
  • the fast-time response provides a means for monitoring the process conditions in a real-time mode allowing the identification of processes changes, e.g., global or local stoichiometry and applying regulation to correct and adjust the process to the desired operating condition.
  • FIG. 1 represents a schematic block diagram illustrating the configuration for industrial monitoring and control
  • FIG. 2 is a graph showing measured O 2 absorbance compared with theoretical Voigt fit
  • FIG . 3 is graph showing the variation of measured O 2 number density with time for a dynamic combustion process
  • FIG . 4 is graph showing the variation of measured CO number density with time for a dynamic combustion process
  • FIG. 5 represents a schematic block diagram illustrating a conceptual application using the diode laser monitoring method on an electric arc furnace
  • FIG. 6 is a graph showing the relationship for increasing O 2 concentration in the oxidant between excess oxidant introduced in the combustion process and percent O 2 observed in the dry flue gas;
  • FIG. 7 represents a schematic block diagram illustrating a conceptual application using the diode laser monitoring method on a glass melting furnace;
  • FIG. 8 is a graph showing the relationship between the observed transmittance through a medium containing particles of specific sizes; and FIG. 9 represents a schematic block diagram illustrating a conceptual method for conducting abso ⁇ tion measurements under high particle loading.
  • Methods for monitoring important species in-situ in the gas phase with fast response times and high accuracy provides a means to regulate many industrial processes for maintaining optimum performance, where performance means global or local stoichiometry, gas temperature, particle density, and air entrainment estimates. Measuring and controlling these quantities provides a means for production quality control, pollutant reduction, and improved energy efficiency.
  • FIG. 1 A single or multiple diode laser 1 is used in this embodiment.
  • the diode laser model 760DFB supplied by Sarnoff Co ⁇ . Princeton, New Jersey is suitable.
  • Each laser has a current controller 2 and temperature controller 3 for stability and wavelength tuning (such as available from Melles Griot, Carlsbad, California, model 56DLD403).
  • the output of diode laser 1 is fiber optically coupled (by a Gould Electronic, Millesville, Maryland, model 22-10676040-4687) and transported to coupler 4 that splits the input energy in half.
  • the divider would be n x 2, where n is the number of inputs with 2 outputs.
  • the output of the coupler is transported by single mode fiber 5 (OZ Optics, Ontario, Canada), core with FC/APC connector/collimator ends which can be hundreds of meters in length, allowing the sensitive laser and associated electronics to be placed in a secure, well controlled environment away from the harsh environment typically found near industrial combustion processes.
  • Beam launch module 6 is mounted at the monitoring point of interest 8 on the process using water or gas cooled pipes 16.
  • the beam exits fiber optic 5 and propagates through shaping and collimating optics 7 (for example OZ Optics anti-reflection coated with a 2mm waist at 1mm).
  • shaping and collimating optics 7 for example OZ Optics anti-reflection coated with a 2mm waist at 1mm.
  • the beam is shaped to the desired diameter and divergences.
  • a typical beam diameter ranging from 1 - 9 centimeters (cm) is preferred.
  • the expanded beam diameter provides a spatial averaging effect that improves the signal-to-noise for particle laden flows and reduces the angular divergence, which reduces beam steering due to temperature gradients.
  • Beam 9 propagates through the cooled pipe 16 on the launch side and traverses across the process where it is received by the detector module 11 mounted opposite beam launch module 6. Both the beam launch module 6 and detector module 1 1 are purged with a gas 15. Any gas can be used provided it does not contain the gaseous species being monitored. For example, N 2 or air can be used if only CO monitoring is being conducted.
  • Detector module 11 receives the beam and directs it to detector 10, which comprises one or more of the following elements: a narrowband pass filter, dispersing elements or narrowband reflectors to selectively direct the laser radiation to the photo detector (e.g., EG&G Optoelectronic, Salem Massachusetts Model UV- 245BQ).
  • the filters are used to suppress any background radiation from the high temperature process.
  • the output of the photo detector 12 is sent to a balanced radiometric detector (BRD) 13 along with the split portion of the beam 14 from the coupler 4, which is used as a reference.
  • the BRD 14 is a noise canceling electronic circuitry.
  • the output from the BRD gives the log ratio measured intensity from the detector 12 and the reference intensity 14.
  • the output from 14 is processed in computer 17 where number density of the measured species can be obtained.
