WO2022243080A1 - Procede de caracterisation de presence et/ou de quantification de polymeres dans un milieu poreux - Google Patents
Procede de caracterisation de presence et/ou de quantification de polymeres dans un milieu poreux Download PDFInfo
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- WO2022243080A1 WO2022243080A1 PCT/EP2022/062455 EP2022062455W WO2022243080A1 WO 2022243080 A1 WO2022243080 A1 WO 2022243080A1 EP 2022062455 W EP2022062455 W EP 2022062455W WO 2022243080 A1 WO2022243080 A1 WO 2022243080A1
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- porous medium
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- 229920000642 polymer Polymers 0.000 title claims abstract description 334
- 238000000034 method Methods 0.000 title claims abstract description 58
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 219
- 238000010438 heat treatment Methods 0.000 claims abstract description 188
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 138
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 127
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 123
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 117
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 109
- 239000011159 matrix material Substances 0.000 claims description 168
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 41
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 41
- 230000001590 oxidative effect Effects 0.000 claims description 35
- 239000004576 sand Substances 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- -1 polyethylene terephthalate Polymers 0.000 claims description 10
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 229920001774 Perfluoroether Polymers 0.000 claims description 3
- 238000005259 measurement Methods 0.000 abstract description 57
- 229960004424 carbon dioxide Drugs 0.000 description 73
- 238000001757 thermogravimetry curve Methods 0.000 description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 229930195733 hydrocarbon Natural products 0.000 description 15
- 239000011435 rock Substances 0.000 description 15
- 238000012512 characterization method Methods 0.000 description 12
- 238000000197 pyrolysis Methods 0.000 description 12
- 238000001514 detection method Methods 0.000 description 9
- 238000011002 quantification Methods 0.000 description 6
- 239000004927 clay Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- BKHJHGONWLDYCV-UHFFFAOYSA-N [C]=O.[C] Chemical compound [C]=O.[C] BKHJHGONWLDYCV-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/12—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using combustion
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/24—Earth materials
- G01N33/241—Earth materials for hydrocarbon content
Definitions
- the invention relates to the field of the characterization and quantification of polymers in a porous medium, in particular to identify the level of pollution of a sediment, a soil of a natural environment such as that of a beach.
- the invention also allows the quantification of the polymers in the porous medium in order to assess the level of environmental pollution.
- plastics polymer-based materials
- these polymers can be found in the environment in a microscopic form invisible to the human eye but still generate significant pollution for fauna and flora.
- these polymers can be transformed in the environment, by physical or chemical phenomena and thus create compounds that are called “neoformed”, that is to say, existing only by the presence of polymers in the 'environment.
- the ROCK-EVAL® device (IFP Energy Energy Supply, France), developed by the applicant, and described in particular in documents FR 2227797 (US 3953171) and FR 2472754 (US 4352673).
- the ROCK-EVAL® device allows pyrolysis in an inert atmosphere (non-oxidizing, i.e. without the presence of oxygen) and oxidation, according to a sequence of predefined temperatures of a sample, for example of sedimentary rock .
- the pyrolysis furnace cooperates with a device for detecting and measuring the amount of hydrocarbon compounds in the pyrolyzed sample.
- the specific detection device comprises, for example, a detector of the flame ionization type, conventionally used in analyzes by gas phase chromatography.
- the detector delivers a signal representative of the quantities of hydrocarbon products measured. This signal can be transmitted to calculation, storage and display means in which specific software calculates, displays and stores the various parameters representative of the characteristics of the hydrocarbons present.
- An infrared detection device is also integrated in the ROCK-EVAL® device in order to measure the quantity of non-hydrocarbon compounds (CO and CO2) coming from the pyrolyzed and then oxidized sample.
- thermogram is a curve representing the revolution of the quantity of a released product (hydrocarbon compounds for example), related to the weight of the sample considered, as a function of time.
- a thermogram generally presents several peaks (cf. for example the peaks of Figure 2) generally well differentiated. From the surface of one of these peaks, we obtain a quantity representative of the quantity of the product released (hydrocarbon compounds for example) during the temperature range surrounding the peak considered.
- TOC total organic carbon
- MinC mineral carbon
- the temperature sequence of this method is characterized by an initial temperature T1 of the pyrolysis furnace generally between 300° C. and 350° C., a temperature which is maintained for a predetermined period of a few minutes. It is during this phase that the so-called “free” hydrocarbons are released (corresponding in reality to hydrocarbons of light to heavy molecular weight) initially contained in the rock sample. Their quantity is estimated by measuring the area of a first peak, denoted Si.
- the pyrolysis temperature is gradually increased to a temperature T2, generally 650°C.
- T2 a temperature
- S2 the area of a second peak
- the so-called “Reservoir” method is also known, which can also be implemented by means of the ROCK-EVAL® device, and dedicated more particularly to samples of reservoir rocks and oils. This method is described in particular in document EP 0691540 B1 (US 5843787).
- the sequence of temperatures of the “Reservoir” method is characterized by an initial temperature T 1 of the pyrolysis furnace of less than 200°C and preferably equal to 180°C. This temperature is maintained for a predetermined period and the amount of light hydrocarbon compounds is estimated by measuring the area of a first peak, denoted Si r .
- the temperature of the pyrolysis furnace is raised to a second temperature T2 of approximately 370°C, during which the quantity of heavier hydrocarbons released is estimated via the estimation of the surface of a second peak , denoted S2 a -
- the temperature T2 corresponds substantially to the end of the thermovaporization of certain hydrocarbons and to the beginning of the cracking by pyrolysis of the heavy compounds.
- the family of hydrocarbon compounds corresponding to the Si r and S2 a peaks of the "Reservoir" method is almost equivalent to the family of hydrocarbon compounds characteristic of the Si peak of the "Basic” method, i.e. hydrocarbons of light to heavy molecular weight .
- the pyrolysis temperature is again increased to a third temperature T3 of at most 650°C.
- the area of a third peak, denoted S2 b representative of heavy hydrocarbon compounds, is estimated during this third heating phase.
- This S2 b peak can be considered as an equivalent of the S2 peak of the “Basic” method.
- the temperature sequence of the “Shale Play” method comprises a succession of three heating stages (ramps corresponding to segments A, C, and E in Figure 1), separated by two temperature maintenance steps (isothermal stages corresponding to segments B and D in Figure 1), allowing the differentiated release of light, heavy and very heavy hydrocarbon compounds. More precisely, the temperature sequence of the “Shale Play” method starts at a first low temperature (T 1 ), between 50 and 120°C, which makes it possible to more completely measure the quantity of so-called free hydrocarbon compounds ( actually light to heavy molecular weight) present in a sample.
- T 1 first low temperature
- thermovaporization of the thermovaporizable hydrocarbon compounds in the considered temperature range.
- FIG. 2 presents an example of a thermogram recorded during the heating sequence under an inert atmosphere as described in Figure 1 .
- S h o three peaks
- S hi the quantity of hydrocarbon compounds released during the various heating stages.
- the ShO peak corresponds to the quantity of hydrocarbon compounds released between the first temperature T1 and the second temperature T2, i.e. during segments A and B of Figure 1.
- This S h o peak is representative of the most heat-vaporizable hydrocarbons. light.
- Peak Sh1 corresponds to the quantity of hydrocarbon compounds released between the second temperature T2 and the third temperature T3, ie during segments C and D of FIG. 1.
- This peak Sm is representative of heavy thermovaporizable hydrocarbons.
- the Sh2 peak corresponds to the quantity of hydrocarbon compounds released between the third temperature T3 and the fourth temperature T4, i.e. during segment E of Figure 1.
- This peak S h 2 is representative of very heavy thermovaporizable hydrocarbons as well as cracking non-volatile organic matter (kerogen).
- the invention relates to a method for characterizing the presence (or absence) of at least one polymer in a porous medium and/or for quantifying at least this polymer in a porous medium, the porous medium preferably being a natural porous medium.
