WO2019204906A1 - Système de séchage, système de surveillance et d'étalonnage de volatils et procédé associé - Google Patents

Système de séchage, système de surveillance et d'étalonnage de volatils et procédé associé Download PDF

Info

Publication number
WO2019204906A1
WO2019204906A1 PCT/CA2019/050463 CA2019050463W WO2019204906A1 WO 2019204906 A1 WO2019204906 A1 WO 2019204906A1 CA 2019050463 W CA2019050463 W CA 2019050463W WO 2019204906 A1 WO2019204906 A1 WO 2019204906A1
Authority
WO
WIPO (PCT)
Prior art keywords
calibration
designated
flow rate
mass flow
sample
Prior art date
Application number
PCT/CA2019/050463
Other languages
English (en)
Inventor
Gilles ROBERTSON
Patrick Mercier
Original Assignee
National Research Council Of Canada
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 National Research Council Of Canada filed Critical National Research Council Of Canada
Publication of WO2019204906A1 publication Critical patent/WO2019204906A1/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
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
    • 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
    • G01N21/27—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using photo-electric detection ; circuits for computing concentration
    • G01N21/274—Calibration, base line adjustment, drift correction
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N2021/3595—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using FTIR

Definitions

  • the present disclosure relates to drying systems and volatile monitoring and analysis systems, and, in particular to a drying system, volatile monitoring and calibration system and method therefor.
  • IR infrared
  • FTIR Fourier Transform infrared spectroscopy
  • the tailings produced by the extraction processes of bitumen from oil sands are also important because a lack of water may result in excessive dust formation and equipment breakdown during the large scale drying processes used to recover the residual solvent from the treated sand.
  • samples of ore, process stream and solvent-diluted bitumen products are analysed routinely to determine their bitumen, water, solids and hydrocarbon solvent contents. Two methods are usually considered. The first one, the Karl Fisher titration technique, is mostly used for determination of water contents in solvent-diluted bitumen products.
  • the second one is most widely used to measure the bitumen, water, solids and solvent contents in oil sands ore and related process streams and products.
  • These two methods have been the industry standard for decades.
  • both the Karl Fisher and Soxhlet-Dean and Stark extraction methods have some considerable drawbacks. They both demand extensive and time-consuming laboratory manipulations, the use of specific chemicals, and a need for solvent disposal. Moreover, the precision of both methods on the hydrocarbon solvent content is poor.
  • some aspects of the herein described embodiments provide a system and method for measuring and/or monitoring evolved gas(es), for example, evolved from a heated sample in a drying system, such as a Large Scale Drying System (LSDS) or furnace.
  • LSDS Large Scale Drying System
  • the systems and methods considered herein provide for selective and/or quantitative monitoring of volatile components evolved from a heated sample.
  • a system and method are provided for measurement of water and hydrocarbon solvent contents within a sample that is fast, does not require a large amount of manipulations and/or does not require specific chemicals beyond chemicals that may be required in embodiments including system calibration and/or recalibration (e.g. naphta, water) of the FTIR module.
  • system calibration and/or recalibration e.g. naphta, water
  • a sample analysis system for analyzing one or more volatile components evolved from a sample and entrained under designated exhaust conditions, the system comprising: a Fourier Transform Infrared (FTIR) spectrometer operable to fluidly interface with the one or more volatile components being entrained to generate a signal representative of an infrared absorbance spectrum representative of the one or more volatile components; and a digital data processor operable to monitor for a designated volatile component of interest by automatically: extracting from said signal an absorbance signature corresponding to said designated volatile component to be monitored; converting said absorbance signature to a mass flow rate value based on a previously established calibration relationship between said signature and said mass flow rate value; and quantifying an absolute mass value over time for said designated volatile component of interest based on said converting.
  • FTIR Fourier Transform Infrared
  • the system further comprises a calibration module comprising: a calibration liquid injection device for injecting a known mass of a calibration liquid at two or more designated mass flow rates; and a heater operable to vaporize said calibration liquid to produce said designated volatile component of interest to be entrained under the designated exhaust conditions to interface with said FTIR spectrometer during calibration.
  • the system further comprises a calibration module comprising: a calibration liquid injection device for injecting a known mass of a calibration fluid; a heater operable to completely vaporize said calibration liquid to produce said designated volatile component of interest during calibration; and a mass flow controller operable to control a mass flow rate of said designated volatile component of interest during calibration to be entrained under the designated exhaust conditions during calibration for at least two designated mass flow rates.
  • a calibration liquid injection device for injecting a known mass of a calibration fluid
  • a heater operable to completely vaporize said calibration liquid to produce said designated volatile component of interest during calibration
  • a mass flow controller operable to control a mass flow rate of said designated volatile component of interest during calibration to be entrained under the designated exhaust conditions during calibration for at least two designated mass flow rates.
  • the digital data processor is further operable to automatically derive said calibration relationship between said absorbance signature of said designated volatile component of interest produced by vaporizing said calibration fluid at said two or more flow rates.
  • the calibration liquid injection device comprises a syringe pump.
  • the digital processor is further operable to concurrently monitor for two or more designated volatile components of interest.
  • the two or more designated volatile components of interest are associated with respective overlapping absorbance signatures, and wherein said digital data processor is operable to automatically distinguish said respective overlapping absorbance signatures via multivariate analysis.
  • the one or more designated volatile components of interest comprise at least one of water, one or more organic solvents, toluene, cyclohexane, pentane or naphtha.
  • the designated exhaust conditions comprise at least one of a temperature controlled chimney or a substantially constant purge gas flow rate.
  • the sample comprises at least one of oil sand ore, an oil sand process stream, an oil sand process feed, an oil sands process tailings or a product associated with a process unit used in oil sands bitumen production operations.
  • the system further comprises a furnace for heating the sample, wherein said heating generates the one or more volatile components; a purge gas input for flowing a purge gas at a substantially constant flow rate into said furnace, wherein said purge gas is substantially transparent to infrared and entrains said one or more volatile components; and an exhaust for exhausting said one or more volatile components and purge gas from said furnace under the designated exhaust conditions.
  • the purge gas is nitrogen.
