Patent Application
20250035601
This application claims the benefit of the filing date of French Patent Application Serial No. FR2308127, filed Jul. 27, 2023, for “GAS-PHASE CHEMICAL ANALYSIS METHOD.”
The present disclosure relates to the field of chemical analysis, and more particularly to gas-phase chemical analysis.
In particular, the present disclosure relates to a method for the chemical analysis of a gaseous sample comprising at least one contaminant species with a view to determining the concentration of the at least one contaminant species in the sample.
Detecting and quantifying contaminant species in industrial gases is essential to guarantee their degree of purity.
In these regards, it is possible to use spectroscopic techniques that are not only stable over time, but also have the advantage of being relatively easy to implement. Nevertheless, there are situations where contaminant species are difficult to detect and/or identify by spectroscopy. This is particularly true of H2S. This compound, with its low spectroscopic activity, is barely detectable when its concentration in a gas is less than 1 ppm.
Thus, one aim of the present disclosure is to provide a method for the chemical analysis of a gaseous sample comprising a contaminant species, with greater sensitivity than methods known to the skilled person.
The present disclosure relates to a method for chemical analysis of a gaseous sample comprising a first species, the first species exhibiting a spectroscopic activity, called first activity, in a predetermined wavelength range, the method of chemical analysis comprising:
According to one embodiment, the second spectroscopic activity is at least ten times greater than the first spectroscopic activity.
According to one embodiment, the second species exhibits a substantially periodic absorption spectrum in the predetermined wavelength range.
According to one embodiment, the first species comprises H2S, while the second species comprises SO2.
According to one embodiment, the conversion reagent comprises I2O5.
According to one embodiment, the conversion reagent is in one of the forms chosen from: powder, pellet, flakes, granules, beads.
According to one embodiment, step b) comprises measuring by way of a spectrograph the absorption spectrum by the gaseous sample of light radiation emitted by a light source.
Other features and advantages of the present disclosure will emerge from the following detailed description of the present disclosure with reference to the appended figure, wherein:
The present disclosure relates to a method for the chemical analysis of a gaseous sample comprising a carrier gas wherein a first species is diluted. In particular, the first species, according to the terms of the present disclosure, has a spectroscopic activity, known as the first activity, in a predetermined range of wavelengths.
Spectroscopic activity according to the terms of the present disclosure can be defined as the level of spectroscopic absorption in the predetermined wavelength range.
Thus, the analysis method according to the present disclosure comprises a step a) for conversion, in a conversion cell, of the first species into a second species by reaction with a reagent, called conversion reagent, the second species exhibiting a spectroscopic activity, called second activity, greater than the first activity;
The method also comprises a step b) for acquiring an absorption spectrum, by spectroscopic measurement, of the gaseous sample after step a) has been carried out, in a measuring cell fluidically connected to the conversion cell;
Step b) is followed by a step c) for mathematical processing of the spectrum to deduce the concentration of the first species in the gaseous sample.
Under the terms of the present disclosure, the first species exhibits spectroscopic activity, called first activity, in the predetermined wavelength range, while the second species exhibits spectroscopic activity, called second activity, in the predetermined wavelength range. The second spectroscopic activity can, for example, be at least 2 times, advantageously 10 times, greater than the first spectroscopic activity.
In other words, and according to the present disclosure, in the predetermined wavelength range, the maximum absorption level (i.e., spectroscopic activity) of the second species is greater (advantageously at least twice, advantageously 10 times, greater) than the maximum absorption level of the first species.
In addition, and advantageously, the second species can exhibit a specific signature in the predetermined wavelength range. In particular, the second species can exhibit a periodic or pseudoperiodic absorption spectrum enabling unambiguous identification of the second species. A periodic or pseudoperiodic absorption spectrum takes the form of a comb.
By way of example, and without being limiting, it will be considered in the following that the first species is H2S while the second species is SO2. The sample gas thus comprises a carrier gas wherein H2S is diluted. The latter can be converted to SO2 using a conversion reagent, such as I2O5.
The conversion reaction of H2S to SO2 by I2O5 follows the following reaction:
5H2S+3I2O5→3I2+5SO2+5H2O
By way of example,
These two pictorials show that the absorption level of SO2 in this wavelength range is higher than the absorption level of H2S.
In other words, the detection threshold of H2S by spectroscopic absorption is much better than that of SO2. By converting H2S into SO2, the presence of H2S can be detected at lower concentrations than with techniques known from the state of the art based on direct absorption of the H2S compound.
This last aspect improves the sensitivity of assay and/or analysis of a chemical compound diluted in a carrier gas.
Furthermore, the periodic nature of the absorption spectrum shown in
Mathematical processing, in particular, involving a Fourier transform, can be used to determine the SO2 concentration in the carrier gas.
By way of example, the chemical analysis method according to the present disclosure can be implemented by the chemical analysis device 10 shown in
The chemical analysis device 10 comprises, in particular, a conversion cell 20 (e.g., a vial) wherein a conversion reagent is arranged, configured to convert the first species of the gaseous sample into the second species.
The conversion cell 20 is generally elongated, and may, for example, be cylindrical. The conversion cell 20 comprises a first inlet 20a at one end and a first outlet 20b at the other end.