- a sample of the porous medium is heated, according to a first heating sequence under an inert atmosphere, and a representative quantity of hydrocarbon compounds, a representative quantity of carbon and/or a representative quantity of carbon dioxide released during the first heating sequence; b) a residue of the sample resulting from the first heating sequence is heated according to a second heating sequence under an oxidizing atmosphere, and a representative quantity of carbon monoxide and/or a representative quantity of the carbon dioxide released is continuously measured during the second heating sequence; c) at least one parameter is determined from at least one curve of the measured quantity representative of hydrocarbon compounds released during the first heating sequence and/or from a curve of the measured quantity representative of carbon monoxide released during the first heating sequence and/or a curve of the representative measured quantity of carbon monoxide released during the second heating sequence and/or a curve of the representative measured quantity of carbon dioxide released during the first heating sequence and/or a curve of the measured quantity representative of carbon dioxide released during the second heating sequence, and this parameter is determined from at least one curve of the measured quantity representative of hydrocarbon
- step c) at least one temperature corresponding to a peak of the curve of the measured quantity representative of hydrocarbon compounds released during the first heating sequence and/or at least one temperature corresponding to a peak of the curve of the representative measured quantity of carbon monoxide released during the first heating sequence and/or at least one temperature corresponding to a peak of the curve of the representative measured quantity of carbon dioxide released during the first heating sequence and/or or at least one temperature corresponding to a peak of the curve of the measured quantity representative of carbon monoxide released during the second heating sequence and or at least one temperature corresponding to a peak of the curve of the measured quantity representative of carbon dioxide released during the second heating sequence.
- the first database is constructed as follows:
- polystyrene resin preferably at least polyethylene terephthalate, polyethylene, polyamide and/or perfluoroalkoxy.
- steps a) and b) are applied to a sample of each type of polymer defined replacing the sample of the porous medium and for each type of polymer defined the at least one reference parameter of the first database, the at least one reference parameter of the first database comprising at least one temperature at which:
- - corresponds to a peak of the curve of the measured quantity representative of hydrocarbon compounds released by the sample of the type of polymer defined during the first sequence of heating and/or
- - corresponds to a peak of the curve of the measured quantity representative of carbon monoxide released by the sample of the type of polymer defined during the first sequence of heating and/or
- - corresponds to a peak of the curve of the measured quantity representative of carbon dioxide released by the sample of the type of polymer defined during the first sequence of heating and/or
- - corresponds to a peak of the curve of the measured quantity representative of carbon dioxide released by the sample of the type of polymer defined during the second heating sequence and the at least one reference parameter of the first database further comprising preferably at least: - a representative quantity of hydrocarbon compounds released by the sample of the type of polymer defined during the first heating sequence, and/or
- the at least one reference parameter from the first database is added to the first database, for each type of polymer defined.
- step II) is repeated with several samples of each type of polymer defined.
- step c) at least one of the temperatures determined in step c) for the sample of porous medium is compared with at least one corresponding temperature of the at least one reference parameter of said first database.
- the second database is constructed in the following manner: i) several types of matrices of porous media are defined, preferably the types of matrices include at least sand, marl, carbonates and clays. ii) for each type of matrix defined, steps a) and b) are carried out with a sample of each type of matrix defined replacing the sample of said porous medium and for each type of matrix defined the at least one reference parameter of the second database, the at least one reference parameter of the second database comprising at least one temperature at which:
- the at least one reference parameter of the second database comprising further preferably at least:
- step ii) is repeated with several samples of each type of matrix defined.
- step c) at least one of the temperatures determined in step c) is compared with at least one corresponding temperature of the at least one reference parameter of said second database.
- the comparison is carried out by calculating at least one difference between at least one temperature corresponding to said peak of one of said curves of the quantities measured on said sample of said porous medium and the corresponding temperature of the at least one reference parameter for each type of polymer defined in the first database, and in step d), if, for at least one of the types of polymer defined, at least one of these differences is less than a predetermined threshold, the presence of this type of polymer defined in said porous medium is concluded, and in the opposite case, the absence of this type of polymer defined in said porous medium is concluded.
- step d) if it has been concluded that said type of polymer defined is present in said porous medium, said type of said polymer defined is quantified in said porous medium by determining a percentage of said type of polymer defined in said porous medium from a ratio between the representative measured quantity of hydrocarbon compounds released during the first heating sequence in the sample of the porous medium and the representative measured quantity of hydrocarbon compounds released by said type of polymer defined during the first heating sequence, and if it has been concluded that said type of polymer defined is absent in said porous medium, a zero quantity is attributed to said type of polymer defined.
- the measured quantities representative of hydrocarbon compounds, of carbon monoxide and of carbon dioxide are normalized by the initial mass of the sample.
- said first heating sequence in an inert atmosphere comprises at least the following step: starting from a temperature between 100° C. and 300° C., the temperature is raised according to a gradient of temperature between 5 and 30°C/minute, up to a temperature between 500 and 650°C.
- said second heating sequence in an oxidizing atmosphere comprises at least the following step: from a temperature between 200° C. and 400° C., the temperature is raised according to a temperature gradient comprised between 10 and 40°C/minute, up to a temperature of between 750 and 950°C.
- Figure 1 illustrates a variant of a heating sequence under an inert atmosphere of the process according to the invention.
- Figure 2 illustrates the evolution of the quantity of hydrocarbon compounds (Q) with time (t) during pyrolysis established on a given sample, according to the sequence of heating under inert atmosphere of Figure 1.
- Figure 3 illustrates a measurement thermogram of one of the quantities during a heating sequence according to the invention.
- Figure 4 illustrates the evolution of the maximum peak temperature (Tpeak) of release of hydrocarbon compounds during heating in the inert phase in different samples of a mixture of sand and PET polymer containing different concentrations of PET.
- FIG. 5 illustrates the curves for the release of hydrocarbon compounds during a heating sequence under an inert atmosphere for a sample of PET polymer and for a sample of PFA polymer.
- FIG. 6 illustrates the carbon monoxide (CO) release curves during a heating sequence under an inert atmosphere for a sample of PET polymer and for a sample of PFA polymer.
- FIG. 7 illustrates the carbon dioxide release curves (CO ⁇ ) during a sequence of heating under an inert atmosphere for a sample of PET polymer and for a sample of PFA polymer.
- FIG. 8 illustrates the carbon monoxide (CO) release curves during a heating sequence under an oxidizing atmosphere for a sample of PET polymer and for a sample of PFA polymer.
- FIG. 9 illustrates the carbon dioxide (CO2) release curves during a heating sequence under an oxidizing atmosphere for a sample of PET polymer and for a sample of PFA polymer.
- Figure 10a illustrates an example of measurement during a heating sequence for different porous media samples, the different porous media consisting of a sand matrix and a single PET polymer, the samples being distinguished from each other by different amounts of PET in the porous medium.
- Figure 10b illustrates the evolution of the amount of total organic carbon released, the amount of hydrocarbon compounds released, the amount of carbon monoxide released and the amount of carbon dioxide released on samples of a mixture of a sand and PET matrix for different concentrations of PET in the sample.
- Figure 11 illustrates the relationships between the quantity measured under a release peak of a product (here hydrocarbon compounds) as a function of the quantity of polymer present in a porous medium for different types of matrices.
- Figure 12 illustrates an example of identification of a polymer in a real porous medium using the method according to the invention.
- the invention relates to a method for characterizing the presence (or absence) of at least one polymer in a porous medium, such as a natural porous medium, and/or for the quantification of at least one polymer in this porous medium.
- the porous medium is preferably taken from a natural environment, possibly polluted by polymers, such as a beach.
- at least the following steps are carried out: a) a sample of the porous medium is heated, according to a first sequence of heating under an inert atmosphere (non-oxidizing, that is to say without oxygen), and continuously a representative quantity of hydrocarbon compounds released during the first heating sequence, a representative quantity of carbon monoxide and/or a representative quantity of carbon dioxide released during the first heating sequence.
