WO2019204906A1

WO2019204906A1 - Drying system, volatile monitoring and calibration system and method therefor

Info

Publication number: WO2019204906A1
Application number: PCT/CA2019/050463
Authority: WO
Inventors: Gilles ROBERTSON; Patrick Mercier
Original assignee: National Research Council of Canada
Current assignee: National Research Council of Canada
Priority date: 2018-04-23
Filing date: 2019-04-16
Publication date: 2019-10-31
Anticipated expiration: 2020-10-23

Abstract

Described are various embodiments of a drying system, volatile monitoring and calibration system and method therefor. One embodiment is described as a sample analysis system comprising: a furnace; a purge gas input; an exhaust for exhausting one or more volatile components and purge gas from the furnace; a sampling line to sample the one or more volatile components; an FTIR spectrometer; and a digital data processor operable to monitor for a designated volatile component of interest by automatically converting an absorbance signature to a mass flow rate value based on a previously established calibration relationship between the signature and the mass flow rate value.

Description

DRYING SYSTEM. VOLATILE MONITORING AND CALIBRATION SYSTEM

AND METHOD THEREFOR

CROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 62/661,153, filed April 23, 2018 and entitled“Drying System, Volatile Monitoring and Calibration System and Method Therefor” which is incorporated by reference herein in its entirety.

FIELD OF THE DISCLOSURE

[0002] 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.

BACKGROUND

[0003] It is commercially valuable for a range of industrial and/or scientific processes to be able to accurately measure the mass of evolved gases or vapours present in the air. A common method is to use infrared (IR) spectroscopy to identify a concentration of designated components present in a sample. Because it is very fast, Fourier Transform infrared spectroscopy (FTIR spectroscopy) is often used. This method covers a wide range of chemical applications, especially for polymers and organic compounds. However, these usually require using a closed cell, within which a gas sample is temporarily contained, to make the measurements. Moreover, most methods assume a linear relationship (Beers-Lambert law) between the measured absorbance of a given component and its concentration, which has its significant limitations in commercial and industrial applications. For instance, current methods are not well suited for certain applications, such as in the analysis of oil sands products. [0004] The most common commercial technology for the extraction of bitumen from oil sands is hot water extraction. However, there are major issues with high energy consumption and water pollution. Solvent extraction has been proposed and investigated as an alternative method to the solvent extraction and solids agglomeration (SESA) process described by Meadus et al. in U.S. Patent No. 4,057,486. The challenge with any bitumen extraction by hydrocarbon solvent process is the recovery of the organic solvent. There is interest in estimating the energy requirements and costs of recovering the valuable solvent and in evaluating the compliance to environmental legislation for residual solvent content in the treated sand, i.e. the tailings produced by the extraction processes of bitumen from oil sands. In addition, the residual amounts of water left in the tailings while drying is 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. In the oil sands industry, 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, the Soxhlet-Dean and Stark extraction technique, 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. However, 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.

[0005] This background information is provided to reveal information believed by the applicant to be of possible relevance. No admission is necessarily intended, nor should be construed, that any of the preceding information constitutes prior art or forms part of the general common knowledge in the relevant art.

SUMMARY

[0006] The following presents a simplified summary of the general inventive concept(s) described herein to provide a basic understanding of some aspects of the disclosure. This summary is not an extensive overview of the disclosure. It is not intended to restrict key or critical elements of embodiments of the disclosure or to delineate their scope beyond that which is explicitly or implicitly described by the following description and claims.

[0007] A need exists for a drying system, volatile monitoring and calibration system and method therefor, that overcome some of the drawbacks of known techniques, or at least, provides a useful alternative thereto. In particular, 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. For example, in some embodiments, the systems and methods considered herein provide for selective and/or quantitative monitoring of volatile components evolved from a heated sample. In some examples, 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.

[0008] In accordance with one aspect, there is provided 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. [0009] In one embodiment, 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.

[0010] In one embodiment, 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.

[0011] In one embodiment, 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.

[0012] In one embodiment, the calibration liquid injection device comprises a syringe pump. [0013] In one embodiment, the digital processor is further operable to concurrently monitor for two or more designated volatile components of interest.

[0014] In one embodiment, 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.

[0015] In one embodiment, 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. [0016] In one embodiment, the designated exhaust conditions comprise at least one of a temperature controlled chimney or a substantially constant purge gas flow rate.