The conversion cell 20 comprises, in its volume, a reagent, called conversion reagent, configured to chemically convert the first species likely to circulate in gaseous form in the cell into the second species.
The conversion reagent can, in particular, comprise I2O5, for example, in powder or even crystal form. Thus, to prevent I2O5 from being carried along by the carrier gas as it flows, membranes, such as PTFE membranes, may be considered.
The chemical analysis device 10 also comprises spectroscopic means configured to measure an absorption spectrum of the gaseous sample after conversion of dichlorine to chlorine dioxide.
More particularly, the spectroscopic means cooperate with a measuring cell 30 (e.g., a vial) to measure the absorption spectrum when the gaseous sample is in the measuring cell.
More particularly, the generally elongated measuring cell 30 comprises two ends 31a and 31b (opposite one another), each provided with a window 32a and 32b transparent to the wavelengths included in the analysis range. These two windows 32a and 32b are parallel to one another.
The conversion cell 20 can comprise a main body, tubular in shape and hermetically sealed at its ends by PTFE membranes that allow gases to pass through and retain the conversion reagent.
Advantageously, the main body can be transparent and comprise, for example, PMMA or glass.
The spectroscopic means comprise a spectrograph 61 and a light source 60 configured to emit light radiation covering the analysis range.
In particular, the light source 60 is arranged opposite the window 32a to enable illumination of a gaseous sample likely to be present in the measuring cell 30.
The spectrograph 61 is positioned opposite the window 32b and is arranged to measure the absorption of light radiation by the gaseous sample in the analysis range. It is understood, but not necessary to specify, that a spectrograph measures an absorption spectrum as a function of wavelength. The spectrograph 61 is advantageously connected to a computer 62 configured to process and/or analyze the spectra collected by the spectrograph 61.
“Computer” is understood to mean an electronic device configured to perform automatic processing of a spectrum collected by the spectrograph. The computer 62 can comprise a memory, a processor, a motherboard, a display and a control interface.
The measuring cell 30 is also fluidically connected to the conversion cell 20. In particular, a fluidic connection means connects the first outlet 20b to an inlet, called second inlet 30a, located proximate to the end 31a of the measuring cell 30. In particular, the fluidic connection means may comprise a fluidic connection tube, called first tube 40a. The fluidic connection means can also be provided with a three-way valve (or solenoid valve) 50. Thus, the fluidic connection means may comprise a tube 40b connecting the first outlet 20b to the three-way valve 50, the tube 40a connecting the three-way valve 50 to the second inlet 30a, and finally a tube 40c connecting a carrier gas source 51 to the three-way valve 50.
The measuring cell 30 also comprises an outlet, called second outlet 30b, located proximate to the end 31b. This second outlet 30b can notably be connected to a pump 52 by way of a fluidic connection tube, called second tube 41. In particular, this latter arrangement can be used to purge and/or transfer the gaseous sample from the measuring cell.
The remainder of this description discloses a method for the chemical analysis of a gaseous sample comprising a carrier gas wherein H2S is diluted. In particular, the carrier gas may comprise dinitrogen, CH4 or H2, without, however, limiting the present disclosure to these gases alone.
In a preferred embodiment, the conversion reagent comprises I2O5, in powder or single-crystal form.
The reaction between H2S and I2O5 is written as follows:
5H2S+3I2O5→3I2+5SO2+5H2O
The chemical analysis method also comprises a step b) for acquiring an absorption spectrum of the gaseous sample after step a) has been carried out in the measuring cell 30.
In these regards, the gas sample is transferred (step al)) from the conversion cell 20 to the measuring cell 30 via the fluidic connection means. In particular, this transfer may involve positioning the three-way valve 50 so as to allow the gas sample to flow from the first outlet 20b to the second inlet 30a.
Acquisition of the absorption spectrum involves illumination of the gas sample present in the measuring cell 30 by the light source 60 and collection of the light signal, after absorption by the gas sample, by the spectrograph 61.
In the 185 nm-225 nm wavelength range, SO2 has a specific “comb” signature, as shown in
The present disclosure also comprises a step c) of mathematically processing the absorption spectrum to deduce the concentration of SO2 in the gaseous sample.
Knowing the SO2 concentration in the gaseous sample gives access to the initial H2S concentration in the gaseous sample.
Mathematical processing step c) can comprise a Fourier transform calculation of the absorption spectrum. In particular, the Fourier transform of the spectrum shown in
Advantageously, mathematical processing step c) can be carried out by way of the computer 62.
Thus, the present disclosure proposes to determine the concentration of diluted H2S in a carrier gas by converting it into SO2. The latter has a higher absorption level than H2S, between 185 nm and 225 nm, and can therefore be used to measure H2S concentrations in a sample below the thresholds usually accepted when using analytical techniques known to the skilled person.
The chemical analysis method can comprise a background measurement step a0), preceding step a), which comprises measuring the absorption spectrum of a gaseous sample, referred to as background, formed solely of the carrier gas. This step a0) notably involves acquiring an absorption spectrum of the (dichlorine-free) carrier gas present in the measuring cell in the same way as in step b).
In particular, the carrier gas may have been taken from the carrier gas source 51.
Of course, the present disclosure is not limited to the described embodiments and variant embodiments may be envisaged without departing from the scope of the invention as defined by the claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2308127 | Jul 2023 | FR | national |