  • the system further comprises a sampling line in fluid communication with said exhaust to sample said one or more volatile components flowing therethrough, wherein said FTIR operatively interfaces with said sampling line to generate said signal.
  • a sample analysis method for analyzing a sample comprising: entraining one or more volatile components evolving from the sample under designated exhaust conditions; sampling said entrained one or more volatile components using a FTIR spectrometer to generate a signal representative of an infrared absorbance spectrum thereof; and using a digital data processor: extracting from said signal an absorbance signature corresponding to a designated volatile component to be monitored; converting said absorbance signature to a mass flow rate value based on a previously established calibration relationship between said signature and said mass flow rate value; and quantifying an absolute mass value over time for said designated volatile component of interest based on said converting.
  • the method further comprises heating the sample to generate the one or more volatile components.
  • the entraining comprises entraining at a substantially constant flow rate.
  • the method further comprises calibrating the system by: injecting a known mass of a calibration liquid at a designated mass flow rate; vaporizing said injected calibration liquid; entraining said vaporized calibration liquid under said designated exhaust conditions; sampling said vaporized calibration liquid using said FTIR spectrometer to generate a calibration signal representative of a calibration infrared absorbance spectrum thereof; and using said digital data processor: extracting from said calibration signal a calibration absorbance signature corresponding to said vaporized calibration liquid; and associating said calibration absorbance signature with said designated mass flow rate; and repeating for two or more designated mass flow rates to establish said calibration relationship.
  • the method further comprises calibrating the system by: vaporizing a known mass of a calibration liquid; injecting said vaporized calibration liquid at a designated mass flow rate; entraining said vaporized calibration liquid under said designated exhaust conditions; sampling said vaporized calibration liquid using said FTIR spectrometer to generate a calibration signal representative of a calibration infrared absorbance spectrum thereof; and using said digital data processor: extracting from said calibration signal a calibration absorbance signature corresponding to said vaporized calibration liquid; and associating said calibration absorbance signature with said designated mass flow rate; and repeating for two or more designated mass flow rates to establish said calibration relationship.
  • the digital data processor is further operable to automatically derive and subsequently apply said calibration relationship between said absorbance signature of said designated volatile component of interest produced by processing said calibration fluid at said two or more flow rates.
  • the method further comprises repeating said calibrating for two or more distinct calibration liquids.
  • a calibration method for quantitative monitoring of a designated volatile component of interest evolved from a sample in a designated sample processing system comprising: vaporizing a calibration liquid into the designated volatile component of interest to be entrained through the designated sample processing system under designated exhaust conditions at a designated mass flow rate; measuring an infrared absorbance signature of the designated volatile component of interest so entrained; associating said infrared absorbance signature with said designated mass flow rate; repeating for at least one distinct designated mass flow rate; and deriving from each said association a calibration function relating subsequent infrared absorbance signature measurements of the designated volatile component of interest to a corresponding mass flow rate evolving from an unknown sample under said designated exhaust conditions.
  • the method is further repeated for two or more calibration liquids.
  • the vaporizing first comprises injecting a known mass of said calibration liquid into the processing system to be vaporized and thereby entrained under said designated exhaust conditions.
  • the vaporizing comprises vaporizing a known mass of said calibration liquid and injecting said vaporized calibration liquid at said designated mass flow rate into the processing system.
  • the processing system is a furnace system and wherein said designated exhaust conditions comprise a substantially constant purge gas flow rate.
  • a calibration module for quantitative monitoring of a designated volatile component of interest evolved from a sample in a sample processing system, the calibration module comprising: a calibration liquid injection device for injecting a known mass of a calibration liquid at two or more designated mass flow rates; a heater operable to vaporize said calibration liquid to produce said designated volatile component of interest during calibration to be entrained through the processing system toward an exhaust FTIR sample line of the processing system under designated exhaust conditions; a digital data processor operatively coupled to an FTIR spectrometer disposed in relation to said sampling line to generate respective signals representative of an infrared absorbance spectrum associated with said designated volatile component of interest, wherein said digital data processor is operable to: extract an infrared absorbance signature of the designated volatile component of interest corresponding to each of said designated mass flow rates from said respective signals; and derive a calibration relationship relating each said infrared absorbance signature with said corresponding designated mass flow rates to relate subsequent infrared absorbance signature measurements of the designated volatile component
  • the digital data processor is further operable to automatically derive said calibration relationship.
  • the calibration liquid injection device comprises a syringe pump.
  • the digital processor is further operable to sequentially derive a respective calibration relationship for two or more designated volatile components of interest using distinct calibration liquids.
  • the designated volatile component of interest is selected from at least one of water, one or more simple organic solvents or naphtha.
  • the sample is selected from at least one of oil sand ore or a processed oil sand ore product.
  • the relationship comprises at least one of a linear relationship and a non-linear relationship.
  • the sample processing system comprises a furnace system.
  • the designated exhaust conditions comprise a substantially constant purge gas flow rate.
  • a sample analysis system for analyzing a sample, comprising: a furnace for heating the sample, wherein said heating generates one or more volatile components; a purge gas input for flowing a purge gas at a substantially constant flow rate into said furnace, wherein said purge gas is substantially transparent to infrared and entrains said one or more volatile components; an exhaust for exhausting said one or more volatile components and purge gas from said furnace; an FTIR spectrometer operable to generate a signal representative of an infrared absorbance spectrum representative of said one or more volatile components being exhausted; and a digital data processor operable to monitor for a designated volatile component of interest by automatically: extracting from said signal an absorbance signature corresponding to said designated volatile component to be monitored; converting said absorbance signature to a mass flow rate value based on a previously established calibration relationship between said signature and said mass flow rate value; and quantifying an absolute mass value over time for said designated volatile component of interest based on said converting.
