The present invention generally relates to method and systems for measuring gas, more specifically to methods and systems for measuring ammonia gas concentration using ultraviolet gas analysers.
Manure in livestock buildings generates ammonia and other toxic gases that affect the health of animals and production staff when the gas concentration reaches and uncontrolled level. Typical use of an ammonia sensor in the barns aims to regulate building ventilation to maintain toxic gas concentration below the maximum gas toxicity exposure limit.
There are many technologies available to measure the ammonia concentration, but no affordable solution exists with a reasonable lifetime and capable of sustain in a constant ammonia environment without loss of accuracy requiring frequent replacement of the measuring element.
Excess levels of ammonia can be dangerous to the health of animal and can widely affect the growing conditions. To warn the farmer of a high concentration of ammonia in the barn’s atmosphere, ammonia level is monitored using an ammonia gas sensor. Environmental conditions in the barns are special by the fact that the concentration of ammonia is almost always between 10 to 40 ppm. Conventional electrochemical type gas sensors are not suitable for those environments by the fact that the chemical-cell cannot be constantly immersed in an environment which is high in ammonia concentration; the lifetime of the chemical cell is greatly reduced so an electrochemical-type gas sensor does not offer and effective solution for this kind of application.
In recent years, optical based gas analysers have been introduced in the marketplace with the bulk of product utilizing infrared wavelengths to measure gas concentration. IR analysers typically have a high measuring accuracy and sensitivity and a high selectivity like photoacoustic based sensor or TDLA spectroscopy, but they are very expensive and not suitable for farming industry. Other NDIR low-cost sensors have been developed for the mass market like CO2, CO and SO2 sensor, but they suffer from poor accuracy with a range of ± 30 ppm that is far away from what the farming industry need.
Many toxic gases absorb ultraviolet radiation in a 190-330 nm wavelength region. The absorption cross section in the ultraviolet band if mostly two orders of magnitude higher than the one in the NIR band. Based on these assumptions, we present an invention to provide an ultraviolet gas analyser capable of measuring the concentration of toxic gas in a harsh atmospheric environment constantly filled with high concentration of ammonia and others toxic gas.
The aforesaid and other objectives of the present invention are realized by generally providing a method and an apparatus for measuring the concentration of gas interacting with ultraviolet light
In an aspect of the present invention, a system for measuring concentration of a gas is provided. The system comprises an absorption chamber comprising an air inlet and an air outlet, an active photodetector within the absorption chamber to measure a light radiation, a light source emitting an ultraviolet radiation within an absorption spectrum of the gas along an absorption path toward the active photodetector, an optical bandpass filter between the light source and the active detector and a reference photodetector positioned to measure the light radiation of the light source entering in the absorption chamber.
The light source may be a controllable ultraviolet “arc type”.
The system may further comprise a first interface for sampling a signal outputted by the active photodetector, a second interface for sampling the signal outputted by the reference photodetector and a computerized device connected to the first and second sampling interfaces, the computerized device being configured to calculate the concentration of the gas as a function of light absorption based on a ratio of the output signals of the reference photodetector and of the active photodetector.
The system may further comprise an optical element between the light source and the absorption chamber used to generate a collimated light beam within the absorption chamber. The system may further comprise a lens adjacent to the active detector for collimating the light emitted in the absorption chamber to the active photodetector. The system may further comprise a heating element adapted to heat the optical bandpass filter at a temperature higher than the dew point temperature of the gas.
The system may further comprise a beam splitter to direct a portion of the light radiation emitted in the absorption chamber towards the reference detector. The system may further comprise a controllable reference light source emitting a light radiation outside of the absorption spectrum of the gas, the light radiation being measurable by the active and the reference photodetector. The system may further comprise a drift compensation mechanism. The drift compensation mechanism may be configured to adjust the measurement of the gas concentration using a proportional ratio of drift values measured by the active photodetector and the reference photodetector since the last calibration.
In another aspect of the invention, a system for measuring concentration of a gas is provided. The system comprises an absorption chamber comprising an air inlet and an air outlet, an active photodetector within the absorption chamber to measure light radiation, a controllable light source emitting an ultraviolet light beam within an absorption spectrum of the gas along an absorption path toward the active photodetector, an optical bandpass filter between the light source and the active detector; and a device to change the length of the light path in the absorption chamber between the light source to the active photodetector.