- Carbon monoxide and carbon dioxide are generally representative of so-called “mineral” carbon, ie derived from carbonated materials for example.
- Polymers are generally composed of the elements carbon and hydrogen.
- the measurement of hydrocarbon compounds is more easily representative of polymers.
- this phase under an inert atmosphere is essential. Indeed, by carrying out this phase under an oxidizing atmosphere, the hydrocarbon compounds would react with the oxygen and would be transformed. Thus, it would be difficult or even impossible to detect them accurately.
- a residue of the sample resulting from the first heating sequence is heated according to a second heating sequence under an oxidizing atmosphere, and a representative quantity of carbon monoxide and/or a representative quantity of the carbon dioxide released is continuously measured during the second heating sequence;
- This phase makes it possible to detect the rest of the carbonaceous materials not detected during the phase under an inert atmosphere. It makes it possible to refine the measurements and therefore the characterizations that will result from these measurements. It also makes it possible to determine the quantity of total organic carbon (TOC) in the samples per mass of polymer analyzed.
- TOC total organic carbon
- At least one parameter is determined from at least one curve of the measured quantity representative of hydrocarbon compounds released during the first heating sequence and/or from a curve of the measured quantity representative of carbon monoxide released during the first heating sequences and/or a curve of the measured quantity representative of carbon monoxide released during the second heating sequence and/or a curve of the measured quantity representative of carbon dioxide released during the first heating sequence and/or a curve of the measured quantity representative of carbon dioxide released during the second heating sequence, and said at least one parameter is compared with at least one reference parameter from a first database relating to at least said polymer, and preferably to at least one reference parameter (or reference characteristic) from a second database relating to at least one matrix representative of the porous medium.
- the sample of the porous medium which is tested and analyzed generally comprises a matrix and potentially one or more polymers which pollute the matrix.
- the matrix is the "pure" porous medium, that is to say free of any polymer.
- the matrix can therefore be clay, sand, marl, carbonates or any other pure (or clean, in the sense unpolluted by polymers) natural porous medium.
- the first database identifies reference parameters for different types of polymers while the second database identifies reference parameters (or reference characteristics) for different types of matrices.
- the reference parameters of the first and second databases serve as a basis for comparison to the parameters determined from the measured quantity curves. d) from the comparison of the parameter determined (preferably the parameters determined) from at least one of the curves of one of the quantities measured with the reference parameters of a first database relating to different types of polymers ( at least one polymer) and preferably to the reference parameters of a second database relating to at least one matrix representative of the porous medium, the presence or absence of at least one polymer in the porous medium is characterized, and/or a quantity of this polymer is determined in the porous medium (this polymer is quantified in the porous medium).
- a characterization parameter can be used which can comprise a vector of binary values, the binary values being equal either to “zero”, or to “one”, “zero” corresponding for example to the absence of polymer in the porous medium and “one” corresponding to the presence of polymer in the porous medium.
- the vector can thus identify, for each polymer defined in the first database, the presence or absence of polymer in the porous medium.
- the characterization parameter corresponding to the vector (1;0;0) identifies the presence PE in the porous medium and the absence of PFA and PTFE in this same porous medium.
- the characterization parameter can also include the estimated quantity (in mass, in percentage of mass of the sample of the porous medium, or in percentage of volume of the sample of the porous medium for example) of each type of polymer of the first base data in the porous medium.
- the characterization parameter can comprise a vector of real values.
- the characterization parameter can include the following vector (2.3;0;0), in addition to or replacing the vector of binary values mentioned above .
- it is estimated at approximately 2.3% by mass of the weight of PE in the porous medium, the other values of PFA and PTFE are zero given the identified absence of these polymers in the medium. porous.
- This method thus makes it possible to evaluate the level of pollution of a natural porous medium with polymers, to identify which are the dominant polymers of the environment of the porous medium, and this method makes it possible to evaluate the evolution of the local pollution of the porous medium.
- porous medium is meant a porous medium which can be “consolidated”, that is to say formed of a single solid block like a rock or which can be “unconsolidated”, that is to say formed of a multitude of solid grains, like sand.
- the porous medium can advantageously be derived from an underground geological formation, such as a sedimentary rock, or from a surface geological formation forming a soil, such as a layer of sand or a surface rock.
- the reference parameters of the first database relating to the polymers and of the second database relating to the matrices of the porous medium correspond to the parameters determined from a curve of at least one measured quantity representative of the hydrocarbon compounds released under an inert atmosphere, of carbon monoxide and/or carbon dioxide released under inert atmosphere and/or under oxidizing atmosphere, released respectively by at least one polymer (for the reference parameters) and by at least one matrix (for the reference characteristics).
- these reference parameters and characteristics can be compared to the measurements carried out on the sample of porous medium under inert atmosphere and under oxidizing atmosphere.
- a reference parameter from the first or from the second database corresponding to a parameter determined in step c it is the same parameter measured on a sample of polymer (for the first base of data) or on a sample of matrix (for the second database) replacing the sample of porous medium.
- the reference parameters and characteristics also include each/each five reference data corresponding to the five thermograms of the porous medium.
- thermograms obtained on the sample of the porous medium one can discredit the part coming from the matrix and the part coming from one or more polymers.
- the first sequence of heating in an inert atmosphere can comprise at least the following step: starting from a temperature of between 100° C. and 300° C., the temperature is raised according to a temperature gradient of between 5 and 30°C/minute, up to a temperature between 500 and 650°C.
- a linear change in temperature is obtained, fast enough to obtain rapid results and slow enough to obtain curves that can be interpreted, that is to say allowing a gradual release of hydrocarbon compounds, carbon monoxide carbon and carbon dioxide as the temperature changes.
- the second sequence of heating in an oxidizing atmosphere can comprise at least the following step: starting from a temperature of between 200° C. and 400° C., the temperature is raised according to a temperature gradient of between 10 and 40°C/minute, up to a temperature between 750 and 950°C.
- a linear evolution of the temperature is obtained, fast enough to obtain rapid results and slow enough to obtain curves that can be interpreted, that is to say allowing a progressive release of carbon monoxide and carbon dioxide. of carbon as the temperature changes.
- the heating sequences of the “Shale Plays” method described previously and represented in FIG. 1 can be used during steps a) and b). Indeed, these heating sequences make it easier to distinguish the peaks between the different polymers.
- the heating sequences of the "Basic” or “Tank” methods can also be used during steps a) and b). These also make it possible to effectively distinguish between different polymers.
- thermogram it is possible to identify one or more release peaks corresponding to a temperature of the heating sequence considered.
- a release peak is defined by an increasing evolution of the measurement upstream of the peak (upstream in time of the heating sequence considered) and by a decreasing evolution of the measurement downstream of the peak (downstream in time of the heating sequence). considered heating sequence), near the peak.
- the measured quantities of hydrocarbon compounds, of carbon monoxide and of carbon dioxide can be normalized by the initial mass of the sample of the porous medium.
- normalization we mean that we divide the quantity considered (hydrocarbon compounds, carbon monoxide or carbon dioxide during the first or second heating sequence) by the initial mass of the sample considered, the initial mass being the mass before the steps of pyrolysis a) and oxidation b).
- all the quantities mentioned are advantageously normalized with respect to the weight of the relative sample (porous medium, polymer or matrix).