  • the apparatus illustrated in FIG. 1 is an example of a preferred apparatus for conducting abso ⁇ tion measurements on industrial combustion processes.
  • a beam is generated by a diode laser and propagated across the gas region of the process and the absorbance measured.
  • the differences between known approaches and methods and apparatus of the present invention lie in how one measures the absorbance signal. Since diode lasers are inherently "noisy" devices and the vibrational overtone and combination band transitions accessible in the near infrared region generally have weak absorbances, noise reduction is necessary.
  • Direct abso ⁇ tion monitoring can be performed in some cases under the following conditions: the abso ⁇ tion transition is strong, the monitored species concentration is high, or the path length is sufficiently long.
  • direct abso ⁇ tion has limited use, requiring implementing a noise suppression technique.
  • Continuos bandwidths of 100 Hz provide superior time response and in special cases bandwidths of 1000 Hz are achievable.
  • the fast-time response allows monitoring of dynamic process conditions with the capability of resolving subtle changes such as CO bursts or variations in air infiltration that can impact the overall performance of the process.
  • I 0 is the incident laser intensity
  • I is the measured laser intensity after propagating a distance 1 through the process
  • S(T) is the temperature dependent abso ⁇ tion line strength
  • g(n) is the frequency dependent lineshape
  • N is the absorber number density. Note that the log (I/I 0 ) is directly recorded from the BRD circuit used in the system illustrated in FIG. 1. Since S(T) is a function of temperature, knowledge of the temperature is needed, or else an abso ⁇ tion line can be selected that is relatively insensitive to temperature within the range of interest.
  • the number density which can be converted to concentration by applying an equation of state, can be obtained by integrating the signal across the abso ⁇ tion lineshape as follows
  • FIG. 3 A demonstration of the real-time monitoring is illustrated in FIG. 3 for measuring the change in the O 2 number density.
  • the stoichiometry is dynamically changing by implementing a square wave (.1 Hz) variation in the fuel (natural gas) flow rate for an average firing rate of 1.5 MMBtu/hr oxygen-fuel flame conducted in the flue of a 4m x lm x lm furnace. Variations in the fuel flow rate cause a dynamic change in the combustion stoichiometry that oscillates between fuel-lean and fuel-rich conditions.
  • Monitoring real-time dynamic process changes provides a means for coupling the sensor to a regulation system that can be used to optimize the process.
  • processes such as electric arc furnaces for processing secondary steel or rotary kilns for secondary aluminum or iron melting operate in a batch mode.
  • the scrap and/or raw material are first loaded into the process and melting begins with the input of electrical and/or chemical energy.
  • Processes of this type produce large quantities of CO that represents an energy loss and an environmental hazard. Improvement in the energy efficiency is obtained by monitoring the flue gas composition and injecting O 2 containing gas with a concentration range of (20%- 100). The excess O 2 oxidizes the CO to recover the thermal energy.
  • the release of CO from these processes can be transient in nature.
  • FIG. 5 An example illustrating diode laser monitoring on a dynamic process is shown in FIG. 5 for an electric arc furnace (EAF).
  • EAF electric arc furnace
  • the sensor beam launch and detector modules as previously discussed are mounted near the flue region at location 1 or 2 on FIG. 5.
  • Location 1 is between the EAF furnace exhaust and water cooled duct. At this position air is entrained and mixed with the flue gas. Therefore monitoring at this location requires setting the optical pathlength between the beam launch and receiver modules such that surrounding air entrainment does not influence the measurement.
  • Location 2 fixes the sensor system on the lid 14 of the process. Since the process operates in batch mode lid 14 is removed to load the raw material 5 in to tank 3. Lid 14 is then replaced along with electrodes 4.
  • Off-gas monitoring at either location 1 or 2 sends the transmittance signal 6 for CO, O 2 and H 2 O to processor 7 which converts the signal to concentration.
  • This information is then transferred to control system 8, e.g., programmable logic controller (PLC), which sends a signal 9 to flow control valves 11 and 13.
  • PLC programmable logic controller
  • the control valve for the auxiliary burner 10 can be adjusted to increase or decrease the O 2 flow rate.
  • the O 2 flow rate can be adjusted on the O 2 lance 12.
  • Inco ⁇ orating a second monitoring location upstream of locations 1 or 2 shown in FIG. 5 that is either conducted on the process or in a diverted stream of the flue gas provides a means to indirectly monitor the H 2 content in the gas.