[0017] In one embodiment, 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.

[0018] In one embodiment, 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.

[0019] In one embodiment, the purge gas is nitrogen.

[0020] In one embodiment, 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.

[0021] In accordance with another aspect, there is provided 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.

[0022] In one embodiment, the method further comprises heating the sample to generate the one or more volatile components. [0023] In one embodiment, the entraining comprises entraining at a substantially constant flow rate.

[0024] In one embodiment, 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.

[0025] In one embodiment, 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.

[0026] In one embodiment, 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.

[0027] In one embodiment, the method further comprises repeating said calibrating for two or more distinct calibration liquids. [0028] In accordance with another aspect, there is provided a calibration method for quantitative monitoring of a designated volatile component of interest evolved from a sample in a designated sample processing system, the method 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.

[0029] In one embodiment, the method is further repeated for two or more calibration liquids. [0030] In one embodiment, 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.

[0031] In one embodiment, 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.

[0032] In one embodiment, the processing system is a furnace system and wherein said designated exhaust conditions comprise a substantially constant purge gas flow rate.

[0033] In accordance with another aspect, there is provided 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 of interest to a corresponding mass flow rate evolving from an unknown sample during heating in the furnace system.

[0034] In one embodiment, the digital data processor is further operable to automatically derive said calibration relationship. [0035] In one embodiment, the calibration liquid injection device comprises a syringe pump.

[0036] In one embodiment, 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. [0037] In one embodiment, the designated volatile component of interest is selected from at least one of water, one or more simple organic solvents or naphtha.

[0038] In one embodiment, the sample is selected from at least one of oil sand ore or a processed oil sand ore product.

[0039] In one embodiment, the relationship comprises at least one of a linear relationship and a non-linear relationship.

[0040] In one embodiment, the sample processing system comprises a furnace system. [0041] In one embodiment, the designated exhaust conditions comprise a substantially constant purge gas flow rate.

[0042] In accordance with another aspect, there is provided 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.

[0043] In one embodiment, 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.

[0044] In accordance with another aspect, there is provided 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. [0045] In one embodiment, 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. [0046] Other aspects, features and/or advantages will become more apparent upon reading of the following non-restrictive description of specific embodiments thereof, given by way of example only with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE FIGURES [0047] Several embodiments of the present disclosure will be provided, by way of examples only, with reference to the appended drawings, wherein:

[0048] 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; [0049] 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; [0050] 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;

[0051] 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;

[0052] Figure 5 is an exemplary plot of FTIR absorbance values measured for water as a function of mass flow rate;

[0053] 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;

[0054] 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 [0055] 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.

[0056] Elements in the several figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be emphasized relative to other elements for facilitating understanding of the various presently disclosed embodiments. Also, common, but well- understood elements that are useful or necessary in commercially feasible embodiments are often not depicted in order to facilitate a less obstructed view of these various embodiments of the present disclosure. DETAILED DESCRIPTION

[0057] Various implementations and aspects of the specification will be described with reference to details discussed below. The following description and drawings are illustrative of the specification and are not to be construed as limiting the specification. Numerous specific details are described to provide a thorough understanding of various implementations of the present specification. However, in certain instances, well-known or conventional details are not described in order to provide a concise discussion of implementations of the present specification.

[0058] Various apparatuses and processes will be described below to provide examples of implementations of the system disclosed herein. No implementation described below limits any claimed implementation and any claimed implementations may cover processes or apparatuses that differ from those described below. The claimed implementations are not limited to apparatuses or processes having all of the features of any one apparatus or process described below or to features common to multiple or all of the apparatuses or processes described below. It is possible that an apparatus or process described below is not an implementation of any claimed subject matter.

[0059] Furthermore, numerous specific details are set forth in order to provide a thorough understanding of the implementations described herein. However, it will be understood by those skilled in the relevant arts that the implementations described herein may be practiced without these specific details. In other instances, well-known methods, procedures and components have not been described in detail so as not to obscure the implementations described herein.

[0060] In this specification, elements may be described as“configured to” perform one or more functions or“configured for” such functions. In general, 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. [0061] It is understood that for the purpose of this specification, 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.

[0062] The systems and methods described herein provide, in accordance with different embodiments, different examples of a drying system, such as a Large Scale Drying System (LSDS), and volatile monitoring and calibration system and method therefor. For example, as noted, above, 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.