- the reference parameter (preferably the reference parameters) of the first database can comprise, for several types of polymer, a temperature at which:
- - corresponds to a peak of the curve of the measured quantity representative of hydrocarbon compounds released by the sample of the type of polymer defined during the first sequence of heating and/or
- - corresponds to a peak of the curve of the measured quantity representative of carbon monoxide released by the sample of the type of polymer defined during the first sequence of heating and/or
- - corresponds to a peak of the curve of the measured quantity representative of carbon dioxide released by the sample of the type of polymer defined during the first sequence of heating and/or
- - corresponds to a peak of the curve of the representative measured quantity of carbon dioxide released by the sample of the type of polymer defined during the second heating sequence and the reference parameter of the first database further comprising preferably at least :
- the quantities and temperatures defined above apply to each type of polymer alone. In other words, these are the quantities and temperatures which would be obtained with a sample of porous medium consisting solely of the polymer considered (the sample would be a sample of the polymer considered alone as “pure”). Thus, for each polymer considered in the first database, the quantities and temperatures listed above are identified which correspond to the reference parameters of the polymer considered and which constitute the identity card of each polymer.
- the corresponding quantities are compared: for example, the representative quantity of hydrocarbon compounds released by the sample of porous medium during said first sequence of heating to this same quantity (the representative quantity of hydrocarbon compounds during said first sequence) released by the polymer considered.
- the representative quantity of hydrocarbon compounds released by the sample of porous medium during the first heating sequence with the representative quantity of carbon monoxide released by the polymer considered during the first sequence.
- the reference parameter (preferably the reference parameters) of the second database may comprise, for several matrices, at least one temperature at which:
- - corresponds to a peak of the curve of the measured quantity representative of hydrocarbon compounds released by the sample of the type of matrix defined during the first sequence of heating and/or
- - corresponds to a peak of the curve of the measured quantity representative of carbon monoxide released by the sample of the matrix type defined during the first sequence of heating and/or
- - corresponds to a peak of the curve of the measured quantity representative of carbon dioxide released by the sample of the type of matrix defined during the first sequence of heating and/or
- - corresponds to a peak of the curve of the representative measured quantity of carbon dioxide released by the sample of the type of matrix defined during the second heating sequence and/or and the reference parameter of the second database further comprising preferably at least:
- the quantities and temperatures defined above apply to the pure matrix alone, i.e. not polluted by any polymer. In other words, these are the quantities and temperatures that would be obtained with a sample of porous medium consisting only of the matrix considered, without polymers (the sample would be a sample of the matrix considered alone “pure”).
- the corresponding quantities are compared: for example, the quantity representative of hydrocarbon compounds released by the sample of porous medium during the first heating sequence to this same quantity (the representative quantity of hydrocarbon compounds during said first sequence) released by the matrix considered.
- the representative quantity of hydrocarbon compounds released by the sample of porous medium during the first heating sequence with the representative quantity of carbon monoxide released by the matrix considered during the first sequence.
- the first database can be constructed as follows:
- polystyrene resin preferably at least polyethylene terephthalate (PET), polyethylene (PE), polyamide (PA), perfluoroalkoxy (PFA) and/or polypropylene (PP).
- PET polyethylene terephthalate
- PE polyethylene
- PA polyamide
- PFA perfluoroalkoxy
- PP polypropylene
- the polymers found in the porous medium it is possible to use several shades of each of these polymers, for example several shades of polyethylene or of polyamide.
- steps a) and b) of the process are applied (i.e. the two sequences of heating simultaneously with the planned measurements) to a sample of each type of polymer defined replacing the sample of the porous medium and we determines at least one reference parameter (preferably several reference parameters) from the first database for each type of polymer defined.
- defined polymer sample is meant a sample of polymer alone (or pure), that is to say without matrix. In other words, the polymer constitutes 100% of the porous medium.
- the reference parameter(s) from the first database are added to the first database, for each type of polymer defined.
- thermograms From the five thermograms obtained on the sample of each defined polymer (pure, without matrix), the five thermograms being the curves of measurements of the quantities measured representative of hydrocarbon compounds during the first heating sequence and of the quantities measured representative of carbon monoxide carbon and carbon dioxide during the first and second heating sequences, the following different standardized quantities can be calculated:
- Total CO2 polymer [IR CO2 Signal polymer /Initial maSS polymer ]
- Total HC p oiymer corresponding to the quantity of total hydrocarbon compounds released by the polymer sample (alone, without matrix) during the phase under inert atmosphere
- Total CO p oiymer corresponding to the total quantity of monoxide released by the polymer sample ( alone, without matrix), corresponding to the sum of the quantity of carbon monoxide released by the polymer sample (alone, without matrix) during the phase under inert atmosphere and during the oxidizing phase.
- Total CO2 p oiymer corresponding to the total quantity of carbon dioxide released by the polymer sample (alone, without matrix), corresponding to the sum of the quantity of carbon dioxide released by the polymer sample (alone, without matrix) during the phase under inert atmosphere and during the oxidizing phase.
- FID p0iymer signal corresponding to the area under the signal measured by the FID sensor (flame ionization) during the phase under inert atmosphere with the polymer sample (pure, without matrix).
- IR CO poiymer signal corresponding to the area under the signal measured by the infrared sensor for measuring carbon monoxide CO during the phase under inert atmosphere and during the phase under oxidizing atmosphere, therefore to the sum of the areas under the signals of these two phases, with the sample of the polymer (pure, without matrix).
- IR CO2 signal p0iymer corresponding to the area under the signal measured by the infrared sensor for measuring carbon dioxide CO2 during the phase under inert atmosphere and during the phase under oxidizing atmosphere, therefore to the sum of the areas under the signals of these two phases, with the sample of the polymer (pure, without matrix).
- Tpeak H Cpolymer temperature of the hydrocarbon compound release peak during the first heating sequence from the defined polymer sample alone (or pure):
- Tpeak HCpoiymer [Temperature of FID signal maximumHCpoi y mer](°C)
- Temperature of FID maximum signal H cp oiymer corresponds to the temperature corresponding to the maximum measurement of the curve measured by the FID sensor (flame ionization), therefore to the peak release of hydrocarbon compounds.
- Tpeak copoiymer si [Temperature of IR maximum signal C opoiymer_si](°C)
- Temperature of IR maximum signal C op oiymer _si corresponds to the temperature corresponding to the maximum measurement of the curve measured by the carbon monoxide infrared detection sensor, therefore to the peak of carbon monoxide release during the first heating sequence .
- Tpeak co poi y mer_si [Temperature of IR maximum signal C o2poiymer_si]( 0 C)
- Temperature of IR signal maximum C o 2poiymer _si corresponds to the temperature corresponding to the maximum measurement of the curve measured by the carbon dioxide detection infrared sensor, therefore to the peak of carbon dioxide release during the first heating sequence .
- Tpeak co Poiymer _s 2 [Temperature of IR maximum signal Copoiymer _s 2 ](°C) Where: Temperature of IR signal maximurrico Poiymer _s2 corresponds to the temperature corresponding to the maximum measurement of the curve measured by the infrared carbon monoxide detection sensor, therefore to the peak release of carbon monoxide during the second heating sequence.
- Tpeak co2 Oiymer _s2 [Temperature of IR signal maximumco2 Poiymer _s2](°C)
- Temperature of IR maximum signal C o2 Poiymer _s2 corresponds to the temperature corresponding to the maximum measurement of the curve measured by the infrared carbon dioxide detection sensor, therefore to the peak of carbon dioxide release during the second heating sequence .
- step II) can be repeated with several samples (at least 2 and preferably between 5 and 10) of each type of polymer defined.
- samples at least 2 and preferably between 5 and 10.
- the second database can be constructed in the following way: i) several types of matrices of porous media are defined, preferably the types of matrices comprise at least sand, marl, carbonates and clays which are the major types of natural matrices. ii) for each type of matrix defined, steps a) and b) of the process are carried out (i.e. the two sequences of heating in an inert atmosphere and in an oxidizing atmosphere simultaneously with the planned measurements) with a sample of each type of matrix defined as a replacement for the sample of the porous medium and for each type of matrix defined, at least one reference parameter from the second database is determined. iii) one adds in the second database, for each type of matrix defined, the reference parameter(s) of the second database.