  • the system further comprises a calibration module comprising: a calibration liquid injection device for injecting a known mass of a calibration liquid at two or more designated mass flow rates to be entrained by said purge gas; and a heater operable to vaporize said calibration liquid to produce said designated volatile component of interest during calibration.
  • a sample analysis method for analyzing a sample in a drying system comprising: heating the sample in the drying system to generate one or more volatile components; entraining the one or more volatile components toward an exhaust at a substantially constant flow rate; sampling said entrained one or more volatile components using a FTIR spectrometer to generate a signal representative of an infrared absorbance spectrum thereof; and using a digital data processor: extracting from said signal an absorbance signature corresponding to a designated volatile component to be monitored; converting said absorbance signature to a mass flow rate value based on a previously established calibration relationship between said signature and said mass flow rate value; and quantifying a total mass value for said designated volatile component of interest based on said converting.
  • the method further comprises calibrating the system by: injecting a known mass of a calibration liquid at a designated mass flow rate; vaporizing said injected calibration liquid; entraining said vaporized calibration liquid at said substantially constant flow rate; sampling said vaporized calibration liquid using said FTIR spectrometer to generate a calibration signal representative of a calibration infrared absorbance spectrum thereof; and using said digital data processor: extracting from said calibration signal a calibration absorbance signature corresponding to said vaporized calibration liquid; and associating said calibration absorbance signature with said designated mass flow rate; and repeating for two or more designated mass flow rates to establish said calibration relationship.
  • Figure 1 is a diagram of a drying system, such as a Large Scale Drying System (LSDS), with selective and/or quantitative monitoring of volatile components evolved from a heated sample, in accordance with one embodiment
  • Figure 2 is a diagram of a calibration method for quantitative monitoring of a designated volatile component of interest evolved from a heated sample, in accordance with one embodiment
  • Figure 3 is a diagram of a drying system, such as a LSDS, further comprising a Vapor Generator System (VGS) for calibrating the system using a method such as shown in Figure 2, in accordance with one embodiment;
  • VGS Vapor Generator System
  • Figure 4 is a diagram of a volatile monitoring system attachment, operatively coupled to a conduit of an existing device, wherein one or more volatile components are flowing, according to one embodiment
  • Figure 5 is an exemplary plot of FTIR absorbance values measured for water as a function of mass flow rate
  • Figure 6 is an exemplary plot of two calibration curves used to extract the functional relationship between mass flow rate and IR absorbance values obtained using a calibration method applied to an exemplary embodiment of a drying system as described herein;
  • Figure 7 is an exemplary plot showing the effects of a flow rate of purge gas on a calibration curve for water, in accordance with one embodiment; and
  • Figures 8 A and 8B are exemplary plots showing IR absorbance of water and naphtha evolved from a model mixture containing bitumen and solids as a function of time, and a rate of change of absorbance as a function of time for naphtha, respectively, in accordance with one embodiment.
  • elements may be described as“configured to” perform one or more functions or“configured for” such functions.
  • an element that is configured to perform or configured for performing a function is enabled to perform the function, or is suitable for performing the function, or is adapted to perform the function, or is operable to perform the function, or is otherwise capable of performing the function.
  • language of“at least one of X, Y, and Z” and“one or more of X, Y and Z” may be construed as X only, Y only, Z only, or any combination of two or more items X, Y, and Z (e.g., XYZ, XY, YZ, ZZ, and the like). Similar logic may be applied for two or more items in any occurrence of“at least one ” and“one or more...” language.
  • a drying system such as a Large Scale Drying System (LSDS), and volatile monitoring and calibration system and method therefor.
  • LSDS Large Scale Drying System
  • a Large Scale Drying System consistent with the embodiments and examples described herein may include a calibrated monitoring system that provides for selective and/or quantitative monitoring of volatile components evolving from a heated sample. Calibration tools and/or methods are also considered herein for the calibration and effective operation of such drying systems once so calibrated.
  • some of the embodiments considered herein invoke a system in which a solid-liquid sample is heated under controlled conditions and evolved volatile components produced therein are transported into a purge gas flow and sampled by a Fourier Transform Infrared (FTIR) spectrometer, for instance in the context of a multicomponent FTIR (quantitative) gas analysis, wherein a measured absorbance infrared (IR) value representative of the volatile component of interest can be taken and converted into a mass flow rate value for this volatile component based on a pre-established calibration of the system.
  • FTIR Fourier Transform Infrared
  • multiple volatile components of interest can be monitored concurrently based on respective IR absorbance signatures and corresponding calibrations, that is, such that respective total mass flow rates and absolute total mass outputs can be resolved and distinguished concurrently for each of the two or more volatile components of interest evolving from a same sample and sample analysis heating process.
  • a total (absolute) mass of the component s) evolved from the sample as a function of time may be determined with precision and used to effectively measure the total mass of such component(s) evolved from a drying sample.
  • concentration i.e. the mass per unit volume
  • the herein described embodiments seek to quantify a mass of evaporated material of interest from a drying sample, which can be identified using the calibration tools and methods described herein from measured volatile flow rates.
  • a sample analysis system in the form of a drying system such as a LSDS and generally referred to using the numeral 100, will now be described.
  • the system 100 is configured to provide quantitative, and optionally selective or concurrently quantitative monitoring of volatile components in a heated sample and is interchangeably referred to herein as a quantitative LSDS or q-LSDS).
  • the system 100 generally comprises a (sealed) furnace 102, for controlled drying of a sample 104.
  • Sample 104 may be, for instance, a tailings sample which contains various levels of solids, water, solvent (e.g. naphtha) and/or bitumen content, for example, though other samples may also or alternatively be considered.
  • the furnace 102 may consist of a steel vessel equipped with a hermetic lid, for example, though other furnace structures and/or configurations may readily be considered. For instance, different furnace sizes and/or dimensions may be considered depending on the nature, dimensions, shape and/or like attributes of the samples to be dried, i.e. to accommodate smaller or larger samples.
  • the furnace 102 will be temperature controlled.
  • the temperature is controlled by using a temperature controller operatively connected to a heating tape and a thermocouple.
  • furnace 102 further comprises a sample holder 106 and a sample pan 107 for holding sample 104.
  • heating of sample 104 will result in the emission of evolved gases 108, which are to subject to monitoring as will be further detailed below.
  • the furnace further comprises a purge gas input
  • the purge gas which will generally be selected to be a substantially IR-transparent gas, such as but not limited to Nitrogen (N 2 ), though other gases may also be used, is shown as sourced form a purge gas source 112, for example.
  • This source 112 is itself connected to a mass flow controller 114 to precisely control the constant flow of purge gas into furnace 102.
  • the purge gas is further heated before entering the furnace with a purge gas pre-heater 116 to avoid cooling the evolved gases before they reach the downstream spectrometer 126 (discussed below).
  • the sample 104 once heated, can produce one or more volatile components that are entrained by the constant flow of purge gas towards an exhaust or open-ended exit port 118.
  • the exit port 118 may be temperature controlled as well, for instance, to ensure or at least assist in maintaining the volatile components at a substantially same temperature as the furnace, which may improve the quality of volatile component monitoring measurements.
  • the volatile components may have a lower temperature than expected when a large sample mass is inserted into the furnace, and thus benefit from further heating at the exit port to reduce the influence different sample dimensions may have on calibrated measurements.
  • exit port 118 should also be large enough to avoid pressure build-ups in the furnace during fast evaporations as this may increase the vapor temperature above the furnace’s expected temperature.
  • this exit port may take the form of a chimney or like structures readily known in the art.
  • a sampling line 120 is operatively connected with exit port 118 so as to sample the gases flowing therethrough, for example, under action of a sampling pump 122 or like configuration.
  • the sampled gases entering the sampling line 120 are pulled into the open-ended probe or gas cell 124 of a Fourier Transform Infrared (FTIR) spectrometer 126.
  • the FTIR spectrometer is used to take IR absorbance measurements of designated volatile component(s) flowing through the sample line in real-time.
  • the pump 122 is optimized for the shortest travel time of vapors in the sampling line (transfer line) and FTIR gas cell without compromising the sensitivity.
  • adjustable system components may allow for system and/or performance optimizations that can be addressed by adequate system calibration, as discussed further below.
  • the gases travelling through the FTIR’s (heated) gas cell are subjected to a beam of infrared (IR) radiation.
  • the gas molecules absorb some of the IR radiation energy, which is then translated into molecular bond vibrational energy, and what is left of the infrared radiation (unabsorbed) is then measured.
  • the resulting data thus takes the form of an absorption spectrum, for example, that can be produced every few seconds in some embodiments depending on scanning rate.
  • Specific bonds for example a C-H bond in an organic solvent molecule or a O-H bond in a water molecule, absorb light of different wavelength, meaning that each molecule has a characteristic absorbance signature.
  • the FTIR spectrometer 126 is further operatively connected to a digital data processor and data recording device, schematically illustrated herein as processor 128, which records the spectral absorbance measurements generated by the FTIR spectrometer 126 at specific preselected wavelengths chosen to characterize the absorbance signature of one or more selected volatile component(s) of interest.
  • processor 128 records the spectral absorbance measurements generated by the FTIR spectrometer 126 at specific preselected wavelengths chosen to characterize the absorbance signature of one or more selected volatile component(s) of interest.
  • the absorbance signatures of each of the monitored volatile components may be well defined and distinct (e.g., a single narrow peak). They may therefore simply be monitored for the selected wavelengths associated with those signatures (e.g., peak absorbance). However, it may also be that one or more volatile components being monitored have more complex absorption spectra, such as a broader spectrum and/or comprising of two or more peaks. Measuring such components may result in overlapping spectral features from two or more components. In this case, multivariate statistical analysis methods may be applied to extract a singular signature for each overlapping component.
  • these may include, without limitation: linear (or non-linear) multivariate regression (MVR), principal component analysis (PCA), principal component regression (PCR), discriminant analysis (DA), hierarchical cluster analysis (HCA), soft independent modeling of class analogy (SIMCA), or similar.
  • MVR multivariate regression
  • PCA principal component analysis
  • PCR principal component regression
  • DA discriminant analysis
  • HCA hierarchical cluster analysis
  • SIMCA soft independent modeling of class analogy
  • complex overlapping spectral signatures may be precisely identified and distinguished in respectively characterising two or more volatile components of interest.
  • a captured absorbance signature may then be converted into a mass flow rate value of this selected volatile component based on a previously established calibration relationship, which will be described in further detail below.
  • a partial or total evolved mass of the selected volatile component of interest can be computed as a function of time, for example, which can be used to compute a total constituent mass of this component within the sample. In doing so, one can then accurately determine a content of this component within a given production volume from which the sample was taken, useful information, for example, in evaluating the extraction, processing and solvent recovery efficiency, for example, for a given content extraction process, e.g. such as within the context of oil sands ore extraction and related downstream products produced thereby.
  • the processor 128 may take various forms, which may include, but is not limited, a dedicated computing or digital processing device, a general computing device, tablet and/or smartphone interface/application, and/or other computing device as may be readily appreciated by the skilled artisan, that includes a digital interface to an FTIR spectrometer output so to acquire and ultimately process readings/spectra captured thereby.
  • results of the sample analysis may be output locally via a graphical user interface operatively associated with the processor 128, or again communicated to a communicatively linked device or interface, such as a computer with digital display screen, tablet, smartphone application or like general computing device, or again to a dedicated device having a graphical or digital display readout amenable for producing consumable analytical results.
  • a communicatively linked device or interface such as a computer with digital display screen, tablet, smartphone application or like general computing device, or again to a dedicated device having a graphical or digital display readout amenable for producing consumable analytical results.
  • analytical outputs whether fully processed or delivered in partially processed and consumable form, can be relayed locally to an operator and/or distributed over a network connection, for example, for further analysis and/or consideration.
  • a calibration method 200 for quantitative monitoring of a designated volatile component of interest evolved from a heated sample will now be described.
  • This method enables the determination of the quantitative calibration relationship between an absorbance signature of a designated volatile component measured using a FTIR spectrometer (such as that shown in the embodiment of Figure 1) and its mass flow rate (or evaporation rate) inside the apparatus. From this quantitative relationship, the total mass of this designated volatile component evaporated from the heated sample may be calculated as a function of time.