[0063] For example, and as will be detailed further below, 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. In some embodiments, 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.

[0064] Furthermore, quantitative measurements can be executed in real-time in respect of ongoing evolving gas flows. From such measurements, 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. Unlike in conventional quantitative FTIR, in which one is generally interested in knowing the concentration (i.e. the mass per unit volume) of a studied gas of interest, 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.

[0065] These and other uses, functions and/or advantages of the herein described systems and methods will be further detailed below, as will be readily appreciated by the skilled artisan. [0066] With reference to Figure 1, and in accordance with one exemplary embodiment, 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. In the illustrated embodiment, 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).

[0067] In this embodiment, 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. In some embodiments, 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. [0068] In general, the furnace 102 will be temperature controlled. For example, in some embodiments, the temperature is controlled by using a temperature controller operatively connected to a heating tape and a thermocouple. The skilled artisan will understand that other controlled heating methods may be available, such as using a heating element, etc. [0069] In the illustrated embodiment, furnace 102 further comprises a sample holder 106 and a sample pan 107 for holding sample 104. In general, 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. [0070] In the illustrated embodiment, the furnace further comprises a purge gas input

110, located below sample holder 106 in some embodiments, for flowing a purge gas at a substantially constant flow rate into furnace 102. The purge gas, which will generally be selected to be a substantially IR-transparent gas, such as but not limited to Nitrogen (N₂), 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. In some embodiments, 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). [0071] With continued reference to Figure 1, 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. In some embodiments, 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. For instance, 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. Moreover, the 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. In some embodiments, this exit port may take the form of a chimney or like structures readily known in the art.

[0072] In the illustrated embodiment, 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.

[0073] In some embodiments, 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.

[0074] In some embodiments, it may be possible to adjust the size and flow rate of the exit port and/or sampling port. For example, adjustable system components may allow for system and/or performance optimizations that can be addressed by adequate system calibration, as discussed further below.

[0075] 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. Tracking these absorbance signatures as a function of time for a specific bond vibration, for example C-H and/or O-H, is equivalent to tracking corresponding signatures of different substances, in this example an organic solvent (C-H band) and/or water (O-H band). [0076] To process acquired data, 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. In some cases, 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. For example, 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. In doing so, complex overlapping spectral signatures may be precisely identified and distinguished in respectively characterising two or more volatile components of interest. [0077] In either event, 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. 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, 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.

[0078] It will be appreciated that 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. While not explicitly illustrated herein, 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. As will be appreciated by the skilled artisan, 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. These and other such considerations should be readily appreciated by the skilled artisan to fall within the general scope and nature of the present disclosure.

[0079] With reference to Figure 2, and in accordance with one exemplary embodiment, 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. For instance, in the embodiment illustrated in Figure 1, 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. For instance, one may select liquid water to calibrate the apparatus for water vapor. To do so, 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. In some embodiments, 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. For example, the calibration fluids may be vaporized first and then introduced into the heating system using a mass flow controller.

[0081] 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. [0082] Following this, in step 230, 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. [0083] With continued reference to Figure 2, the next step (240) is to vaporize the calibration fluid at the designated mass flow rate. In one embodiment, as will be described below with reference to Figure 3, 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.

[0084] In 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.

[0085] In 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. In 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. Once the device has been calibrated for one designated volatile component, one may select (step 290) another component for calibration. In some embodiments, 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.

[0086] 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. 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.

[0087] With reference to Figure 3, and in accordance with one exemplary embodiment, 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.

[0088] 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.

[0089] 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.

[0090] Again, 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.

[0091] To process acquired data, 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. [0092] 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. Generally, 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. For example, in the illustrated embodiment, 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. [0093] In some embodiments, 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. For example, in some embodiments, 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. 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 properly. In the case of injection system 352, 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 q-LSDS 300. [0094] In one exemplary calibration operation, 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. As explained above, using a series of known mass flow rates and measuring the corresponding IR absorbance values with the FTIR spectrometer 326 at the selected wavelength characteristic of this designated substance (absorbance signature), a quantitative relationship between them may be extracted. The skilled artisan will understand that other configurations may be possible, for instance, 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.

[0095] With reference to Figure 4, and in accordance with one exemplary embodiment, a volatile monitoring system, generally referred to using the numeral 400, and operable to be installed or retrofitted on a pre-existing system 405, itself operable to produce one or more volatile components from an exit port 410, will now be described. In this example, 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.