- step ii) can be repeated with several samples (at least 2 and preferably between 5 and 10) of each type of matrix defined.
- samples at least 2 and preferably between 5 and 10.
- thermograms From the five thermograms obtained on the sample of each defined matrix, the five thermograms being the measurement curves of the representative quantities of hydrocarbon compounds during the first heating sequence and of the representative quantities of carbon monoxide and carbon dioxide during the first and second heating sequences, the following different standardized quantities can be calculated:
- Total HC matrix corresponding to the quantity of total hydrocarbon compounds released by the matrix sample (alone, without polymer, i.e. "pure” or unpolluted) during the phase under inert atmosphere
- Total CO m atrix corresponding to the total quantity of monoxide released by the matrix sample (alone, without polymer, i.e. "pure” or unpolluted), corresponding to the sum of the quantity of carbon monoxide released by the sample of the matrix (alone, without polymer, that is to say “pure” or not polluted) during the phase under an inert atmosphere and during the oxidizing phase.
- Total CO 2 matnx corresponding to the total quantity of carbon dioxide released by the matrix sample (alone, without polymer, i.e. "pure” or unpolluted), corresponding to the sum of the quantity of carbon dioxide released by the sample from the matrix (alone, without polymer, that is to say “pure” or uncontaminated) during the phase under an inert atmosphere and during the oxidizing phase.
- FID signal matrix corresponding to the area under the signal measured by the FID sensor (flame ionization) during the phase under inert atmosphere, with the matrix sample (alone, without polymer, i.e. “pure e » or unpolluted).
- IR CO signal matrix corresponding to the area under the signal measured by the infrared sensor for measuring carbon monoxide CO during the phase under inert atmosphere and during the phase under oxidizing atmosphere, therefore to the sum of the areas under the signals of these two phases, with the matrix sample (alone, without polymer, that is to say “pure” or unpolluted).
- IR CO 2 signal mathx corresponding to the area under the signal measured by the infrared sensor for measuring carbon dioxide CO 2 during the phase under inert atmosphere and during the phase under oxidizing atmosphere, therefore to the sum of the areas under the signals of these two phases, with the matrix sample (alone, without polymer, that is to say “pure” or unpolluted).
- Tpeak HC matTM [Temperature of FID signal maximum HC matrix](°C)
- Temperature of FID maximum signal H cmatrix corresponds to the temperature corresponding to the maximum measurement of the curve measured by the FID sensor (flame ionization), therefore to the peak release of hydrocarbon compounds, with the matrix sample (alone, without polymer, i.e. "pure” or unpolluted).
- Tpeak comatrix_si [Temperature of IR maximum signal C om atnx _si ]( 0 C)
- Temperature of IR signal maximum C omatnce_si corresponds to the temperature corresponding to the maximum measurement of the curve measured by the carbon monoxide infrared detection sensor, therefore to the peak release of carbon monoxide during the first heating sequence, with the matrix sample (alone, without polymer, that is to say "pure” or unpolluted).
- Tpeak C02matrixe_si [Temperature of IR maximum signal C o2m atrix _si ](°C)
- Temperature of IR signal maximum C o 2 matnx_si corresponds to the temperature corresponding to the maximum measurement of the curve measured by the carbon dioxide detection infrared sensor, therefore to the peak of carbon dioxide release during the first heating sequence , with the matrix sample (alone, without polymer, that is to say “pure” or unpolluted).
- the temperature of the carbon monoxide release peak during the second heating sequence from the matrix sample defined alone (or pure):
- Tpeak com atrix _s 2 [Temperature of IR signal maximumcom atrix _s 2 ]( 0 C)
- Temperature of IR signal maximumcom atrix _s 2 corresponds to the temperature corresponding to the maximum measurement of the curve measured by the infrared sensor for detecting carbon monoxide, therefore to the peak release of carbon monoxide during the second heating sequence, with the matrix sample (alone, without polymer, that is to say “pure” or unpolluted).
- Tpeak C o 2matrix _s 2 [Temperature of IR signal maximumco 2matrix _s 2 ](°C)
- Temperature of IR maximum signal C o 2matnx _s 2 corresponds to the temperature corresponding to the maximum measurement of the curve measured by the carbon dioxide detection infrared sensor, therefore to the peak of carbon dioxide release during the second sequence of heated, with the matrix sample (alone, without polymer, that is to say "pure” or unpolluted).
- the constructions of the first and second databases described previously can be carried out prior to step a), step b) or step c).
- the comparison can be carried out by calculating at least one difference between a temperature corresponding to the peak of a curve (or of several peak temperatures of several curves) quantities measured on the sample of the porous medium and the corresponding temperature of a reference parameter for each type of polymer defined in the first database.
- temperature or corresponding measured quantity of a reference parameter is meant the temperature resulting from the same type of measurement curve.
- the parameter of the determined porous medium is the peak temperature of a curve measuring the representative quantity of hydrocarbon compounds during the first heating sequence
- the corresponding temperature will be that of the peak of a curve measuring the representative quantity of hydrocarbon compounds during the first heating sequence obtained from the different types of polymers defined in the first database or the different types of matrices defined in the second database
- FIG. 3 schematically and non-limitingly illustrates an example of a thermogram representing a quantity Q measured over time t during a heating sequence.
- the quantity Q can correspond to a representative quantity of the hydrocarbon compounds, of carbon monoxide or of carbon dioxide and the heating sequence can be the first or the second heating sequence.
- the thermogram includes three measurement peaks P1, P2 and P3. In the vicinity of each of these peaks P1, P2 and P3, upstream (i.e. to the left) of each of these peaks P1, P2 and P3, the curve is increasing and downstream (i.e. say to the right) of each of these peaks, the curve is decreasing.
- peaks being separated by troughs C1 and C2 for which, in the vicinity of these troughs, the curve is decreasing before the trough (to the left of the trough) and the curve is increasing after the trough (to the right of the trough).
- each peak is associated with a time t1 for peak P1, t2 for peak P2 and t3 for peak P3.
- each instant of the heating sequence corresponds to a specific temperature.
- each peak of the thermogram corresponds to a specific peak temperature.
- peaks P1 to P3 can correspond to the matrix and/or to one or more polymers.
- peak P1 may correspond to the marl matrix
- peak P2 to a first polymer (PET for example)
- peak P3 to a second polymer (PFA for example).
- thermogram of measurement of hydrocarbon compounds it is preferable to use the thermogram of measurement of hydrocarbon compounds.
- the other thermograms can be used to confirm this initial identification or to refine it: one or more of these other thermograms can be used.
- To quantify the quantity of each polymer in the porous medium it is possible to identify the part of the measurement associated with each peak. For example, one can calculate the area (area) under the curve of each peak.
- first area A1 which stops at the first hollow C1
- this area being associated with the marl of the porous medium (the first peak P1 having been attributed to the marl type matrix)
- second area A2 under the curve between the first hollow C1 and the second hollow C2, this area A2 being associated with the polymer PET, and the third area A3 from the second hollow C2, this area A3 being associated with the polymer PFA.
- FIG. 4 schematically and non-limitingly illustrates an example produced by the applicant.
- different blend samples of a sand matrix (same sand in all samples) and one (single) PET polymer are mixed.
- Each sample has a different Ct content of PET, the content being measured as a mass percentage of PET in the sample.
- the five samples produced have a PET content in the mixture of 0.2%, 0.6%, 1.1%, 1.9% and 3.1% respectively.
- FIG. 4 represents the temperature Tpeak of the release peak of the hydrocarbon compounds measured during the inert phase as a function of the PET content of the sample considered.
- the measurement curve of the representative quantities of the hydrocarbon compounds in the inert phase comprises for all its samples only a single peak.
- the different diamonds represent the peak temperature values Tpeak obtained for each of the samples.