  • the first step 205 concerns choosing the operational parameters of the heating system. This includes any parameter that may affect the quality of the measured IR absorbance values of the FTIR spectrometer.
  • these include the type of purge gas used, the purge gas flow rate, the temperature of the furnace and other heated components (e.g. purge gas pre-heater, exit port and/or sampling line). If the vapors sampled by the FTIR probe are not at the same temperature as the calibration temperature then the absorbance data may be impacted. Moreover, it is understood that no physical alterations (i.e. dimensions, etc.) should done on the device between the calibration procedure and the measurements of a heated sample, as these could also affect the measurements. [0080] Once the operational parameters are decided, in the next step 210, one may select a calibration fluid which vaporizes into a designated volatile component.
  • the calibration method 200 further uses a calibration subsystem for vaporizing the selected calibration fluid inside the heating system at a controlled mass flow rate.
  • this apparatus may comprise a fluid injection system coupled to a liquid heater, as will be described with reference to the embodiment of Figure 3 below.
  • Other embodiments may use different calibration subsystems.
  • the calibration fluids may be vaporized first and then introduced into the heating system using a mass flow controller.
  • Step 220 is a pre-calibration procedure wherein the VGS (Vapor Generator System) itself is calibrated with the chosen calibration fluid to ascertain a good control over the mass flow rate of vapors introduced into the system during the calibration procedure proper.
  • VGS Vehicle Generator System
  • a desired mass flow rate is chosen for the vapors of the calibration fluid. In principle, any mass flow rate may be chosen, as long as it doesn’t impede total vaporization of the calibration fluid inside the apparatus or lead to pressure build-ups. However, one would usually choose values close to the expected mass flow rate of evaporation during a subsequent measurement.
  • the next step (240) is to vaporize the calibration fluid at the designated mass flow rate.
  • the liquid may be pre-weighted and introduced into the purge gas line using a vaporization system at a controlled injection rate using suitable equipment such as a syringe pump or like injection system. It will be appreciated that different means of introducing the vapors of the calibration fluid inside the apparatus at a controlled mass flow rate may be chosen without departing from the general scope and nature of the present disclosure.
  • step 250 the vapors of the calibration liquid enter the furnace and are entrained toward the exit port, where they can be sampled by the FTIR spectrometer, which is operated to measure the absorbance signature corresponding to a designated volatile component for which the apparatus is being calibrated.
  • step 260 the data pair represented by the known mass flow rate and the measured absorbance signature is recorded. Once this measurement is complete, the procedure may be repeated (270) from step 230 but using a different mass flow rate.
  • step 280 a quantitative functional relationship describing the data is extracted. In the limiting case of two data points, only a linear relationship may be used but, in some cases, the functional relationship may be more complex, as will be seen later. It is generally agreed that the more calibration data points one acquires allows for a better functional relationship to be extracted. For larger sets of data points, any functional form which fits the data well may be used, including higher degree polynomials.
  • step 290 another component for calibration.
  • a multivariate calibration may be alternatively or additionally executed to address two or more volatile components having overlapping spectral features (as introduced above), by using mixtures of the two or more components, for example, uniformly mixed and inserted into the system at multiple known flow rates one after the other.
  • step 220 The steps are then repeated from step 220 wherein another calibration fluid is chosen.
  • the process may be repeated for any number of designated volatile components.
  • the device Once the calibration procedure is complete, the device may then be used with an unknown sample, and the volatile component(s) of interest evolving therefrom quantitatively monitored accordingly. Namely, measured IR absorption signatures corresponding to designated volatile component s) of interest for which the device was calibrated may be converted to a mass flow rate value for this designated volatile component. Hence, the mass of one or more designated volatile components from a heated sample may be measured and monitored in real-time.
  • a q-LSDS system generally referred to using the numeral 300, and operable to be calibrated using an embodiment of the calibration method described above with reference to Figure 2, will now be described.
  • the system 300 is similar to the one described above with reference to Figure 1, in that it also generally comprises a (sealed) furnace 302 for controlled drying of a sample 304 from a sample holder 306 and a sample pan 307, or like configuration, which will generally result in the emission of evolved gases 308 to be monitored.
  • the furnace 302 again comprises a purge gas input 310 for flowing a IR- transparent purge gas at a substantially constant flow rate into furnace 302 from a purge gas source 312, for example.
  • a purge gas mass flow controller 314 and pre-heater 316 are also provided to control the substantially constant flow of purge gas into furnace 302 and pre-heat the purge gas accordingly.
  • the sample 304 once heated, can again produce one or more volatile components that are entrained by the constant flow of purge gas towards an exhaust or open-ended (temperature controlled) exit port 318, such as a chimney or like structure.
  • an exhaust or open-ended (temperature controlled) exit port 318 such as a chimney or like structure.
  • a sampling line 320 is operatively connected with exit port 318 so as to sample the gases flowing therethrough, for example, under action of a sampling pump 322 or like configuration.
  • the sampled gases entering the sampling line 320 are pulled into the open-ended probe or gas cell 324 of a Fourier Transform Infrared (FTIR) spectrometer 326 to acquire IR absorbance spectra, as described above.
  • FTIR Fourier Transform Infrared
  • the FTIR spectrometer 326 is further operatively connected to a digital data processor and data recording device, schematically illustrated herein as processor 328, which records the spectral absorbance measurements generated by the FTIR spectrometer 326 at specific preselected wavelengths chosen to characterize the absorbance signature of one or more selected volatile component(s) of interest.
  • This absorbance signature may then be converted into a mass flow rate value of this selected volatile component based on a previously established calibration relationship, as described above. From these mass flow rate values, a partial or total evolved mass of the selected volatile component of interest can be computed as a function of time, for example.
  • the system 300 illustrated in Figure 3 further comprises a calibration subsystem, schematically illustrated and referred to herein as a vapor generator system (VGS) 350.
  • VGS vapor generator system
  • the VGS is operable to calibrate the system 300 using known quantities of one or more calibration fluids (e.g. water, naphtha, etc.) that can be vaporized and entrained through the system to be measured using the FTIR equipment, and thus used to produce reliable calibration metrics to be applied to subsequent measurements.
  • the VGS 350 is operable to generate a stable and constant mass flow rate of hot vapors of a designated volatile component that can be entrained to flow in the FTIR gas cell 324 at a known temperature.