[0096] As shown in Figure 4, 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. To process acquired data, 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.

[0097] The described embodiment further comprises a VGS 448, which may be operatively connected to pre-existing system 405 via an input port 450. As described before, 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. For example, in the illustrated embodiment, 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.

[0098] In some embodiments, 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. As described above, in some embodiments, 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. In the case of 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.

[0099] In some embodiments, the system 405 may be operable to precisely control the mass flow rate of the one or more volatile component. In such a case, the monitoring device may be calibrated using the method described before but without the need for a VGS.

EXAMPLES

[00100] The following provides a number of non-limiting examples of specific embodiments designed and tested to validate, and in some instances, optimize, operation of the above described embodiments. The person of ordinary skill in the art will readily appreciate that various features and details of the below-described examples may be altered or varied without departing from the general scope and nature of the present disclosure. [00101] Furthermore, while the below examples describe various detailed implementations of systems and methods as described herein, other implementation form factors may be considered, for example, to address larger or smaller scale projects and objectives, and that without departing from the general scope and nature of the present disclosure. Namely, while LSDS are considered in some embodiments, other embodiments may be adapted to accommodate different sample sizes, volumes and/or conditions. These and other such considerations are thus considered to be within the purview of the herein described embodiments as would be readily understood by a person of ordinary skill in the art.

Example 1 [00102] In this first example, 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. In this example, 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. [00103] 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.

[00104] 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.

[00105] 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. In the current example, 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. For instance, 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. Eight (8) different rates of injection are displayed leading to 8 different plateaus. Calibration was executed at VGS and FTIR sampling line and gas cell temperatures of 250°C, with a nitrogen purge gas rate of 8 L/min. [00106] The third step in calibrating the FTIR spectrometer was to correlate the

FTIR’s 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.

[00107] 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. The results in Table 1, below, show 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.

Table 1

[00108] The weights calculated by FTIR listed in Table 1 were obtained by conversion of the total surface areas of the absorbance profiles for water (wavenumber 3744 cm ¹) and naphtha (2878 cm ¹) into total masses by using the functional relationships from Figure 6. Every single FTIR absorbance data point (every 4 seconds here) was converted into a flow rate using these equations and those individual flow rates were then readily converted into mass for every 4-second time delay between each data point. The sum of every converted FTIR data point into mass of water or naphtha resulted into the total FTIR calculated mass of water or naphtha.

Example 2

[00109] In this second example, 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. In this embodiment, 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. In addition, probing of the exiting hot vapors was performed by the FTIR with a sampling flow rate set to 220 cc per minute. A series of tests was then performed for comparison of the total mass of materials inserted in the furnace with the total mass of the same evaporating materials as captured by the calibrated FTIR system; the results are displayed in Table 2, below. In particular, evaporation tests were done on pure water (wavenumber 3744.20 cm ¹), naphtha (wavenumber 2878.50 cm ¹) and surrogate oil sands (SOS) (wavenumber 2855. dlcm ¹ for sample ID 57 and 61) after calibration of the FTIR using the VGS.

Table 2

[00110] In order to effectively calibrate the system, it should be calibrated consistent with the range of absorbance susceptible to be observed during sample drying experiments. It is also preferable to select wavenumbers for which maximum absorbance remain within a suitable range to avoid detector saturation. That was not an issue for water as the maximum absorbance for wavenumber 3744 cm ¹ rarely exceeded 0.8. On the other hand, samples with large quantities of organic solvents showed high maximum absorbance sometimes well above 2 therefore the wavenumbers used in the calibration and drying experiments had to be properly selected to maintain the maximum absorbance around 1. [00111] In the results presented at Table 2, the wavenumber 2878 cm ¹ was used for monitoring naphtha in all the experiments except for sample ID 57 and 61. 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. [00112] In Table 2, all the FTIR total weights for naphtha were calculated using the linear equations resulting from the calibration curves such as the one from Figure 6. As seen in Table 2, the relative difference between total weight measured by FTIR and balance was 3.9% for sample ID 61. A better fit using a 3^rd order polynomial trend line instead of linear would have resulted in a smaller relative difference of 1.7%. As seen in Figure 6, the FTIR calibration for water is non-linear but it is also important to remain within a low absorption range due to the exponential nature of the curve; a small difference in absorption will result in larger flow variation when dealing with high absorption values. [00113] Following the acquisition of the results shown in table 2, a series of calibrations and measurements were done with nitrogen purge gas flow rates below and above the initial flow rate to observe the effects on quantitative precision of the q-LSDS. 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. Water samples were then tested for evaporation in the q-LSDS with the different purge gas flow rates of 6 L/min and 10 L/min and then, as before, the total weight losses by balance and by FTIR were compared for assessing the precision of the system. The results are shown in Table 3, below, for the lOL/min and 6L/min purge gas flow rates.