- step c) it is possible to determine, as a parameter from at least one curve of a quantity measured in steps a) and b), at least one temperature corresponding to a peak of the curve of said representative measured quantity of hydrocarbon compounds released during the first heating sequence and/or at least one temperature corresponding to a peak of the curve of the representative measured quantity of carbon monoxide released during the first heating sequence and/or at least one temperature corresponding to a peak of the curve of the measured quantity representative of carbon dioxide released during the first heating sequence and/or at least one temperature corresponding to a peak of the curve of the measured quantity representative of carbon monoxide released during the second heating sequence and/or at least one temperature corresponding to a peak of the curve of the representative measured quantity of carbon dioxide released during the second heating sequence.
- step c) it is possible to compare at least one of these temperatures with at least one temperature corresponding to the reference parameters of the first database and preferably to those of the second database (characteristics of reference).
- the comparison of this at least one temperature with the corresponding temperature of a polymer from the first database and possibly with the corresponding temperature of a matrix from the second database can make it possible to identify one or more polymer(s) and/ or the matrix of the porous medium.
- corresponding measurement or temperature is meant the same type of measurement or temperature between those carried out or obtained in steps a) and/or b) on the sample of the porous medium and those of the reference parameters of the first and second bases data for the different types of polymers and matrices from these databases. These corresponding measurements and/or temperatures are those which allow valid comparisons between the sample of the porous medium and the polymers of the first database and the matrices of the second database.
- the reference parameters of the first and second databases can then be the temperatures of the peak obtained from the curve of the measured quantity of hydrocarbon compounds during the first sequence of heating on the sample of each type of polymer defined from the first database or from each type of matrix defined from the second database.
- thermograms obtained on the sample of the porous medium can also be calculated:
- T Otai CO porous medium [I R CO Signal porous medium /Initial aSS porous medium]
- T Otai CO2 porous medium [I R CO2 Signal porous medium /Initial maSS porous medium ]
- Total HC porous medium corresponding to the total quantity of hydrocarbon compounds released by the porous medium sample during the phase under inert atmosphere
- Total CO pore medium corresponding to the total quantity of monoxide released by the porous medium sample , corresponding to the sum of the amount of carbon monoxide released by the sample of the porous medium during the phase under an inert atmosphere and during the oxidizing phase.
- Total CO2 orous medium corresponding to the total quantity of carbon dioxide released by the sample of porous medium, corresponding to the sum of the quantity of carbon dioxide released by the sample of the porous medium during the phase under inert atmosphere and during the phase oxidative.
- FID müe up o r e ux signal corresponding to the area under the signal measured by the FID sensor (flame ionization) during the phase under inert atmosphere with the sample of porous medium.
- IR CO signal m ü eu porous corresponding to the area under the signal measured by the infrared sensor for measuring carbon monoxide CO during the phase under inert atmosphere and during the phase under oxidizing atmosphere, therefore to the sum of the areas under the signals of these two phases, with the sample of porous medium.
- IR CO2 porous medium signal corresponding to the area under the signal measured by the infrared sensor for measuring carbon dioxide CO2 during the phase under inert atmosphere and during the phase under oxidizing atmosphere, therefore to the sum of the areas under the signals of these two phases, with the sample of porous medium.
- the temperatures of the hydrocarbon compound release peaks during the first heating sequence may be sufficient to identify one or more polymers in the porous medium. For example, if a peak is detected at a certain temperature corresponding to a reference parameter of a specific polymer, the parameter in question being the temperature of the peak of release of hydrocarbon compounds from a sample of polymer alone (or pure , without matrix) during the first heating sequence, one can identify (characterize) the presence (or absence) of this particular polymer.
- the temperature corresponds we mean a difference below a predefined criterion (20 * C for example and preferably 10°C) in absolute value. For example, when the difference between the temperature of the parameter is that of a reference parameter between -20°C and +20°C, these two temperatures can be considered to be corresponding.
- the peak temperature is found (within the predefined criterion, for example at +/-20°C, preferably + /-10°C) corresponding to the representative thermogram of the corresponding hydrocarbon compounds of a particular polymer of the first database, it can be considered that this particular polymer is present in the porous medium.
- the peak temperatures of other thermograms can also be used to refine or confirm the identification.
- thermograms carried out on the sample of porous medium all the peak temperatures are found (within the predefined criterion, for example at +/-10°C) corresponding to the corresponding thermograms of a particular polymer of the first base data, the presence of this polymer in the porous medium can be confirmed and the evaluation of the quantity of this polymer in the porous medium can be more precise.
- the matrix of the porous medium is sand
- the sand composed mainly of silica generating no hydrocarbon compound, nor any carbon monoxide or dioxide, whether under an inert or oxidizing atmosphere
- data representative of different porous medium matrices if we take sand from a beach, the matrix of this porous medium (pure sand, i.e. not polluted by polymers) will present thermograms without any peak.
- the peaks identified on the sampled polluted sand should directly correspond to polymers.
- the matrix of the porous medium may include carbon compounds capable of generating hydrocarbon compounds, carbon monoxide and/or carbon dioxide
- the use of a second database representative of the matrix may be useful.
- the peak temperature is found (within a predefined criterion, for example +/- 20°C, preferably +/-10°C) corresponding to the thermogram representative of the hydrocarbon compounds corresponding to a particular matrix of the second database, it can be considered that the matrix of the porous medium corresponds to this particular matrix. This makes it possible to identify, among the identified peaks of the porous medium, those which correspond to the matrix and those which correspond to one or more polymers.
- thermograms of the other measured quantities can be compared in the same way to refine the characterization.
- other peaks may correspond neither to a matrix of the second database, nor to a polymer of the first database.
- these peaks may correspond either to a matrix not identified in the second database, to a polymer not identified in the first database, or to a newly formed compound, i.e. a material which has been generated by the chemical reactions of the presence of a polymer in the matrix.
- the comparison can be carried out by calculating at least one difference between a temperature corresponding to the peak of a curve (or of several peak temperatures of several curves ) quantities measured on the sample of the porous medium and the corresponding temperature of a reference parameter for each type of polymer defined in the first database, in step d), if, for at least one of the types of polymer defined, at least one of these differences (the absolute value of the difference) is lower than a predetermined threshold (for example lower than 20°C, preferably lower than 10°C), one can conclude the presence of this type of polymer defined in the porous medium, and in the opposite case, one can conclude the absence of this type of polymer defined in the porous medium.
- a predetermined threshold for example lower than 20°C, preferably lower than 10°C
- the type of polymer defined in the porous medium can be quantified (the quantity of this defined polymer in the porous medium) by determining a percentage of the type of polymer defined in the porous medium from a ratio between the representative measured quantity of hydrocarbon compounds released during the first sequence of heating in the sample of the medium porous medium and the representative measured quantity of hydrocarbon compounds released by the type of polymer defined during the first heating sequence, and if it has been concluded that the type of polymer defined is absent in the porous medium, a zero quantity is attributed to the type of defined polymer.
- Figures 5 to 9 illustrate, in a schematic and non-limiting manner, the quantities measured (respectively the quantity of hydrocarbon compounds during the inert phase HC, the amount of carbon monoxide during the inert phase COJnert, the amount of carbon dioxide during the inert phase C02_inert, the amount of carbon monoxide during the oxidative phase CO_oxyd and the amount of carbon dioxide during the oxidative phase C02_oxyd) released over time t in minutes, during a heating sequence SC where the temperature T (in °C) varies over time t for a first sample Poli of pure PET (without matrix) and for a second sample Pol2 of PFA pure (without matrix).
- the heating sequences SC of the same figure are identical for the two samples Poli and Pol2.
- the release peak temperature of hydrocarbon compounds is generally preferred to distinguish polymers (because the curves in Figure 5 are sharper and the peaks are more marked, the width of the curve around the peaks being weaker ) and that it may be sufficient. It can be noted that, for this example, the curves of measurements of carbon monoxide in the oxidizing phase CO_oxyd of FIG. 8 are much less clear and that these curves are therefore less favorable to the distinction of the different polymers.