The system may further comprise a first interface for sampling the ultraviolet light beam detected by the active photodetector, a second interface for controlling position of the device to change the length of the light path within the absorption chamber and a computerized device connected to the first and the second interfaces, the computerized device being configured to calculate the concentration of the gas as a function of light absorption measured by the signal ratio before and after changing the length of the light path through the absorption chamber.
The device to change the length of the light path may be a light pipe being insertable in the light path yet removable from the light path between the light source and the active photodetector.
The device to change the length of the light path between the light source and the active photodetector may be a support movable toward and away from the light source, the active photodetector being mounted to the movable support. The support may be moved using an electromotive force. The support may be a carriage. The support may comprise two mating portions, the first portion slidingly moving within the second portion to change the length of the light path.
The light source and the active photodetector may be oriented in the same direction toward the absorption chamber. The device to change the length of the light path may comprise a first reflecting member in the absorption chamber returning the ultraviolet light beam to the active photodetector setting a long light path and a second reflecting member insertable between the first reflecting member and the light source to set a short light path.
The system may further comprise an optical element between the light source and the absorption chamber used to generate a collimated light beam within the absorption chamber. The system may further comprise a lens adjacent to the active detector for collimating the light emitted in the absorption chamber to the active photodetector. The system may further comprise a heating element adapted to heat the optical bandpass filter at a temperature higher than the dew point temperature of the gas.
In yet another aspect of the invention, a method for measuring a concentration of a gas present in an absorption chamber is provided. The method comprises emitting a light beam through the absorption chamber at a wavelength absorbed by the gas, measuring a reference intensity of the emitted light entering in the absorption chamber, measuring an active intensity of the emitted light after passing through the gas in the absorption chamber at a predetermined distance of the emission of the light and calculating the gas concentration based on the ratio of the of measured active intensity and of the measured reference intensity.
The method further may further comprise filtering the emitted light entering the absorption chamber at a wavelength absorbed by the gas. The measuring of the reference intensity may be performed by a first photodetector and the measuring of the active intensity being performed by a second photodetector.
The method may further comprise deflecting a portion of the emitted light to measure the reference intensity.
In another aspect of the invention, a method for measuring a concentration of a gas present in an absorption chamber comprising a light path having a variable length between a light source and a photodetector is provided. The method comprises reducing the length of the light path in the absorption chamber, emitting a light beam through the absorption chamber at a wavelength absorbed by the gas in the reduced light path, measuring a reference intensity of the emitted light in the reduced light path, increasing the length of the light path in the absorption chamber, emitting the light beam through the absorption chamber at a wavelength absorbed by the gas in the increased light path, measuring an active intensity of the emitted active light beam in the increased light path and calculating the gas concentration based on the ratio of the measured intensities from the reduced light path and the increased light path.
The reducing of the length of the light path in the absorption chamber may further comprise inserting into the emitted light beam a light pipe inert to the gas. The reducing of the length of the light path in the absorption chamber may further comprise moving the light source and the photodetector toward one another.
The photodetector and the light source may be oriented in the same direction, the photodetector receiving the light beam through a first reflecting member, the reducing of the length of the light path in the absorption chamber further comprising placing a second reflecting member between the light source and the first reflecting member.
In a further aspect of the present invention, a method to correct for short and long terms drifts of the system is provided. The method further comprises turning off all of the active light source and the reference light source, measuring a reference intensity when the active light source and the reference light source are turned off, measuring an active intensity when the active light source and the reference light source are turned off, turning on the reference light source through the absorption chamber at a wavelength outside of the absorption spectrum of the gas, measuring a reference intensity when the reference light source is turned on, measuring an active intensity when the active light source is turned on, calculating a reference signal drift based on the difference between the measured reference intensities, calculating an active signal drift based on the difference between the measured active intensities, calculating a drift ratio of the reference signal drift and the active signal drift and correcting calculation of the gas concentration using the calculated drift ratio.
The features of the present invention which are believed to be novel are set forth with particularity in the appended claims.