  • H 2 can also be present in high concentrations.
  • Injection of O 2 at the second location into the hot process gas will react with H2 off-gas and any unburned hydrocarbon, with H20 being the product species.
  • the O 2 injection can be ambient or heated using a heat exchanger utilizing thermal energy from the flue itself or another means such as, secondary burner or electrical, etc.
  • the change in H 2 O content can be attributed to the amount of H 2 and/or unburned hydrocarbons.
  • Dynamic processes such as the EAF can experience rapid changes in the off- gas composition on a 10's of seconds time scale.
  • the response time of conventional industrial flow control valves can be the rate-limiting step in this scheme, since adjustment of these valves can take many 10's of seconds.
  • the preferred system uses the fast-time response of the diode laser sensor with a regulation system and a solid state proportioning control valve such as described and claimed in U.S. Patent 5,222,713, inco ⁇ orated by reference herein.
  • the diode lasers measure the exhaust gas composition. Based on the CO and O 2 content in the exhaust the controller would change the amplitude of the proportional valve to the desired value to either decrease or increase the O 2 flow rate.
  • the proportional valve response is on the order of milliseconds which can be considered essentially instantaneous.
  • This control valve can also be pulsed which will improve process gas mixing further reducing the residence time.
  • the diode laser measurement location is preferably located at the point of interest in the process, thus further reducing delay times, since measurement delays on very large volume processes can still be an issue.
  • the tolerance for excess O 2 is process dependent and can impact the production operation in terms of quality, capacity, thermal efficiency, in addition to environmental effects related to NOx formation. Air entrainment into the process increases the oxidant level along with introducing additional N 2 contributing to energy losses and/or increased NOx formation. Similarly, the presence of CO indicates a reducing atmosphere that can affect the process quality, production, and can be a safety hazard due to the toxicity and combustibility of CO.
  • a diode laser sensing method of the invention is applied to a glass melting tank 1 as illustrated in FIG. 7.
  • the raw material enters melting tank 1 at the left side and flows to the right into refining zone 2 where it is then distributed for fiber or container manufacturing.
  • the furnace exhaust 3 is located in the same area as the raw material inlet.
  • the furnace can operate with O 2 - fuel or O 2 enriched air fuel burners 4.
  • Beam launch modules 6 and detector modules 5 are mounted at selected locations on furnace 1. For illustration pu ⁇ oses, three monitoring locations are shown in FIG. 7. In principle N monitoring points can be selected.
  • the laser system 10 is located away from the process and delivers N selected wavelengths by fiber optic 8 to the beam launch module 6.
  • Beam 7 consisting of N wavelengths temporally separated propagates along line-of-sight path through the process to detector module 5.
  • the resulting transmittance signal 9 is sent back to laser system 10 for processing the information into physical quantities, e.g., temperature and concentration.
  • Measured results are sent to the furnace supervisory system 12 by connection 13. Based on the measured results supervisory system 12 using a regulation algorithm will send signal 11 to the appropriate flow control valves.
  • Regenerative or recuperative furnaces are also suitable for the monitoring and control method.
  • hybrid furnaces consisting of regenerative or recuperative type using O 2 lances and/or auxiliary burners are also adaptable for the method. Monitoring at three locations as illustrated in FIG. 7 provides information at different zones in the process.
  • the measured values are near the exhaust of the furnace and can provide global information on the O 2 , CO, air entrainment, and particulate carry over.
  • the path length observed may be adjusted to localize the measured region since the monitoring technique is line- of-sight path integration.
  • the pathlength control is shown by extending the cooled pipes (as discussed in FIG. 1) 14 thus shorting the path. Shorter pathlength is desirable for high particulate loading that can result in significant beam attenuation over longer path distances due to extinction.
  • Zones B and C can monitor the average stoichiometry and Temperature observed in this region.
  • variations in particulate density can be observed by changing operating conditions such burner momentum.
  • Measurements conducted in the exhaust provide global process stoichiometry monitoring by following the O 2 and CO concentration. Using these measurements in combination with the air entrainment rates estimated from the H 2 O measurements provide a means for tuning the burner oxidizer input and furnace pressure. In addition, the air entrainment preferably alerts operators of possible furnace leaks from refractory damage.