- the temperature of the peaks is a precise parameter with little variation, which makes it easier to know how to distinguish the polymers.
- Figure 10a illustrates, in a schematic and non-limiting manner, various measurements of a quantity Q (here a representative quantity of the hydrocarbon compounds during the inert phase but the other quantities described in the present description could be measured alternately) over time t (in minutes) during a heating sequence SC during which temperature T changes.
- Q here a representative quantity of the hydrocarbon compounds during the inert phase but the other quantities described in the present description could be measured alternately
- the Total_Q parameter represents the area measured under each of the curves of each sample during the duration of time materialized between the vertical arrows joined by a horizontal segment, duration during which a release of the quantity Q is observed.
- the different samples Pol_C1, Pol_C2, Pol_C3, Pol_C4 and Pol_C5 were made from a sand matrix to which PET polymer was added (the only polymer added to the sand).
- the different samples Pol_C1, Pol_C2, Pol_C3, Pol_C4 and Pol_C5 are distinguished by different polymer concentrations in the porous medium. These Pol_C1, Pol C2, Pol_C3, Pol C4 and Pol C5 samples are artificial and are intended to verify the quantification of polymer in a porous medium.
- the polymer concentration of the Pol_C1 sample is higher than that of the Pol_C2 sample, itself higher than that of the Pol_C3 sample, itself higher than that of the Pol_C4 sample and itself higher than that of the Pol_C5 sample. It is observed that the release peak temperature of the quantity Q is the same for all the samples and that the height of the peak depends on the polymer concentration of the sample. The more polymer the sample contains, the greater the height of the peak of the quantity Q. Thus, the quantity Total_Q of the sample Pol_C1 is greater than that of Pol_C2, itself greater than that of Pol_C3, itself greater than that of Pol_C4 and itself greater than that of Pol_C5.
- the Total_Q quantity depends on the polymer concentration of the porous medium.
- Figure 10b illustrates, in a schematic and non-limiting way, the evolution of the representative quantities of total organic carbon TOC, of hydrocarbon compounds Total HC, of carbon monoxide Total CO and of carbon dioxide Total C02 for samples of a medium porous media composed of a sand matrix and PET polymer, for different concentrations of the PET polymer in the porous medium.
- the PET polymer is characterized by a quantity of total organic carbon released by a sample of pure PET (without matrix) of 51.5+/-1.4%.
- the diagram at the top left represents the evolution of the representative quantity of total organic carbon TOC (in percentage %) released by the sample of porous medium as a function of the mass concentration c_pol (in percentage %) of PET in the porous medium .
- TOC 47.673 c pol + 0.0296
- the diagram at the top right represents the evolution of the representative quantity of hydrocarbon compounds released (in mg/g of sample) by the sample of porous medium as a function of the mass concentration c_pol (in percentage %) of the PET in the porous medium.
- the diagram at the bottom left represents the evolution of the representative quantity of carbon monoxide (in mg/g of sample) released by the sample of porous medium as a function of the mass concentration c_pol (in percentage %) of the PET in the porous medium.
- the diagram at the bottom right represents the evolution of the representative quantity of carbon dioxide released (in mg/g of sample) by the sample of porous medium as a function of the mass concentration c_pol (in percentage %) of the PET in the porous medium.
- FIG. 11 illustrates, in a schematic and non-limiting manner, relationships between the total quantity measured under a Total_Q peak (for example which may correspond to TotalJHC when the measurement concerns the representative quantity of hydrocarbon compounds) and the quantity of polymer q_pol (here the polymer is PET) inside the porous medium sample.
- a Total_Q peak for example which may correspond to TotalJHC when the measurement concerns the representative quantity of hydrocarbon compounds
- polymer q_pol here the polymer is PET
- the polymers are determined (by peak temperatures), and the corresponding amount to the area under each peak of a polymer present is determined, it is possible to quantify the quantity of each of these polymers present in the porous medium.
- step d) if at least one reference parameter (preferably several reference parameters and more preferably all the reference parameters) of a polymer is found in the measurements carried out on the sample of porous medium , the presence of this polymer in the porous medium is proven.
- the use of several reference parameters found (or preferably all of them) makes it possible to characterize more precisely the presence of the polymer under consideration.
- the deviation (difference) between the parameter and the corresponding parameter of the first base of data is less than a predetermined threshold (which may be approximately 10% on the quantities and/or 10°C (preferably 5°C) when the reference parameters are temperatures).
- the invention is not limited to the detection of a single polymer in the porous medium but can make it possible to identify several polymers. Indeed, it is possible to identify the (at least one) reference parameters of several polymers in the porous medium and thus ensure the presence of several polymers in the porous medium.
- the matrix seems to correspond to that of the porous medium.
- the matrix of the porous medium may not completely correspond to the matrices of the second database. In this case, one can retain the matrix which is closest to it, which can be for example, the matrix which has the most reference characteristics found within +/- 10% in the measurements of the porous medium or at the matrix whose average of the deviations (differences) between the measurement and the corresponding reference characteristic is the smallest.
- the absolute value of the difference (the difference) between the parameter and the corresponding parameter of the second database is lower than a predetermined threshold (which can be approximately 10% on the quantities and/or 20° C. (preferably 10° C.) when the reference parameters are temperatures).
- a predetermined threshold which can be approximately 10% on the quantities and/or 20° C. (preferably 10° C.) when the reference parameters are temperatures.
- the identification of this temperature of the release peak of the hydrocarbon compounds generally makes it possible to identify a particular polymer. Thus, if a peak of this temperature is found within a predefined criterion (within +/-10°C for example) in the thermogram for measuring hydrocarbon compounds by a sensor such as an FID sensor from the sample porous medium, the presence of that particular polymer can be identified.
- thermogram of the hydrocarbon compounds from the sample of the porous medium and the temperature Tpeak H cp oiymer . If this difference (its absolute value in particular) is less than the predefined criterion (at 10° C. for example), the presence of the particular polymer is characterized.
- Tpeak H cp oiymer can in the same way as for Tpeak H cp oiymer serve either to confirm the presence of the particular polymer or serve to identify it.
- thermogram considered from the sample of the porous medium and the corresponding temperature of the particular polymer. If this difference (its absolute value) is below the predetermined threshold (10° C. for example), the presence of the particular polymer can be characterized or confirmed.
- the accuracy of polymer determination can be refined.
- the identification of the temperature of the release peak of the hydrocarbon compounds generally makes it possible to identify a particular matrix.
- a peak of this temperature is found to within a predetermined threshold (at +/-10°C for example) in the thermogram for measuring hydrocarbon compounds by a sensor such as an FID sensor from the sample of porous medium, one can identify the presence of this particular matrix.
- a sensor such as an FID sensor from the sample of porous medium
- a predetermined threshold at +/-10°C for example
- Tpeak H Cmatrix serve either to confirm that the porous medium comprises a particular matrix or serve to identify it.
- thermogram considered from the sample of the porous medium and the corresponding temperature of the particular matrix. If this difference (its absolute value) is less than the predefined criterion (10° C. for example), it can be considered that the porous medium comprises the particular matrix.
- the parameter CO polymer/miiie u pore u x corresponds to the percentage of carbon monoxide released by the polymer contained in the porous medium during the first and second heating sequences.
- the parameter C02 p0iymer/miiie u porous corresponds to the percentage of carbon dioxide released by the polymer contained in the porous medium during the first and second sequences of heating.
- the parameter HC poiymer/miiie u porous corresponds to the percentage of hydrocarbon compounds released by the polymer contained in the porous medium during the first sequence of heating.