Table 3

[00114] 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.

Table 4

[00116] Results show that the relative difference on water evaporation samples went from -8% to -4%, compared to the previous exemplary embodiment, a significant improvement. Moreover, 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.

[00117] All of the water evaporation tests done so far using the VGS and a syringe indicated that when the vapours had reached 250°C before arriving at the FTIR probe then the FTIR detected the water mass within 1% precision. It was also demonstrated that the FTIR calibration curve for water was not affected by a change in exhaust size. These observations encourage temperature control of the substance’s vapours prior to sampling by the FTIR probe. Indeed, if the vapours sampled by the FTIR probe are not at the same temperature as the calibration temperature then the absorbance data may be impacted.

Example 4

[00118] In this example, 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. The diffusion of air is easily observable by monitoring the presence of carbon dioxide present in air; the absence of C0₂ signals is an indication that the probe is only reading purge gas and volatiles coming from the furnace. Diffusion of air was not identified as an issue in previous examples due to the smaller exhaust port sizes in those examples.

[00119] 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 calibration curves were fitted, as seen before in Figure 6, with a linear fit for naphtha (R²=0.99995) and a 3^rd degree polynomial fit for water (R²=0.99994). 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. The FTIR detector gain was kept constant at 1 and each data point was separated by 4 seconds which corresponded to 2 full scans from 4000 to 650 cm ¹ with 2 cm ¹ resolution. As before, the total masses of evaporated material as measured by the q-LSDS are listed in Table 5, below, for comparison with the original composition (prepared by balance) for a series of pure substances and surrogate oil sands mixtures. Table 5

[00120] 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%

±2% (excluding syringe test).

[00121] 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, as displayed in Figure 8B, shows the rate of change of the absorbance data or, in other words, the rate of change of the mass flow of evaporating naphtha. One can see that the rate is largely positive for increasing evaporation followed by negative, decreasing evaporation, and then oscillates until around 37 minutes where the rate of change stabilizes as noise. It is fair to assume that before the 37 minutes mark, mainly naphtha evaporated whereas after 37 minutes some naphtha was still coming out but possibly with some interference from slow evaporating low fraction bitumen. Following this assumption, the total mass content found by FTIR for naphtha was reported in Table 5 as two values, the first one is for time 0 to 37 minutes while the second value is for the total drying time of 59 minutes. The difference in weight between the two values is not very large and the real naphtha content lies somewhere in between those two values. It is also worthwhile mentioning that those two values fall within the precision error reported in the previous section therefore bitumen interference, if any, can be considered as minimal for this system.

[00122] 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.

[00123] It has been observed that some of the volatile bitumen fractions may contaminate the FTIR cell and impact the FTIR detector’s response. It is apparent that the data point acquired after such contamination would be impacted by lower sensitivity when compared to the initial calibration. Fortunately, the design of the currently described embodiment has a chimney and the bitumen vapours which caused such coating contamination in the FTIR gas cell before, could not make it up the chimney as observed by an unchanged FTIR sensitivity after testing sample ID 120.

[00124] Moreover, 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. Once again, 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.

Table 6

[00125] While the present disclosure describes various embodiments for illustrative purposes, such description is not intended to be limited to such embodiments. On the contrary, the applicant's teachings described and illustrated herein encompass various alternatives, modifications, and equivalents, without departing from the embodiments, the general scope of which is defined in the appended claims. Except to the extent necessary or inherent in the processes themselves, no particular order to steps or stages of methods or processes described in this disclosure is intended or implied. In many cases the order of process steps may be varied without changing the purpose, effect, or import of the methods described.