  • the level of particulate matter in the exhaust is measured by tuning at least one of the lasers off an abso ⁇ tion transition. Here this information is preferably used as feedback regarding the burner placement within the glass tank, burner momentum, and angle of the flame with respect to the glass bath. It is known that variation in these parameters can influence the volatilization that leads to higher levels of particulate matter (ref) in the flue exhaust.
  • any large variation or sudden changes in the particulate level can alert furnace operators of potential problems, e.g., flame impingement due to deflection toward the crown or refractory damage near the burner exit.
  • Measurements of the temperature from at least two rotational allows determination of the linestrength value needed for determining the concentration of all species measured. This allows the measured value to be converted in to a percentage reading, instead of number density, which is accepted more favorably by furnace operators.
  • Process monitoring can also be conducted at a selected location within the process, as illustrated in FIG. 7. Because the measurement is optical, no disturbances are introduced to the process as in the case of sampling probe measurements. In this case, the measurement is conducted along the pathlength providing an integrated average across the line-of-sight path. Thus, the spatial location of high or low levels of O 2 detected along the path is not known.
  • the observed abso ⁇ tion signals can be weighted toward higher or lower temperatures depending on the transition being monitored. The preferred method would be to select an abso ⁇ tion transition that has a weak temperature dependence over a given temperature range of the process.
  • This application allows local stoichiometry control for a particular zone in the process.
  • a control loop integrating the sensor and flow control provides a means for optimizing the desired stoichiometry. In the case of glass, melting furnaces operating with reducing atmospheres will cause instabilities in glass color.
  • the basic principles outlined above for application in a glass melting tank can be similarly applied to steel reheat furnaces.
  • the stoichiometry is a critical control parameter to minimize scale formation on the billets.
  • desirable sensor locations can be positioned such that the beam propagates near the billet surface to regulate O 2 concentration and temperature uniformity.
  • the process is different from glass melting the method and integration with a regulation system is the same.
  • the key parameters in optimizing and controlling the process can be different.
  • Other applications using the diode laser sensor methods of the invention can be found in the chemical industry on processes that can be highly corrosive. The non-intrusive nature of the methods of the invention are ideal for applications on such processes.
  • sulfur recovery units are used to recycle sulfur used in the production of MMA (methyl methacrylate) for the Plexiglas industry. Improvements on this process have been demonstrated by using pure O 2 as a replacement for a fraction of air which leads to increased capacity, overall pollutant reduction (SOx and NOx), improved fuel efficiency and reduction in CO 2 emission.
  • the sensor is positioned on the first stage of the process. Monitoring real-time O 2 , CO and T, the process O 2 inlet flow rate is adjusted through a regulation system to minimize NOx.
  • organic compounds are present in the spent acid, which need to be burned. Here CO monitoring is used to insure complete combustion of all organic entering the process with appropriate regulation to adjust oxidant inlet conditions.
  • a variation of the monitoring method can be considered for industrial processes where the particulate loading is extremely high causing severe attenuation of the beam energy.
  • the effect of particulate concentration and pathlength is shown in FIG. 8.
  • the attenuation of the laser intensity can be completely absorbed.
  • Shortening the pathlength is the preferred solution but in some cases, a shorter pathlength may not be sufficient.
  • a dilution method shown in FIG. 9 can be applied.
  • a dirty process gas is flowing through a duct lin the direction shown by 2.
  • a portion of the flow is diverted into 3 where a dilution gas 4 is used to mix and dilute the particulate density.
  • Mounted on the external chamber is the diode laser monitoring system 7.
  • the preferred dilution gas would be any gas that does not contain the target species monitored by the diode laser.
  • To convert back to the process gas concentration the flow rate of the dilution gas must be known.
  • the amount of dilution gas can be high since the sensitivity of the diode laser monitoring method is high.