- CO polymer/porous medium [Total 00 polymer/porous medium/ TotSl 00 porous medium] 100 (%)
- HC polymer/porous medium [Total HC polymer/porous medium/Total HC porous medium] 100 ( °/o )
- a single type of polymer has been identified in the porous medium (by determining a single peak temperature of hydrocarbon compounds corresponding to the predefined criterion close, for example +/- 10°C, to that of a polymer of the first database for example), it is then possible to directly reduce the percentage of hydrocarbon compounds resulting from this single particular polymer.
- the porous medium comprises only this polymer during the first heating sequence.
- the quantity of hydrocarbon compounds resulting from the polymer contained in the porous medium is known: Total HC poiymer/miiieu porous and the quantity of hydrocarbon compounds (normalized) of a polymer alone (without matrix) Total HC poiymer is known.
- the mass of polymer in the porous medium can be deduced.
- a mass ratio (or mass percentage) of polymer in the porous medium can be deduced therefrom.
- Figure 12 illustrates an example of a sample of sand taken from the environment for which the method according to the invention was applied to characterize the presence of polymer in the porous medium.
- Figure 12 shows the representative quantity Q of hydrocarbon compounds released during a heating sequence under an inert atmosphere, the heating sequence being linear between temperature T1 and temperature T2 for a determined duration (approximately 14 minutes) for a sample of pure polymer Pol (here the polymer is PET) and for a sample of the sand taken Mil.
- the sand matrix does not show any peak release of hydrocarbon compounds, nor of dioxide monoxide or carbon dioxide during the inert and oxidizing phases.
- the release peak observed on the Mil sample curve cannot correspond to the matrix and therefore corresponds to pollution.
- the temperature of this peak Tpeak2 is very close to the temperature Tpeak1 , which is the temperature of the release peak observed on the curve of the sample Pol of the pure PET polymer (without matrix).
- the difference between the temperature Tpeak2 and the temperature Tpeakl is within an acceptable tolerance interval (the tolerance interval being for example between 10 and 20° C., preferably close to 10° C.) with respect to the temperature Tpeakl of the pure polymer.
- the peak of the curve of the sample of the porous medium Mil thus identifies the presence of the PET polymer in the porous medium.
- the method according to the invention makes it possible to identify the presence of polluting polymer in a porous medium.
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- Biochemistry (AREA)
- Combustion & Propulsion (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Pathology (AREA)
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CA3215803A CA3215803A1 (fr) | 2021-05-17 | 2022-05-09 | Procede de caracterisation de presence et/ou de quantification de polymeres dans un milieu poreux |
EP22728428.8A EP4341682A1 (fr) | 2021-05-17 | 2022-05-09 | Procede de caracterisation de presence et/ou de quantification de polymeres dans un milieu poreux |
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FRFR2105123 | 2021-05-17 | ||
FR2105123A FR3122926B1 (fr) | 2021-05-17 | 2021-05-17 | Procédé de caractérisation de présence et/ou de quantification de polymères dans un milieu poreux |
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WO2022243080A1 true WO2022243080A1 (fr) | 2022-11-24 |
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PCT/EP2022/062455 WO2022243080A1 (fr) | 2021-05-17 | 2022-05-09 | Procede de caracterisation de presence et/ou de quantification de polymeres dans un milieu poreux |
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EP (1) | EP4341682A1 (fr) |
CA (1) | CA3215803A1 (fr) |
FR (1) | FR3122926B1 (fr) |
WO (1) | WO2022243080A1 (fr) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2227797A5 (fr) | 1973-04-27 | 1974-11-22 | Inst Francais Du Petrole | |
FR2472754A1 (fr) | 1979-12-28 | 1981-07-03 | Inst Francais Du Petrole | Methode et dispositif pour determiner notamment la quantite de carbone organique contenue dans un echantillon |
FR2753271A1 (fr) * | 1996-09-12 | 1998-03-13 | Inst Francais Du Petrole | Methode et dispositif d'evaluation d'une caracteristique de pollution d'un echantillon de sol |
US5843787A (en) | 1994-07-05 | 1998-12-01 | Institut Francais Du Petrole | Method allowing the fast assessment of at least one petroleum characteristic of a rock sample-application to a reservoir comprising heavy oils |
US20150346179A1 (en) | 2014-06-03 | 2015-12-03 | IFP Energies Nouvelles | Method of assessing at least one petroleum characteristic of a rock sample |
FR3072173A1 (fr) * | 2017-10-09 | 2019-04-12 | IFP Energies Nouvelles | Procede pour estimer la quantite d'hydrocarbures libres dans un echantillon de roche sedimentaire |
DE102019106806A1 (de) * | 2019-03-18 | 2020-09-24 | Bundesrepublik Deutschland, vertreten durch den Bundesminister für Wirtschaft und Energie, dieser vertreten durch den Präsidenten der Bundesanstalt für Materialforschung und –prüfung (BAM) | Verfahren zur Bestimmung des Mikroplastikgehalts in Umweltproben |
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2021
- 2021-05-17 FR FR2105123A patent/FR3122926B1/fr active Active
-
2022
- 2022-05-09 WO PCT/EP2022/062455 patent/WO2022243080A1/fr active Application Filing
- 2022-05-09 EP EP22728428.8A patent/EP4341682A1/fr active Pending
- 2022-05-09 CA CA3215803A patent/CA3215803A1/fr active Pending
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FR2227797A5 (fr) | 1973-04-27 | 1974-11-22 | Inst Francais Du Petrole | |
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FR2472754A1 (fr) | 1979-12-28 | 1981-07-03 | Inst Francais Du Petrole | Methode et dispositif pour determiner notamment la quantite de carbone organique contenue dans un echantillon |
US4352673A (en) | 1979-12-28 | 1982-10-05 | Institut Francais Du Petrole | Method and device for determining the organic carbon content of a sample |
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FR2753271A1 (fr) * | 1996-09-12 | 1998-03-13 | Inst Francais Du Petrole | Methode et dispositif d'evaluation d'une caracteristique de pollution d'un echantillon de sol |
US20150346179A1 (en) | 2014-06-03 | 2015-12-03 | IFP Energies Nouvelles | Method of assessing at least one petroleum characteristic of a rock sample |
FR3021749A1 (fr) | 2014-06-03 | 2015-12-04 | IFP Energies Nouvelles | Procede pour l'evaluation d'au moins une caracteristique petroliere d'un echantillon de roche |
FR3072173A1 (fr) * | 2017-10-09 | 2019-04-12 | IFP Energies Nouvelles | Procede pour estimer la quantite d'hydrocarbures libres dans un echantillon de roche sedimentaire |
DE102019106806A1 (de) * | 2019-03-18 | 2020-09-24 | Bundesrepublik Deutschland, vertreten durch den Bundesminister für Wirtschaft und Energie, dieser vertreten durch den Präsidenten der Bundesanstalt für Materialforschung und –prüfung (BAM) | Verfahren zur Bestimmung des Mikroplastikgehalts in Umweltproben |
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BANERJEE DWIJEN K ET AL: "Analysis of Hydrocarbon-Contaminated Soil by Thermal Extraction-Gas Chromatography", ENVIRONMENTAL SCIENCE & TECHNOLOGY, vol. 31, no. 3, 27 February 1997 (1997-02-27), pages 646 - 650, XP055869310, ISSN: 0013-936X, DOI: 10.1021/es960063a * |
DAVID JAN ET AL: "Introducing a soil universal model method (SUMM) and its application for qualitative and quantitative determination of poly(ethylene), poly(styrene), poly(vinyl chloride) and poly(ethylene terephthalate) microplastics in a model soil", CHEMOSPHERE, vol. 225, 14 March 2019 (2019-03-14), pages 810 - 819, XP085666153, ISSN: 0045-6535, DOI: 10.1016/J.CHEMOSPHERE.2019.03.078 * |
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EP4341682A1 (fr) | 2024-03-27 |
FR3122926B1 (fr) | 2024-04-05 |
FR3122926A1 (fr) | 2022-11-18 |
CA3215803A1 (fr) | 2022-11-24 |
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