  • the VGS 350 comprises an injection system 352 that can inject a calibration fluid 354 into a temperature-controlled calibration liquid heater 356 connected to the purge gas line 310 of the q-LSDS 300 that vaporizes the calibration liquid whose quantifiable vapors are entrained by the purge gas to be sampled by the FTIR probe 326.
  • the injection system 352 comprises a syringe and a syringe pump, although other systems may be used to inject a controlled amount of calibration fluid into the system during calibration, and that, without departing from the general scope and nature of the present disclosure.
  • the calibration fluid 354 is injected at a known mass flow rate. Using the calibration liquid heater 356, or like equipment, the calibration fluid can be completely vaporized before it reaches the purge gas line 310 to be entrained thereby.
  • the calibration fluid 354 may be injected directly into the purge gas pre-heater 316, as can other vaporization and injection techniques be considered without departing from the general scope and nature of the present disclosure.
  • system 405 which may be a scientific measuring apparatus and/or part of an industrial processing apparatus, comprises any system or apparatus by which one or more volatile component is generated, for instance but not limited to, a furnace, an exhaust from an internal combustion engine, etc. This includes any means by which one or more volatile component is produced from a solid-liquid or liquid substance.
  • the described embodiment has the advantage of being easily calibrated and used without the need to extensively modify the pre-existing system 405.
  • the gases flowing through port 410 may be directed to another subsystem 415 or directed to the outside air.
  • the sampling line 420 is operatively connected with exit port 410 so as to sample the gases flowing therethrough, for example, under action of a sampling pump 422 or like configuration.
  • the sampled gases entering the sampling line 420 are pulled into the open-ended probe or gas cell 424 of a Fourier Transform Infrared (FTIR) spectrometer 426 to acquire IR absorbance spectra, as described above.
  • FTIR Fourier Transform Infrared
  • the FTIR spectrometer 426 is further operatively connected to a digital data processor and data recording device, schematically illustrated herein as processor 428, which records the spectral absorbance measurements generated by the FTIR spectrometer 426 at specific preselected wavelengths chosen to characterize the absorbance signature of one or more selected volatile component(s) of interest.
  • This absorbance signature may then be converted into a mass flow rate value of this selected volatile component based on a previously established calibration relationship, as described above. From these mass flow rate values, a partial or total evolved mass of the selected volatile component of interest can be computed as a function of time, for example.
  • the described embodiment further comprises a VGS 448, which may be operatively connected to pre-existing system 405 via an input port 450.
  • the VGS is operable to calibrate the monitoring system 400 using known quantities of one or more calibration fluids (e.g. water, naphtha, etc.) that can be vaporized and entrained through the pre-existing system 405 to be measured using the FTIR equipment, and thus used to produce reliable calibration metrics to be applied to subsequent measurements.
  • the VGS 448 is operable to generate a stable and constant mass flow rate of hot vapors of a designated volatile component that can be entrained to flow in the open-ended FTIR gas cell 424 at a known temperature.
  • the VGS 448 comprises an injection system 452 that can inject a calibration fluid 454 into a temperature-controlled calibration liquid heater 456 that vaporizes the calibration liquid whose quantifiable vapors are entrained within pre-existing system 405 and exited through exit port 410 to be sampled by the FTIR probe 426.
  • the injection system 452 comprises a syringe and a syringe pump, although other systems may be used to inject a controlled amount of calibration fluid into the system during calibration, and that, without departing from the general scope and nature of the present disclosure. As mentioned previously, depending on the injection system chosen, it may be necessary to first calibrate the injection system itself before proceeding with the calibration procedure proper.
  • injection system 452 this is done by pumping a calibration liquid using the syringe and syringe pump and measuring the weight of liquid delivered over a period of time, using a precision balance for instance. From these measurements, the injection flow rate in grams per minute may then be precisely controlled for calibration of the monitoring system 400.
  • the system 405 may be operable to precisely control the mass flow rate of the one or more volatile component.
  • the monitoring device may be calibrated using the method described before but without the need for a VGS.
  • a q-LSDS consists of one-liter vessel wrapped into heating tape for heating. Such an embodiment is optimized for sample masses ranging from 10 to 100 grams of materials.
  • a secondary heat source in the form of a copper coil is also provided to carry a hot purge gas into the furnace.
  • an exhaust of the furnace is of the same size copper tubing as a purge gas inlet into the furnace.
  • the temperature inside the furnace is monitored by installing a thermocouple between the outside wall and the insulation in order to avoid sudden heat fluctuations.
  • a temperature- controlled setting of 275°C for the heating tape provided a temperature reading of 250°C inside the furnace, just above an enclosed sample pan.
  • a VGS for vaporizing calibration liquids is also included, which includes a syringe and a syringe pump for injecting the calibration liquid into a purge gas pre-heater system set within a temperature range of 220°C to 240°C.
  • the calibration liquids entering the purge gas pre-heater at a known flow rate were completely vaporized.
  • the vapors were stabilized by entering a temperature-controlled heating coil, comprised of a copper tubing system, before entering the furnace.
  • the syringe pump was first calibrated using specific syringe sizes and pump settings for both water and naphtha.
  • the weight of the liquids was measured using a precision balance with an accuracy of +/- 0.0001 g.
  • the calibration for these two liquids provided one of the parameters used for the FTIR calibration, the flow rate in grams per minute of the liquids.
  • the second step involved vaporizing the calibration liquids using the VGS before sampling the vapours by the FTIR probe.
  • the calibration method is based, as mentioned earlier, on vaporizing at a series of known mass flow rates a selected liquid substance in the VGS and measuring the corresponding IR absorbance values with the FTIR at the selected wavelength characteristic of this selected substance.
  • the system was calibrated for measuring water and naphtha evolved from drying a set of samples.
  • the infrared absorbance of water (O-H bond 3744 cm 1 ) and naphtha (C-H bond 2878 cm 1 ) were correlated with different injection flow rates of the respective substances into the VGS.
  • Figure 4 shows a plot of the FTIR absorbance intensity signal for water (3744 cm 1 ) detected as a function of time during which water was injected in the VGS.
  • FTIR absorbance response with the flow rate of the substance as delivered by the syringe pump.
  • Figure 6 shows the syringe pump flow rate of vaporized liquid passing through the VGS at 250°C as a function of the infrared absorbance intensity for water (3744 cm 1 ) and naphtha (2878 cm 1 ). The same figure also shows the functional relationship extracted for both substances. A linear correlation for naphtha is measured while a polynomial of the third order was required to fit the water calibration data.
  • a validation experiment was performed on the exemplary embodiment described above after doing the FTIR calibration as described above in Figures 5 and 6 with the FTIR probe installed near the exhaust of the VGS, bypassing the furnace.
  • the hot vapors exiting the VGS were immediately probed by the FTIR therefore these conditions are considered optimum and the precision obtained here is the best achievable precision because all the variables associated with the sample evaporation in the furnace have been removed.
  • the validation consisted of injecting, using a syringe and the syringe pump, known masses of water or naphtha into the VGS while varying the flow rates by selecting different settings on the syringe pump for simulating different evaporation rates as in the real samples.
  • Table 1 shows the correlation between the total masses injected into the VGS and the total masses found by FTIR. Namely, Table 1 compares the mass of liquid injected in the VGS as measured by a balance with the mass of the vapor as measured by the calibrated FTIR spectrometer, again using VGS and FTIR transfer line and gas cell temperatures of 250°C, and a nitrogen purge gas rate of 8 L/min.
  • a q-LSDS and VGS similar to that of Example 1 were modified to remove the copper coil from the furnace and enlarge the exhaust port to 11 mm in diameter.
  • the q-LSDS was calibrated using the VGS as before for both water and naphtha circulating in the system at a temperature of 250°C and carried by a nitrogen purge gas flow rate of 8 liters per minute.
  • probing of the exiting hot vapors was performed by the FTIR with a sampling flow rate set to 220 cc per minute.
  • Surrogate oil sand sample 57 had a large amount of naphtha which resulted in an intense naphtha evaporation peak.
  • Sample 61 was the injection of naphtha at different rate of addition using the syringe pump and one of the settings was a very fast rate of addition.
  • Wavenumber 2855 cm-l was preferred to 2878 cm-l for samples 57 and 61 because the maximum absorbance was in the range 0 - 1.2 as opposed to 0 - 2.2. The main reasons were to avoid detector saturation and to stay within the linear range for naphtha because it was observed that the fastest flow rates produced maximum absorbance that would begin to deviate from the linear trend.
  • Figure 7 shows the effect on the FTIR calibration for water (3744.20 cm 1 ) with a system temperature of 250°C when changing the nitrogen purge gas flow rate from the initial flow rate of 8 L/min to 6 L/min and then 10 L/min.
  • a slower purge gas flow rate makes the curve less exponential but still not linear for water.
  • the results from Figure 7 show that increased dilution of the water vapour (10 L/min) causes reduced absorbance and conversely for the reduced (6 L/min) flow rate.
  • Table 3 shows that the total mass results as measured by the FTIR were good, within 1%, when a syringe and the syringe pump were used to inject a known weight of water in the system regardless of the purge gas flow. Inversely, the results were clearly worse for water evaporated from a sample pan; the relative difference which was +8% before when the purge gas flow was 8 L/min became +13% with higher flow but -13% with lower flow. It became evident that pressure and/or temperature affected the FTIR data when real samples in sample pans were inserted in the furnace as opposed to syringed in the q-LSDS.
  • Example 3 [00115] In this example, a q-LSDS and VGS similar to those described above in Example 2 were further modified. Notably, the exhaust port was enlarged by a factor of 4, from 11 mm diameter to 23 mm, to minimize pressure build-up in the furnace during evaporation. A calibration of the FTIR and a series of evaporation tests were conducted on water using the same operating conditions (8 L/min of purge gas flow and 250°C system temperature) as the experiments done with the exemplary embodiment of Example 2 and described in Table 4 for the purpose of comparison.
  • Results show that the relative difference on water evaporation samples went from -8% to -4%, compared to the previous exemplary embodiment, a significant improvement.
  • the FTIR water calibration curve prepared from this exemplary embodiment was a perfect overlap of the one in Figure 7. They were overlapping despite the fact that the exhaust size of this embodiment was four times larger than the one on the embodiment of Example 2. This is an indication that the velocity of the gases exiting the furnace during calibration had insignificant impact on the FTIR measurements for as long as the temperature and concentration of the gases remained the same.
  • a fourth exemplary embodiment of the q-LSDS and VGS are further modified by enlarging the exhaust port from 23 mm to 35 mm in diameter and adding a l25-mm high chimney with regulated temperature at 250°C to further stabilize the vapour temperature before FTIR sampling.
  • a copper tubing was inserted in the chimney as a good thermal conductor in an attempt to increase the surface area in contact with the exhaust gases for better temperature control.
  • a small l/8-inch copper tubing used in the probing of the vapours for the FTIR was bent towards the interior of the chimney and the purge gas flow was raised from 8 L/min to 9 L/min to prevent diffusion of ambient air into the FTIR probe.
  • This exemplary embodiment was stabilized at 250°C and 9 L/min of nitrogen gas purge and then calibrated as before for water and naphtha using the syringe pump and the VGS.
  • the monitored wavenumbers for water and naphtha were 3744.20 and 2878.50 cm 1 respectively and the calibration ranges of infrared radiation absorbance were 0 to 1 for water and 0 to 1.5 for naphtha.
  • Table 5 shows that the total mass measurements for water by FTIR are, by far, the best results so far with a relative difference of only ⁇ 2% for the samples tested. For naphtha, the total mass results compare to those of Example 2 with an average of -3%
  • the FTIR profile of the organic solvent shows a long tail on the FTIR evaporation profile for the organic vapors as can be seen in Figure 8A during the drying of sample ID 120 which contained some bitumen.
  • the long tail can be due to slowly evaporating naphtha trapped in bitumen but it could also be from naphtha and low fraction bitumen evaporation.
  • a simple derivative of the absorbance profile of naphtha shows the rate of change of the absorbance data or, in other words, the rate of change of the mass flow of evaporating naphtha.
  • the rate of change illustrated by the derivative of Figure 8B may provide a better tool than the FTIR absorbance profile for identifying the point in time where there is a change in the evaporation process. It is an arbitrary point where the oscillating signal becomes noise.
  • the derivative can help describe the evaporation processes taking place, for example, a potential description of the naphtha evaporation from sample ID 120 would be: stage 1 (0 to 15 min) flash evaporation of free naphtha, stage 2 (15 to 37 min) diffusion of naphtha out of the solids, stage 3 (37 to 59 min) diffusion of naphtha trapped inside the solids and inside the bitumen and also potential bitumen evaporation.
  • model mixture ID 120 had evaporation profiles for naphtha and water similar to sample T2.
  • Table 6, below compares the relative standard deviation for multiple Soxhlet test results (12 repetitions for T2 and T4, 18 repetitions for Tl and T5) on the four tailings samples with the relative difference obtained for sample ID 120 for the percentages of water and solvent.
  • the relative difference is the difference between FTIR measured content and the balance measured content during the preparation of the sample.
  • the two measurements are of different nature but nevertheless, they give some indication of the differences in precision between the two methods.
  • the precision for water content is similar when using Soxhlet or q-LSDS, around 2%.
  • the results for naphtha show improved precision for when naphtha content was measured by q-LSDS when compared to Soxhlet.