Abstract

L'invention concerne un procédé et un appareil utilisant des diodes laser accordables pour surveiller et/ou réguler un processus à température élevée, à l'aide d'un oxydant qui contient O2 et un combustible organique. La surveillance en temps réel des espèces-clé telles que O2, CO, et H2O permet de déterminer la stoechiométrie globale ou locale, la température des gaz, la concentration particulaire, et les niveaux d'entraînement d'air dans ledit processus. Le couplage des informations mesurées avec un système de régulation fournit des moyens d'optimiser et de réguler ce processus.
PCT/US2000/028869 1999-11-04 2000-11-01 Procede permettant de surveiller de maniere continue des especes chimiques et une temperature dans des gaz de processus chauds WO2001033200A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU17517/01A AU1751701A (en) 1999-11-04 2000-11-01 Method for continuously monitoring chemical species and temperature in hot process gases
JP2001535035A JP2003513272A (ja) 1999-11-04 2000-11-01 高温プロセスガスの化学種および温度の連続モニタリング方法
EP00980224A EP1230535A1 (fr) 1999-11-04 2000-11-01 Procede permettant de surveiller de maniere continue des especes chimiques et une temperature dans des gaz de processus chauds

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US43366799A 1999-11-04 1999-11-04
US09/433,667 1999-11-04
US52291500A 2000-03-10 2000-03-10
US09/522,915 2000-03-10

Publications (1)

Publication Number Publication Date
WO2001033200A1 true WO2001033200A1 (fr) 2001-05-10

Family

ID=27029934

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/028869 WO2001033200A1 (fr) 1999-11-04 2000-11-01 Procede permettant de surveiller de maniere continue des especes chimiques et une temperature dans des gaz de processus chauds

Country Status (4)

Country Link
EP (1) EP1230535A1 (fr)
JP (1) JP2003513272A (fr)
AU (1) AU1751701A (fr)
WO (1) WO2001033200A1 (fr)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003046497A1 (fr) * 2001-11-30 2003-06-05 L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Gorges Claude Methode de conduite et de controle de procedes de traitement thermique de produits dans des fours continus
WO2003060491A1 (fr) * 2002-01-17 2003-07-24 L'air Liquide - Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede de surveillance et de reglage d'une atmosphere de combustion reduisant les hautes temperatures
WO2003046522A3 (fr) * 2001-11-30 2004-06-10 Air Liquide Dispositif et procedes de lancement et de reception d'une source a gamme de longueur d'onde etendue
FR2859283A1 (fr) * 2003-09-01 2005-03-04 Air Liquide Procede de mesure d'especes gazeuses par derivation
FR2859467A1 (fr) * 2003-09-09 2005-03-11 Air Liquide Procede de controle de la fusion de verre dans un four
FR2859469A1 (fr) * 2003-09-09 2005-03-11 Air Liquide Procede de controle du formage de verre plat
WO2005024398A1 (fr) * 2003-09-01 2005-03-17 L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede de mesure d'especes gazeuses par derivation
EP1703206A3 (fr) * 2005-02-08 2006-10-04 The General Electric Company Procede et appareil pour la détection optique de produits de combustion a phases multiples
WO2007017616A2 (fr) * 2005-08-11 2007-02-15 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede de controle par spectroscopie d'absorption au cours du formage de verre plat et dispositif de controle
DE102006036563A1 (de) * 2006-08-04 2008-02-07 Siemens Building Technologies Hvac Products Gmbh Überwachung von Verbrennungsvorgängen an einem Ort durch schnellen Sauerstoffsensor
US7462218B2 (en) * 2001-11-29 2008-12-09 L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Aluminum melting method using analysis of fumes coming from the furnace
EP2664884A1 (fr) * 2012-05-18 2013-11-20 Air Products and Chemicals, Inc. Procédé et appareil pour chauffer des métaux
US8717488B2 (en) 2011-01-18 2014-05-06 Primesense Ltd. Objective optics with interference filter
US8786757B2 (en) 2010-02-23 2014-07-22 Primesense Ltd. Wideband ambient light rejection
CN107064060A (zh) * 2017-03-13 2017-08-18 中国人民解放军装备学院 一种用于燃烧场测量的光纤阵列光学探头
CN109270013A (zh) * 2018-11-28 2019-01-25 润电能源科学技术有限公司 一种炉内多维燃烧气体温度和多组分浓度测量方法和系统
CN109270008A (zh) * 2018-10-31 2019-01-25 润电能源科学技术有限公司 一种基于tdlas的燃烧气体温度和多组分浓度测量方法和系统
US10302558B2 (en) 2015-03-31 2019-05-28 Mitsubishi Heavy Industries, Ltd. Gas analysis system and boiler
CN110346315A (zh) * 2019-08-19 2019-10-18 大连世有电力科技有限公司 一种烟气测量装置