The above and other objects, features and advantages of the invention will become more readily apparent from the following description, reference being made to the accompanying drawings in which:
A novel method and apparatus for measuring the concentration of gas interacting with ultraviolet light will be described hereinafter. Although the invention is described in terms of specific illustrative embodiment(s), it is to be understood that the embodiment(s) described herein are by way of example only and that the scope of the invention is not intended to be limited thereby.
As indicated above, a method and an apparatus for measuring the concentration of gas interacting with ultraviolet light is disclosed. In a preferred embodiment, the measured gas is a toxic gas such as ammonia. Understandably, other toxic gases may also be considered. As shown in
Referring to
Referring back to
The broadband collimated optical beam passes through a narrow bandpass filter 18 so that the UV emitted radiation is in accordance with a wavelength that is strongly absorbed by the gas whose concentration is to be determined. In some embodiments, the system 10 comprises an optical shield 20 made with a non-transparent material. The optical shield 20 is typically used to encloses the bandpass filter 18 to avoid broadband emission in the absorption chamber 11. For this exemplary embodiment, the bandpass filter 18 may have a centered wavelength of 200 nm ± 3 nm and a bandwidth of 10 nm ± 2 nm FWHM chosen to interact with ammonia absorption lines. Other filters center wavelength and bandwidth in the ultraviolet may be used depending on the gas and the concentration, within the scope of this invention.
Referring back to
The light travels along the absorption path and reach the collimation lens 32 located at the end of the absorption chamber that collects and focused the light to a second photodetector 34, also referred to as the active detector. The active detector 34 is almost identical to the reference detector 30 describe above, both are illustrated in
The transmitted intensity IT is related to incident light said the incident intensity IR, by the Beer-Lambert law:
where σ is the absorption cross-section of the gas at a particular wavelength in cm2/molecule, n is the volume number density of the gas in molecule/cm3 and L the length of the optical absorption path in cm.
Since the flashlamp spectrum is not flat in the UV band, the narrow band filter 18 may have a non-rectangular shape, the absorption cross-section σ is a function of the wavelength and the optical absorption path length may vary, we define the coefficient K = σL and replace n in unit of number density by C the concentration in unit of ppm. The coefficient K is obtained at the time of calibration with a gas of known concentration C. The Beer-Lambert law applied to calculate the gas concentration based on the ratio of the transmitted intensity IT to the incident intensity IR can be rewritten as follow.
The correction factor ρ0 is calculated under 0 ppm of gas concentration C and it is the ratio of the UV transmitted intensity at 0 ppm, IT0, measured by the active detector 34 to the UV incident intensity at 0 ppm, IR0, measured by the reference detector 30.
The correction coefficient ρ0 generally compensates for the inherent differential optical intensity of UV light falling on the reference 30 and active 34 detectors at 0 ppm gas concentration and compensates for the analog gain difference of the reference 30 and active 34 detector. The absorption path length between the beam splitter 28 and the said active detector can be extended in an advantageous manner to increase the absorption and the sensitivity of the gas analyser apparatus.
In another aspect, this invention includes a method to compensate for short term drifts due to temperature change and long-term drifts namely due to components aging. The method uses a gas analyser which does not require further calibration and where the measurement of the gas concentration is very stable over different temperature levels. The reference 30 and active 34 detector circuits comprise one or more photodiode. The photodiodes are sensitive to temperature variations, similarly to other semiconductor devices. For example, the temperature coefficient of a typical UV enhanced photodiode is 0.1%/°C. By comparison, the ultraviolet light attenuation in the presence of ammonia in the absorption chamber is 0.075%/ppm for a 10 cm absorption path length. A small difference of the temperature-coefficient of each photodiode for the reference 30 and active 34 detectors may result of gas concentration measurements errors that must be compensated. This invention comprises a method to measure the drift of the optoelectronic components and compensate for said measured drift. The compensation method is described in the preferred embodiment described and as shown at
The method uses an emitter 24 that provides light emission outside of the absorption spectrum of the gas of interest, also referred as the optical compensation signal, an injection beam splitter 22 injecting the said optical compensation signal into the optical path of the absorption chamber 11. The method may include an antireflection cavity 26 adapted to absorb the useless signal passing through the beam splitter 22 that has not been injected in the optical path. As examples, the emitter 24 may be an heterostructure semiconductor laser, a vertical-cavity surface-emitting laser or a LED. As an example, and as a preferred embodiment, the emitter 24 is made with a 380 nm collimated LED. The injection beam splitter 22 is typically made of ultraviolet transmitting material, with or without coated surfaces, such as UV fused silica. It may be shaped as a right-angle prism, a pentaprism or other geometrical forms that split or divide the incident light in two beams. For example, and as a preferred embodiment, the injection beam splitter 22 may comprise a 1.5 mm thickness uncoated UV fused silica window having 4% of reflectivity on each surface.
The optical compensation signal is detected by both the reference 30 and the active 34 detectors. The microprocessor 62 calculates the ratio of the optical compensation signal falling on the active detector 34, also referred as CT, to the optical compensation signal falling on the reference detector 30, also referred as CR. The microprocessor 62 uses the compensation coefficient α to compensate for the short and long-term drift of optoelectronic components.
The compensation coefficient α0 which is equivalent to α but referring to the ratio of the compensation signal CT / CR under 0 ppm gas concentration.
The UV transmitted intensity IT is now related to the UV incident intensity IR by the following corrected Beer-Lambert law:
Referring now to
The equations eq(4) and eq(5) are valid for both the optical compensation signal generated by the emitted source 24 in the first embodiment and by the flashlamp/bandpass filter source presented in the second embodiment when the light pipe 13 is across the optical absorption path. The incident and transmitted intensity, IR and IT, are measured when the light pipe 13 is not across the optical absorption path
The light pipe 13 may be made of material not sensitive to the gas of interest and may have a cross-section shaped as a circle, a square, a hexagonal or any geometrical shape surrounding the optical beam in the absorption path. For example, and as a preferred embodiment, the light pipe 13 may be made of an ultraviolet transmitting material such as UV fused silica or quartz. The input and/or output surfaces may be flat and/or have a small bevel angle. The light pipe 13 may also have an antireflection coating on both input and output surfaces. In one embodiment, the light pipe 13 may be fabricated with an uncoated UV-fused silica rod of 25 mm diameter cross section with an input and output bevel angle of 8 to 12 degrees.
The light pipe 13 is maintained parallel or slightly tilted compared to the optical axis by two cylinders 17 and 19 each having two holes, one for supporting the light pipe 13 and another hole 15 for allowing the UV light to pass through the absorption path when measuring the gas concentration. The light pipe 13 may be periodically inserted into the optical absorption path to measure the compensation coefficient α.
As shown on
Referring now to
Referring now to
Still referring to
As an example, and as a preferred embodiment, the optomechanical assembly 27 may be attached to a linear rail 29 parallel to the optical axis. The optomechanical assembly 27 comprising the active detector 34 and the lens 32 is moved towards or away from the beam splitter 28. The assembly 27 is generally moved using a mechanical subsystem which may comprise a linear rail 29 positioned parallel to the optical axis, a captive worm screw 31 in a stepping motor 33 and two mechanical stops 35. In such embodiment, the rotation of the stepping motor moves the optomechanical assembly 27 on the rail 29 according to the direction of rotation of the stepping motor 33. Two physical positions programmed by two mechanical stops 35 define the position of the mechanical assembly 27 for both measuring the optical compensation coefficient α and the incident and transmitted intensity, IR and IT respectively. The compensation signal CT is sampled on the active detector 34 when the active detector 34 is close to the beam splitter 28, thus when the absorption path is short. The transmitted intensity IT is sampled on the active detector 34 when the active detector 34 is far from the beam splitter 28. Thus, when the absorption path is long. Other mechanical systems may be used to move the optomechanical assembly 27, such as belt driver linear actuator, rod-style actuator, or linear servo.
In a fourth embodiment and referring now to
The length of the absorption path may be shortened by inserting an optical element 41 into the collimated optical beam which may then deflect the signal towards the focusing lens 32 so that the energy measured by the active detector 34 is stronger than the energy measured in the long absorption path. The optical element 41 may also be a pivoting element allowing a first position in which the signal is deflected and a second position in which the signal is not deflected.