Landscapes

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

Abstract

L'invention concerne différents modes de réalisation d'un système de séchage, d'un système de surveillance et d'étalonnage de volatils et un procédé associé. Un mode de réalisation est décrit en tant que système d'analyse d'échantillon comprenant : un four ; une entrée de gaz de purge ; un échappement pour évacuer un ou plusieurs composants volatils et un gaz de purge provenant du four ; une ligne d'échantillonnage pour échantillonner le ou les composants volatils ; un spectromètre FTIR ; et un processeur de données numériques utilisable pour surveiller un composant volatil désigné d'intérêt par conversion automatique d'une signature d'absorbance en une valeur de débit massique sur la base d'une relation d'étalonnage établie précédemment entre la signature et la valeur de débit massique.
PCT/CA2019/050463 2018-04-23 2019-04-16 Système de séchage, système de surveillance et d'étalonnage de volatils et procédé associé WO2019204906A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201862661153P 2018-04-23 2018-04-23
US62/661,153 2018-04-23

Publications (1)

Publication Number Publication Date
WO2019204906A1 true WO2019204906A1 (fr) 2019-10-31

Family

ID=68293412

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA2019/050463 WO2019204906A1 (fr) 2018-04-23 2019-04-16 Système de séchage, système de surveillance et d'étalonnage de volatils et procédé associé

Country Status (1)

Country Link
WO (1) WO2019204906A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111413291A (zh) * 2020-04-09 2020-07-14 中国科学院上海应用物理研究所 一种气体氟化物的红外光谱定量分析方法
CN111537325A (zh) * 2020-06-17 2020-08-14 中检(河南)计量检测有限公司 一种水浴氮吹仪的校正方法
CN112827779A (zh) * 2020-12-31 2021-05-25 广州钰铂机械设备制造有限公司 大巴车局部车漆修补快速烘干系统

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2597809A1 (fr) * 2007-08-17 2009-02-17 Gushor Inc. Methode de mesure de la viscosite et de la densite de petrole brut et d'huile lourde
US20180127658A1 (en) * 2016-10-19 2018-05-10 Fort Hills Energy L.P. Bitumen production in paraffinic froth treatment (pft) operations with near infrared (nir) monitoring

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2597809A1 (fr) * 2007-08-17 2009-02-17 Gushor Inc. Methode de mesure de la viscosite et de la densite de petrole brut et d'huile lourde
US20180127658A1 (en) * 2016-10-19 2018-05-10 Fort Hills Energy L.P. Bitumen production in paraffinic froth treatment (pft) operations with near infrared (nir) monitoring

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NIKAKHTARI ET AL.: "Solvent Screening for Non-Aqueous Extraction of Alberta Oil Sands", CAN. J. CHEM. ENG., vol. 91, June 2013 (2013-06-01), pages 1153 - 1160, XP055231407, DOI: 10.1002/cjce.21751 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111413291A (zh) * 2020-04-09 2020-07-14 中国科学院上海应用物理研究所 一种气体氟化物的红外光谱定量分析方法
CN111537325A (zh) * 2020-06-17 2020-08-14 中检(河南)计量检测有限公司 一种水浴氮吹仪的校正方法
CN112827779A (zh) * 2020-12-31 2021-05-25 广州钰铂机械设备制造有限公司 大巴车局部车漆修补快速烘干系统
CN112827779B (zh) * 2020-12-31 2021-09-10 广州钰铂机械设备制造有限公司 大巴车局部车漆修补快速烘干系统

Similar Documents

Publication Publication Date Title
WO2019204906A1 (fr) Système de séchage, système de surveillance et d'étalonnage de volatils et procédé associé
US7248370B2 (en) Method to reduce background noise in a spectrum
Bueno et al. Photoacoustic measurements of amplification of the absorption cross section for coated soot aerosols
Stec et al. Quantification of fire gases by FTIR: experimental characterisation of calibration systems
Bendana et al. Line mixing and broadening in the v (1→ 3) first overtone bandhead of carbon monoxide at high temperatures and high pressures
CN102410993B (zh) 基于激光诱导等离子体发射光谱标准化的元素测量方法
US11592398B2 (en) Augmented Raman analysis of a gas mixture
Kachko et al. Comparison of Raman, NIR, and ATR FTIR spectroscopy as analytical tools for in-line monitoring of CO2 concentration in an amine gas treating process
Giron et al. High temperature polymer degradation: Rapid IR flow-through method for volatile quantification
CN108444976B (zh) 一种基于拉曼光谱的天然气热值测量方法
Qu et al. Towards a dTDLAS-based spectrometer for absolute HCl measurements in combustion flue gases and a better evaluation of thermal boundary layer effects
Federherr et al. A novel high‐temperature combustion based system for stable isotope analysis of dissolved organic carbon in aqueous samples. I: development and validation
CN105136682B (zh) 一种燃油中芳烃含量快速、准确测定的新方法
Wong et al. Raman spectroscopic study on the equilibrium of carbon dioxide in aqueous monoethanolamine
Liebergesell et al. A milliliter-scale setup for the efficient characterization of isothermal vapor-liquid equilibria using Raman spectroscopy
CN107966499B (zh) 一种由近红外光谱预测原油碳数分布的方法
Islam et al. Methods and methodology for FTIR spectral correction of channel spectra and uncertainty, applied to ferrocene
CN108982401B (zh) 一种从混合气体的红外吸收光谱中解析单组分流量的方法
Ma et al. The spectral resolution of unknown mixture based on THz spectroscopy with self-modeling technique
CN106198405A (zh) 用于大气水汽氢氧稳定同位素比率监测的系统
Alroe et al. Determining the link between hygroscopicity and composition for semi-volatile aerosol species
Haaland et al. Multivariate calibration of carbon Raman spectra for quantitative determination of peak temperature history
Gaynullin et al. A practical solution for accurate studies of NDIR gas sensor pressure dependence. Lab test bench, software and calculation algorithm
WO2015005074A1 (fr) Appareil de mesure de constituants d'un gaz
Kruger et al. Monomer fraction data of dilute alcohol/acetone systems measured with transmission Fourier transform infrared spectroscopy

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19791890

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19791890

Country of ref document: EP

Kind code of ref document: A1