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008175611A (ja) * 2007-01-17 2008-07-31 Fuji Electric Systems Co Ltd ガス濃度測定装置およびガス濃度測定方法
JP5336394B2 (ja) * 2007-02-26 2013-11-06 ヨコガワ・コーポレーション・オブ・アメリカ 燃焼ガス分析
EP2158472B1 (fr) * 2007-06-15 2010-12-01 BP Chemicals Limited Procédé d'analyse en ligne d'un flux de traitement en phase vapeur
JP5412749B2 (ja) * 2008-05-16 2014-02-12 横河電機株式会社 透過散乱形濁度計
JP4950151B2 (ja) 2008-08-29 2012-06-13 株式会社日本自動車部品総合研究所 炭素量検出センサ
US7957001B2 (en) * 2008-10-10 2011-06-07 Ge Infrastructure Sensing, Inc. Wavelength-modulation spectroscopy method and apparatus
CN112964667B (zh) * 2021-02-05 2022-11-25 清华大学 一种受限空间设备内温度和组分集成化在线测量系统

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4126396A (en) * 1975-05-16 1978-11-21 Erwin Sick Gesellschaft Mit Beschrankter Haftung, Optik-Elektronic Device for the non-dispersive optical determination of the concentration of gas and smoke components
GB2057680A (en) * 1979-08-29 1981-04-01 Econics Corp Electro-optical flue gas analyzer
US5134276A (en) 1990-10-09 1992-07-28 International Business Machines Corporation Noise cancelling circuitry for optical systems with signal dividing and combining means
US5252060A (en) * 1992-03-27 1993-10-12 Mckinnon J Thomas Infrared laser fault detection method for hazardous waste incineration
WO1994023191A1 (fr) * 1993-03-30 1994-10-13 Brqt Corporation Moteur a deux temps a emissions d'hydrocarbures reduites
US5621166A (en) * 1995-04-06 1997-04-15 Ford Motor Company Exhaust emissions analysis apparatus and method
WO1999026058A1 (fr) * 1997-11-14 1999-05-27 American Iron And Steel Institute Procede et appareil de detection de la composition de gaz residuels

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4126396A (en) * 1975-05-16 1978-11-21 Erwin Sick Gesellschaft Mit Beschrankter Haftung, Optik-Elektronic Device for the non-dispersive optical determination of the concentration of gas and smoke components
GB2057680A (en) * 1979-08-29 1981-04-01 Econics Corp Electro-optical flue gas analyzer
US5134276A (en) 1990-10-09 1992-07-28 International Business Machines Corporation Noise cancelling circuitry for optical systems with signal dividing and combining means
US5252060A (en) * 1992-03-27 1993-10-12 Mckinnon J Thomas Infrared laser fault detection method for hazardous waste incineration
WO1994023191A1 (fr) * 1993-03-30 1994-10-13 Brqt Corporation Moteur a deux temps a emissions d'hydrocarbures reduites
US5621166A (en) * 1995-04-06 1997-04-15 Ford Motor Company Exhaust emissions analysis apparatus and method
WO1999026058A1 (fr) * 1997-11-14 1999-05-27 American Iron And Steel Institute Procede et appareil de detection de la composition de gaz residuels

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
B.L. UPSCHULTE ET AL.: "Measurements of CO, CO2, OH, and H2O in room-temperature and combustion gases by use of a broadly current-tuned multisection InGaAsP laser", APPLIED OPTICS., vol. 38, no. 9, 20 March 1999 (1999-03-20), OPTICAL SOCIETY OF AMERICA,WASHINGTON., US, pages 1506 - 1512, XP000828580, ISSN: 0003-6935 *
M.G. ALLEN: "Diode laser absorption sensors for gas-dynamic and combustion flows", MEASUREMENT SCIENCE AND TECHNOLOGY., vol. 9, 1988, IOP PUBLISHING, BRISTOL., GB, pages 545 - 562, XP000780563, ISSN: 0957-0233 *
R.M. MIHALCEA ET AL.: "A diode-laser absorption sensor system for combustion emission measurements", MEASUREMENT SCIENCE AND TECHNOLOGY., vol. 9, 1998, IOP PUBLISHING, BRISTOL., GB, pages 327 - 338, XP000777465, ISSN: 0957-0233 *
vol. 1376, 1 January 1990, P.C.HOBBS, article SCIETY OF PHOTO-OPTICAL INSTRUMENTATION ENGINEERS: ""Shot noise -limited optical measurements at baseband with noisy lasers, "Lasers Noise""
vol. 1435, 1 January 1991, K.L. HALLER & P.C.B. HOBBS, article OPTICAL METHODS FORULTRASENSITIVE DETECTION AND ANALYSIS: TECHNIQUES AND APPLICATIONS: "Shot noise-Limited Performance t Baseband with a Novel Electronic Noise Canceller"", pages: 298

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7462218B2 (en) * 2001-11-29 2008-12-09 L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Aluminum melting method using analysis of fumes coming from the furnace
FR2833018A1 (fr) * 2001-11-30 2003-06-06 Air Liquide Methode de conduite et de controle de procedes de traitement thermique de produits dans des fours continus
WO2003046522A3 (fr) * 2001-11-30 2004-06-10 Air Liquide Dispositif et procedes de lancement et de reception d'une source a gamme de longueur d'onde etendue
US7005645B2 (en) 2001-11-30 2006-02-28 Air Liquide America L.P. Apparatus and methods for launching and receiving a broad wavelength range source
WO2003046497A1 (fr) * 2001-11-30 2003-06-05 L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Gorges Claude Methode de conduite et de controle de procedes de traitement thermique de produits dans des fours continus
WO2003060491A1 (fr) * 2002-01-17 2003-07-24 L'air Liquide - Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede de surveillance et de reglage d'une atmosphere de combustion reduisant les hautes temperatures
US7223978B2 (en) 2003-09-01 2007-05-29 L'Air Liquide, Société Anonyme à Directoire et Conseil de Surveillance pour l'Étude et l'Exploitation des Procédés Georges Claude Method for measuring gaseous species by derivation
FR2859283A1 (fr) * 2003-09-01 2005-03-04 Air Liquide Procede de mesure d'especes gazeuses par derivation
WO2005024398A1 (fr) * 2003-09-01 2005-03-17 L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede de mesure d'especes gazeuses par derivation
FR2859467A1 (fr) * 2003-09-09 2005-03-11 Air Liquide Procede de controle de la fusion de verre dans un four
FR2859469A1 (fr) * 2003-09-09 2005-03-11 Air Liquide Procede de controle du formage de verre plat
WO2005023720A1 (fr) * 2003-09-09 2005-03-17 L'Air Liquide, Société Anonyme à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Procédés Georges Claude Procede de controle du formage de verre plat
US7324203B2 (en) 2005-02-08 2008-01-29 General Electric Company Method and apparatus for optical detection for multi-phase combustion systems
EP1703206A3 (fr) * 2005-02-08 2006-10-04 The General Electric Company Procede et appareil pour la détection optique de produits de combustion a phases multiples
CN1818617B (zh) * 2005-02-08 2010-11-17 通用电气公司 多相燃烧系统的光学探测方法和装置
WO2007017616A2 (fr) * 2005-08-11 2007-02-15 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede de controle par spectroscopie d'absorption au cours du formage de verre plat et dispositif de controle
US8220291B2 (en) 2005-08-11 2012-07-17 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method for monitoring by absorption spectroscopy during the forming of flat glass and monitoring device
WO2007017616A3 (fr) * 2005-08-11 2007-03-29 Air Liquide Procede de controle par spectroscopie d'absorption au cours du formage de verre plat et dispositif de controle
DE102006036563A1 (de) * 2006-08-04 2008-02-07 Siemens Building Technologies Hvac Products Gmbh Überwachung von Verbrennungsvorgängen an einem Ort durch schnellen Sauerstoffsensor
US8786757B2 (en) 2010-02-23 2014-07-22 Primesense Ltd. Wideband ambient light rejection
US8717488B2 (en) 2011-01-18 2014-05-06 Primesense Ltd. Objective optics with interference filter
EP2664884A1 (fr) * 2012-05-18 2013-11-20 Air Products and Chemicals, Inc. Procédé et appareil pour chauffer des métaux
US9091484B2 (en) 2012-05-18 2015-07-28 Air Products And Chemicals, Inc. Method and apparatus for heating metals
US10302558B2 (en) 2015-03-31 2019-05-28 Mitsubishi Heavy Industries, Ltd. Gas analysis system and boiler
CN107064060A (zh) * 2017-03-13 2017-08-18 中国人民解放军装备学院 一种用于燃烧场测量的光纤阵列光学探头
CN109270008A (zh) * 2018-10-31 2019-01-25 润电能源科学技术有限公司 一种基于tdlas的燃烧气体温度和多组分浓度测量方法和系统
CN109270013A (zh) * 2018-11-28 2019-01-25 润电能源科学技术有限公司 一种炉内多维燃烧气体温度和多组分浓度测量方法和系统
CN110346315A (zh) * 2019-08-19 2019-10-18 大连世有电力科技有限公司 一种烟气测量装置

Also Published As

Publication number Publication date
JP2003513272A (ja) 2003-04-08
EP1230535A1 (fr) 2002-08-14
AU1751701A (en) 2001-05-14

Similar Documents

Publication Publication Date Title
US20020031737A1 (en) Method for continuously monitoring chemical species and temperature in hot process gases
WO2001033200A1 (fr) Procede permettant de surveiller de maniere continue des especes chimiques et une temperature dans des gaz de processus chauds
US6045353A (en) Method and apparatus for optical flame control of combustion burners
US5829962A (en) Method and apparatus for optical flame control of combustion burners
KR910006273B1 (ko) 화로시스템
EP2118638B2 (fr) Analyse de gaz de combustion
CN101287976B (zh) 二谱线气体光谱校准
CA2351792C (fr) Methode et appareil de controle de processus ameliore dans des applications de combustion
US7244936B2 (en) Chemical species detection including a multisection laser for improved process monitoring
US20030003590A1 (en) Method for measuring concentrations of gases and vapors using controlled flames
US20030132389A1 (en) Method for monitoring and controlling the high temperature reducing combustion atmosphere
US20110062056A1 (en) Excess Air Control For Cracker Furnace Burners
Von Drasek et al. Multifunctional industrial combustion process monitoring with tunable diode lasers
KR20090051244A (ko) 산화 에틸렌을 제조하기 위한 공정의 개선된 제어 및 최적화 방법
US20140221718A1 (en) Excess air control for cracker furnace burners
JP2000275171A (ja) 気体中の浮遊粒子の原子吸光分析方法および装置
Li et al. A mid‐infrared laser absorption sensor for calibration‐free measurement of nitric oxide in laminar premixed methane/ammonia cofired flames
Tadanaga et al. N 2 O analysis device and analysis method
CN114112936A (zh) 一种锅炉水冷壁的近壁烟气成分测量装置及方法
Von Drasek et al. Oxy-fuel combustion emission monitoring using tunable diode laser sensors
Von Drasek et al. Optimization of Oxy‐Fuel Combustion with Optical Sensors
Jenkins et al. Diode laser temperature measurements
Faber et al. High temperature in-situ IR laser absorption CO-sensor for combustion control
MUTA et al. P2-4 In-situ Measurement of CO by Tunable Diode Laser Absorption Spectroscopy in a Large Scale Waste Test Furnace
Baer et al. Diode laser sensors for combustion measurements and control

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2000980224

Country of ref document: EP

ENP Entry into the national phase

Ref country code: JP

Ref document number: 2001 535035

Kind code of ref document: A

Format of ref document f/p: F

WWP Wipo information: published in national office

Ref document number: 2000980224

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642