The Beer-Lambert law eq(2) is applied to calculate the gas concentration based on the ratio of the measured transmitted intensity IT to the measured incident intensity IR. The incident intensity, IR is measured when the optical element 41 is inserted into the optical beam. The transmitted intensity IT is measured when the optical element 41 is not present into the optical beam or pivoted not to deflect the signal. The correction coefficient ρ0 calculated in eq(3) compensates for the inherent differential optical intensity of UV light falling on the active 34 detectors at 0 ppm gas concentration for incident IR0 and transmitted IT0 intensities.
As an example, and as a preferred embodiment, the optical elements 41 and 47 may be prisms made of transparent material such a synthetic fused silica, but any other ultraviolet-transparent material such as quartz, CaF2 or MgF2 may be used. The incident angle on the prism input surface is preferably less than the Brewster angle for complete internal reflection on the opposite surfaces in the UV band. Other optical element 41 and 47 may be used to deflect the optical beam, such as a corner cube or aligned mirrors.
Now referring to
In another embodiment of the present invention, a method to periodically recalibrate the system 10 without the need of a known gas concentration in the absorption chamber is provided. The method comprises inserting a semi-transparent material 43 in the optical path such that the transmitted intensity is attenuated by a known value corresponding to a precise gas concentration. This method implies that the system has been previously characterized with a precise concentration gas sample compared to the attenuation element 43. For example, and as a preferred embodiment, the attenuation element 43 may be a simple window having 4% reflection on each surface but could be any other semi-transparent optical element in the UV band such as neutral density filter, band pass filter or broadband filter with or without coating. This embodiment is illustrated in
The long-term stability of the system 10 depends on the stability of certain element such as the bandpass filter 18. It is well known that bandpass filters change in centered wavelength and are influenced by the ambient relative humidity. Such elements will influence the long-term stability of the gas analyser 10. To avoid this drift, a system and method to maintain the bandpass filter 18 at a temperature higher than the internal temperature of the system 10 is provided. The method may allow for the temperature of the filter 18 to be higher than the dew point temperature of gases present in the system 10. A system may accordingly comprise a heating element 9 and a temperature sensor, not shown, in physical contact with the filter 18 to raise its temperature above the internal ambient temperature of the system 10.
. Now referring to
Referring the now to
Now referring to
The compensation signal CR is measured on the reference detector 30 and the compensation signal CT on the active detector 34 to provide the compensation coefficient α of the known ppm concentration. The coefficient K is finally calculated in C6 with eq(7) by measuring the incident intensity IR, and the transmitted intensity IT with the flashlamp. The embodiment with the moving prism architecture is a simplified version of the ones having two detectors. There is no compensation signal and the compensation coefficients α and α0 in all equation must be replace by 1 for both.
The gas concentration is simply measured by rewriting eq(7) as follow.
Referring now to
Certain aspects of the present invention include process steps and sequences described herein in the form of a sequence. It should be noted that the sequence necessary to measure the gas concentration could be embodied in software, firmware, or hardware, and when embodied in firmware, could reside and be operated from different platforms used by a variety of operating systems.
An advantage of the present invention is to provide an UV non-dispersive gas analyser that is insensitive for the presence of interfering gas, such as CO2, O2, CO, CH4 and /or water vapor. According to another embodiment, the present invention provides the advantage to be insensitive to the light emission spectrum degradation due to lamp aging effects provided. Finally, this invention further comprises methods to compensate for short and long terms drift of the components. This method may further comprise a gas analyser which does not require further calibration and where the measurement of the gas concentration is very stable over temperature and lifetime differences.
While illustrative and presently preferred embodiment(s) of the invention have been described in detail hereinabove, it is to be understood that the inventive concepts may be otherwise variously embodied and employed and that the appended claims are intended to be construed to include such variations except insofar as limited by the prior art.
The present patent application claims the benefits of priority of American Pat. Application No. US 62,991,885, entitled “METHOD AND APPARATUS FOR LONG TERM ACCURATE MEASUREMENT OF AMMONIA GAS CONCENTRATION IN A PERMANENT AMMONIA GAS ENVIRONMENT” and filed at the United States Patent and Trademark Office on Mar. 19, 2020, the content of which is incorporated herein by reference.
Filing Document | Filing Date | Country | Kind |
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PCT/CA2021/050371 | 3/19/2021 | WO |
Number | Date | Country | |
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62991885 | Mar 2020 | US |