[00126] Information as herein shown and described in detail is fully capable of attaining the above-described object of the present disclosure, the presently preferred embodiment of the present disclosure, and is, thus, representative of the subject matter which is broadly contemplated by the present disclosure. The scope of the present disclosure fully encompasses other embodiments which may become apparent to those skilled in the art, and is to be limited, accordingly, by nothing other than the appended claims, wherein any reference to an element being made in the singular is not intended to mean "one and only one" unless explicitly so stated, but rather "one or more." All structural and functional equivalents to the elements of the above-described preferred embodiment and additional embodiments as regarded by those of ordinary skill in the art are hereby expressly incorporated by reference and are intended to be encompassed by the present claims. Moreover, no requirement exists for a system or method to address each and every problem sought to be resolved by the present disclosure, for such to be encompassed by the present claims. Furthermore, no element, component, or method step in the present disclosure is intended to be dedicated to the public regardless of whether the element, component, or method step is explicitly recited in the claims. However, that various changes and modifications in form, material, work-piece, and fabrication material detail may be made, without departing from the spirit and scope of the present disclosure, as set forth in the appended claims, as may be apparent to those of ordinary skill in the art, are also encompassed by the disclosure.

Claims

CLAIMS What is claimed is:

1. 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.

2. The system of claims l, further comprising 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.

3. The system of claim 1, further comprising 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.

4. The system of claim 2 or claim 3, wherein said 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.

5. The system of claim 2 or claim 3, wherein said calibration liquid injection device comprises a syringe pump.

6. The system of any one of claims 1 to 5, wherein said digital processor is further operable to concurrently monitor for two or more designated volatile components of interest.

7. The system of claim 6, wherein said 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.

8. The system of any one of claims 1 to 7, wherein said one or more designated volatile components of interest comprise at least one of water, one or more organic solvents, toluene, cyclohexane, pentane or naphtha.

9. The system of any one of claims 1 to 8, wherein the designated exhaust conditions comprise at least one of a temperature controlled chimney or a substantially constant purge gas flow rate.

10. The system of any one of claims 1 to 9, wherein 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.

11. The system of any one of claims 1 to 9, further comprising:

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.

12. The system of claim 10, wherein said purge gas is nitrogen.

13. The system of claim 10 or claim 11, further comprising 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.

14. 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

15. The sample analysis method of claim 14, further comprising heating the sample to generate the one or more volatile components.

16. The sample analysis method of claim 14 or claim 15, wherein said entraining comprises entraining at a substantially constant flow rate.

17. The method of any one of claims 14 to 16, further comprising, 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.

18. The method of any one of claims 14 to 16, further comprising, 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;

using said digital data processor:

19. The method of claim 17 or claim 18, wherein said 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.

20. The method of any one of claims 17 to 19, further comprising repeating said calibrating for two or more distinct calibration liquids.

21. A calibration method for quantitative monitoring of a designated volatile component of interest evolved from a sample in a designated sample processing system, the method 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.

22. The method of claim 15, wherein the method is further repeated for two or more calibration liquids.

23. The method of claim 21 or claim 22, wherein said 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.

24. The method of claim 21 or claim 22, wherein said 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.

25. The method of any one of claims 21 to 24, wherein the processing system is a furnace system and wherein said designated exhaust conditions comprise a substantially constant purge gas flow rate.

26. 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 of interest to a corresponding mass flow rate evolving from an unknown sample during heating in the furnace system.

27. The calibration module of claim 26, wherein said digital data processor is further operable to automatically derive said calibration relationship.

28. The calibration module of claim 26 or claim 27, wherein said calibration liquid injection device comprises a syringe pump.

29. The calibration module of any one of claims 26 to 28, wherein said 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.

30. The calibration module of any one of claims 26 to 29, wherein said designated volatile component of interest is selected from at least one of water, one or more simple organic solvents or naphtha.

31. The calibration module of any one of claims 26 to 30, wherein the sample is selected from at least one of oil sand ore or a processed oil sand ore product.

32. The calibration module of any one of claims 26 to 31, wherein said relationship comprises at least one of a linear relationship and a non-linear relationship.

33. The calibration module of any one of claims 26 to 32, wherein the sample processing system comprises a furnace system.

34. The calibration module of claim 33, wherein said designated exhaust conditions comprise a substantially constant purge gas flow rate.

35. 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

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

36. The system of claims 35, further comprising 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.

37. 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;

using a digital data processor:

extracting from said signal an absorbance signature corresponding to a designated volatile component to be monitored;

quantifying a total mass value for said designated volatile component of interest based on said converting.

38. The method of claim 37, further comprising, 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;

using said digital data processor: