• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    - A rock sample is subjected to a heating sequence in an inert atmosphere, the effluents from this heating are oxidized, the hydrocarbon compounds, CO, CO2 and SO2 released are measured, and a sulfur content is deduced therefrom pyrolysis pyritic. Then the residue from the heating in an inert atmosphere is heated in an oxidizing atmosphere and the CO and CO 2 released are measured. The pyritic sulfur content is determined from at least the pyritic sulfur content from pyrolysis and from a parameter which is a function of the hydrogen content and of the oxygen content of the organic material of the sample. The organic sulfur content can also be determined from the pyritic sulfur content and a measurement of SO2 during the heating sequence in an oxidizing atmosphere.
    公开号:FR3083316A1
    申请号:FR1856042
    申请日:2018-06-29
    公开日:2020-01-03
    发明作者:Anabel ABOUSSOU；Violaine Lamoureux-Var；Daniel Pillot；Isabelle Kowalewski；Bruno GARCIA；Thomas Wagner；Christian MARZ
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    The present invention relates to the technical field of the petroleum industry, and more particularly the field of exploration and exploitation of a geological formation in which hydrocarbons are trapped.
    More specifically, the present invention relates to the characterization and quantification of the sulfur present within a sedimentary rock, such as a marine clay rich in organic matter.
    In order to meet growing energy demand, the petroleum industry is increasingly turning to the production of unconventional crude oils, which are richer in sulfur than conventional oils. However, the sulfur content of an unconventional crude oil, as well as the type of organic sulfur compounds it contains, are key parameters of the quality of this oil and of the refined products produced from it. In addition, regulations impose increasingly low sulfur contents for products from refining. For these reasons, it is important to know how to characterize and precisely quantify the sulfur present in the rocks which are at the origin of these crude sulfur oils.
    In the case of petroleum source rocks, the two main sulfur compounds are organic sulfur and pyritic sulfur. The quantification of organic sulfur, independently of pyritic sulfur, is of great importance in petroleum exploration, because it makes it possible to know exactly the quantity of sulfur associated with the organic matter of the parent rocks, which is at the origin of the sulfur present in the oil generated by these parent rocks. In particular, the separate quantification of pyritic sulfur and organic sulfur makes it possible to:
    - characterize the type of organic matter in the source rock and predict the quality of the oil generated by the source rock with regard to its sulfur content: in fact, the characterization of the type of organic matter in the source rocks is conventionally based on the elementary content of this organic matter in Carbon (C), Hydrogen (H) and Oxygen (O). This classic characterization of the type of organic matter is done using the classic Van Krevelen diagram, which represents the hydrogen / carbon atomic ratio (H / C), as a function of the oxygen / carbon atomic ratio (O / C). The potential of an organic matter to generate petroleum depending on its composition in H, C and O, this diagram makes it possible to distinguish three types of organic matter according to their petroleum potential. Indeed, this diagram can be correlated to the origin and the environment of deposition of organic matter. Classically, a distinction is made between organic matter of the lake type (type I), marine type (II) and terrestrial type (III). The quantification of the sulfur of organic matter independently of the sulfur of pyrite (or pyritic sulfur) provides an additional parameter which allows a finer characterization of the type of organic matter and therefore a finer characterization of its deposition environment and of the type of petroleum. that it can generate. This finer characterization is done with the Van Krevelen diagram extended to three dimensions: H / C as a function of O / C and of S org / C where S org is the organic sulfur content. This extended diagram makes it possible to distinguish with more finesse the different types of organic matter, in particular to identify organic matter of type IS and IIS which have the same origins as types I and II, but containing sulfur, and which are probably deposited in an anoxic or Ellesinic environment. This presence of sulfur also indicates that the oil resulting from the cracking of this organic matter will be more sulfur. In general, information on the type of organic matter in the source rock provides information on the potential of the source rock to generate petroleum and on the expected quality of this petroleum, in particular with regard to its sulfur content;
    - provide an additional parameter to the oil-source rock correlation: indeed, the oil-source rock correlation is a very important study that a person skilled in the art must carry out to assess the petroleum system. It consists in making the link between the oils contained in a reservoir and the mother rock or rocks which generated these oils. Knowing that the cracking of source rocks containing organic matter rich in sulfur results in the formation of oils and gases also rich in sulfur, a method of quantifying the sulfur of organic matter, independently of the sulfur of pyrite, therefore provides a key parameter for the oil-rock correlation.
    State of the art
    The following documents will be cited in the following description:
    Acholla, F.V., Orr, W.L., 1993. Pyrite removal from kerogen without altering organic matter: The chromous chloride method. Energy Fuels 7, 406-410.
    Behar, F., Beaumont, V., De B. Penteado, H. L, 2001. Rock-Eval 6 Technology: Performances and Developments. Oil & Gas Science and Technology - Rev. IFP 56, HI134.
    Bolin, T.B., 2010. Direct determination of pyrite content in Argonne premium coals by the use of sulfur X-ray near edge absorption spectroscopy (S-XANES). Energy and Fuels 24, 5479-5482.
    Canfield, D.E., Raiswell, R., Westrich, J.T., Reaves, C.M., Berner, R.A., 1986. The use of chromium reduction in the analysis of reduced inorganic sulfur in sediments and shales. Chemical Geology 54, 149-155.
    Landais, P., Michels, R., Benkhedda, 7., Kister, J., Dereppe, J.-M., 1991. Behavior of Oxidized Type II Kerogen during Artificial Maturation. Energy and Fuels 5, 860-866.
    Orr W., 1986, “Kerogen / asphaltene / sulfur relationships in sulfur-rich Monterey oils”, Org. Geochem. Flight. 10, pp. 499-516, 1986.
    Vairavamurthy, MA, Maletic, D., Wang, S., Manowitz, B., Eglinton, T., Lyons, T., 1997. Characterization of sulfur-containing functional groups in sedimentary humic substances by X-ray absorption near-edge spectroscopy structure. Energy and Fuels 11, 546-553.
    Vandenbroucke, M., Largeau, C., 2007. Kerogen origin, evolution and structure. Organic Geochemistry 38, 719-833.
    Laboratory methods are known which make it possible to quantify pyritic sulfur separately from organic sulfur, such as the following techniques:
    • Elementary analysis of kerogens, as described in the document (Vandenbroucke and Largeau, 2007). It is one of the most commonly used methods in routine laboratory work. It takes place in 2 stages:
    Isolation of kerogen (or even isolation of organic matter): kerogen is isolated from raw rock by a series of chemical attacks with hydrochloric and hydrofluoric acid aimed at destroying the mineral matrix, carbonates and silicates. Pyrite (FeS 2 ), other metallic sulfides, as well as certain minor oxides including iron oxides, being resistant to these various chemical attacks, remain conserved in the organic residue obtained. Thus we obtain a kerogen free of the mineral matrix but still containing pyrite.
    - Elemental analysis of iron (by atomic emission spectrometry with plasma coupled by induction, known under the term ICP-AES in English) and sulfur (by infrared analysis): here we assume that the iron present in kerogen obtained, would only be in the form of pyrite (FeS 2 ). Therefore from the measurement of the iron content (ICP-AES) of the kerogen, the pyrite content can be calculated stoichiometrically, thus making it possible to determine the pyritic sulfur content. Then, from the measurement of the sulfur content (IR) of the kerogen, the organic sulfur content is deduced therefrom by difference between the total sulfur (measured by infrared) and the pyritic sulfur.
    This first laboratory method according to the prior art has the following drawbacks:
    - the length of the analysis time: approximately one week;
    - It requires preparation steps, chemical separation, which are heavy, dangerous because using strong acids;
    - it does not allow the automation of measurements;
    - it is based on the assumption that all the iron contained in organic matter is pyritic. However if the iron contained in the organic matter is also in other forms such as oxides or other sulphides than FeS 2 , then one overestimates the content of pyritic sulfur and one underestimates the content of organic sulfur .
    • Extraction of pyrite by chromium chloride II and by elemental analysis of the starting rock, as described in the documents (Canfield et al., 1986; Acholla and
    Orr, 1993). According to this approach, a chemical attack with hot hydrochloric acid (HCl) is first carried out to extract all the volatile sulfur contained in rock samples. Once this step has been carried out, the samples are then treated, hot, with a solution consisting of hydrochloric acid (HCl) and chromium II chloride (CrCI 2 ) making it possible to extract the pyrite (FeS 2 ). The sulfur effluent (H 2 S), released by the reduction of pyrite by this solution, passes into a trap composed of a solution of silver nitrate (AgNO 3 ), where it precipitates in the form of silver sulphide (Ag 2 S). The precipitate of Ag 2 S obtained is weighed, which makes it possible to stoichiometrically quantify the content of pyritic sulfur, assuming that the pyrite has been entirely transformed into silver sulphide. Then the organic sulfur content is deduced by difference between the total sulfur content, obtained by elementary analysis of the starting rock, and the pyritic sulfur content. This method is based on the assumption that all pyrite is reduced to H 2 S.
    This second laboratory method according to the prior art has the following drawbacks:
    - It requires preparation steps, chemical separation, which are heavy, dangerous because using strong acids;
    - it does not allow the automation of measurements; and
    - it is based on the assumption that all pyrite is reduced to H 2 S. If part of the pyrite is not reduced, then the pyritic sulfur content is underestimated and the organic sulfur content is overestimated . In particular, samples rich in pyrite may be in this case.
    • Structural spectroscopy near the absorption front of X-rays of sulfur (SXANES in English), as described in the documents (Vairavamurthy et al., 1997; Bolin, 2010): according to this approach, the S-XANES provides information on the oxidation state of the sulfur compounds. In a typical analysis, the spectrum of a sample is deconvolved with various linear combinations of the spectra of different sulfur standards. The best fit is chosen to indicate the actual composition of the various sulfur compounds in this sample. This technique therefore allows quantitative determination of pyritic sulfur, organic sulfur and sulfates. In the case of rock analysis, it should be noted that very fine grinding of the sample is often necessary in order to better quantify the pyritic sulfur, the peak of which is attenuated in the unfinished samples.
    This third laboratory method according to the prior art has the following drawbacks:
    - it requires very fine grinding of the samples; and
    - it requires access to a synchrotron, which is very heavy and very expensive equipment.
    Also known is patent EP 2342557 (US 8796035) which relates to a device and a method for the characterization and quantification of sulfur in a sample of sedimentary rocks or petroleum products. More specifically, the method described in this patent comprises the following steps:
    - the sample in question is heated in a pyrolysis oven in a non-oxidizing atmosphere,
    a part of the pyrolysis effluents is oxidized, and the quantity of SO 2 contained in this part of the oxidized effluents is continuously measured,
    the pyrolysis residues are transferred to an oxidation oven and the quantity of SO 2 contained in the effluents resulting from the oxidative heating of the pyrolysis residue is continuously measured,
    - and we deduce the sulfur content in the sample.
    However, this method makes it possible to determine the total sulfur content present in the sample studied, but does not make it possible to quantify pyritic sulfur separately from organic sulfur. Indeed, this method makes it possible to quantify the total sulfur content of a rock sample, by measuring the sulfur effluents released by this sample during pyrolysis and then oxidation. Two profiles corresponding to sulfur are thus obtained: the first during the pyrolysis phase, and the second during the oxidation phase. At the sulfur pyrolysis signal, it is possible to discriminate organic sulfur from mineral sulfur due to pyrite, since they systematically form two sufficiently distinct peaks. However, in oxidation, the signals of these two sulfur compounds are confused, which prevents speciation of organic and pyritic sulfur. In addition, many chemical reactions occur in the rock during the analysis itself. If some involve organic sulfur and / or pyritic sulfur, then they are likely to modify their signals, which adds a level of difficulty to the quantification of organic sulfur and pyritic sulfur by means of the method as described in the aforementioned patent. .
    Also known is patent application FR 17/59447 (filing number) which describes a method for the quantification of pyritic sulfur in a sample of sedimentary rock. More precisely, this method according to the prior art comprises at least the following steps:
    A. heating said sample in an inert atmosphere, between a first temperature between 100 ° C and 320 ° C and a second temperature between 600 ° C and 700 ° C, following a first temperature gradient between 1 ° C / min and 30 ° C / min;
    B. at least part of the effluents from said heating of said sample are continuously oxidized in an inert atmosphere, a first quantity of SO 2 released as a function of the time of said heating in an inert atmosphere is continuously measured, and at least one is determined sulfur content of pyrolysis S Pyrol and a pyritic sulfur content of pyrolysis S Py rot from said first amount of SO 2 ;
    C. the residue of said sample from said heating in an inert atmosphere is heated in an oxidizing atmosphere between a third temperature between 280 ° C and 320 ° C and a fourth temperature greater than or equal to 800 ° C, following a second temperature gradient between 1 ° C / mh and 30 ° C / min;
    D. continuously measuring a second quantity of SO 2 released as a function of the time of said heating in an oxidizing atmosphere, determining at least one sulfur content of oxidation S Oxy from said second quantity of SO 2 , and determining at least one total sulfur content S Total by the sum of said pyrolysis sulfur content S Pyrol and said oxidation sulfur content S Oxy ;
    Then this process according to the prior art provides for the determination of at least one content of pyritic sulfur s Pyrit contained in said sample from a formula of the type:
    where ρ (α, β, γ) is a weighting function depending on a parameter a representing a proportion of said pyritic pyrolysis sulfur relative to said total sulfur, of a parameter β representing an effect of the mineral matrix on said proportion, a parameter y representing an effect of the organic matrix on said proportion, the values of said parameters being predetermined.
    Furthermore, according to a preferred variant of this method according to the prior art, the weighting function ρ (α, β, γ) is written in the form:
    ρ (α, β, γ) = (1+ ^ + y)
    However, the values of the parameters a, ^, ety must be predefined, prior to the implementation of the method according to the invention. Patent application FR 17/59447 describes default values, in particular values of the parameter γ as a function of the type of organic matter presumed present in the sample of sedimentary rock considered. Thus, according to a variant of the method according to the prior art, if the rock sample contains an organic material of lacustrine and / or marine origin, it is possible to use 0 as the value for the parameter y. According to another variant of the method according to the prior art, if the rock sample contains an organic matter of terrestrial origin, the value of the parameter y can be chosen between 0.23 and 0.29, and is preferably 0.26.
    Thus, the method according to the prior art describes a method for directly quantifying the parameter y, taking into account the standard types of organic matter, which are pure poles. However, it may for example prove that the rock sample to be analyzed contains more complex types of organic matter, such as resulting from weathering or from the mixture of standard type organic matter. Indeed, by weathering processes, an organic matter of the marine standard type can have the chemical signature of an organic matter of the terrestrial standard type. In addition, most sedimentary formations contain mixtures of the various standard types of organic matter. In proximal marine environments, for example, it is possible to find in sediments a mixture of organic matter of terrestrial type and organic matter of marine type. In such cases, the value of the parameter y recommended by patent application FR 17/59447 would not be suitable for the sedimentary rock studied.
    In addition, the preferred form of the method according to the prior art for the weighting function ρ (α, β, γ), which is written in the form:
    ρ (α, β, γ) = (1+ ^ + y) is an approximate formula. Indeed, as demonstrated in the application example described below, this formula, if it gives satisfactory results for the quantification of the pyritic sulfur present in a rock sample, remains however imprecise.
    The present invention aims to overcome these drawbacks. Thus, the present invention relates to a method for a very precise quantification of the pyritic sulfur contained in a sample of sedimentary rock, in particular from measurements carried out on the rock sample itself to quantify the effect of the organic matrix. In addition, the implementation of the method according to the invention is simple and rapid. The method according to the invention also makes it possible, in one of its variants, to quantify the organic sulfur present in the sample, in addition to the pyritic sulfur.
    The method according to the invention
    The invention relates to a method for the quantification of pyritic sulfur in a sample of sedimentary rock, in which at least the following steps are applied:
    A. heating said sample in an inert atmosphere, between a first temperature between 80 ° C and 320 ° C and a tenth temperature between 600 ° C and 700 ° C, following a first sequence of temperatures, and measuring continuously an amount of hydrocarbon compounds, an amount of CO and an amount of CO 2 released during said first temperature sequence;
    B. at least part of the effluents from said heating in an inert atmosphere of said sample are continuously oxidized, a quantity of SO 2 released by said oxidation of said effluents is continuously measured as a function of the time of said heating in an inert atmosphere, and determines at least one pyritic sulfur content for pyrolysis from said quantity of SO 2 ;
    C. the residue of said sample from said heating in an inert atmosphere is heated in an oxidizing atmosphere between a third temperature between 280 ° C and 320 ° C and a fourth temperature above or equal to 800 ° C, by following a second sequence of temperatures , and continuously measuring an amount of CO and an amount of CO 2 released during said second temperature sequence;
    characterized in that at least one content of pyritic sulfur S Pyri £ contained in said sample is determined from a formula of the type:
    ^ Pyrit Pyrit ^ + 1-β + 1-γ ) pyrol * ™ where a is a parameter representing a proportion of said pyrolysis pyritic sulfur relative to said total sulfur, β is a parameter representing an effect of the mineral matrix on said proportion, y is a parameter representing an effect of the organic matrix on said proportion, the values of said parameters a and β being predetermined, and said parameter γ being determined from a formula of the type:
    y = β (ΟΙ, ΗΓ) where / is a function of at least one oxygen index 01 and of a hydrogen index HI, said hydrogen index HI being a function of at least said quantity of hydrocarbon compounds measured during said heating in an inert atmosphere and said quantities of CO and CO 2 measured during said first and second temperature sequence, and said oxygen index 01 being a function at least of said quantities of CO and C0 2 measured during said first and second temperature sequences.
    According to an implementation of the invention, said function / can be a linear combination of said oxygen index 01 and said hydrogen index HI expressed according to a formula of the type: y = a * 01 + b * HI + c, where a, b and c are predetermined constants.
    Advantageously, said constant a can be between 0.28 and 0.46, and can preferably be equal to 0.37.
    Preferably, said constant b can be between -0.007 and -0.005 and can preferably be equal to -0.006.
    Preferably, said constant c may be between 4.99 and 6.49 and may preferably be 5.74.
    According to an implementation of the invention, said hydrogen index HI can be determined according to a formula of the type:
    100 * 52
    H1 -.
    TOC where
    S2 is an amount of hydrocarbon compounds which are cracked during said first temperature sequence, S2 being determined from said amount of hydrocarbon compounds released during said heating in an inert atmosphere,
    - TOC is a total organic carbon content of said sample written in the form T0C (wt%) = PC + RC, where PC is an organic carbon content of pyrolysis of said sample determined from said measurements of CO and CO 2 released during said first temperature sequence, and where RC is a residual organic carbon content of said sample determined from said measurements of CO and CO 2 released during said second temperature sequence.
    According to an implementation of the invention, said oxygen index 01 can be determined according to a formula of the type:
    _ rioo * s3cO;, j - [toc J 'where:
    - S3CO 2 is an amount of C0 2 measured between said first temperature of said first temperature sequence and a first intermediate temperature of said first temperature sequence between 350 ° C and 450 ° C, and preferably equal to 400 ° C;
    - TOC is a total organic carbon content of said sample and is written TOC (wt ° / o) = PC + RC, where PC is an organic carbon content of pyrolysis of said sample determined from said CO and CO2 measurements released during said first temperature sequence, and where RC is a residual organic carbon content of said sample determined from said measurements of CO and CO2 released during said second temperature sequence.
    According to an implementation of the invention, said organic carbon content of pyrolysis PC of said sample can be determined according to a formula of the type:
    PC (wt%) = [Q * 0.083] + [(S3CO + ± S3'CO) * ^] + [s3CO 2 * ^], with
    - S3CO2 is an amount of CO 2 measured between said first temperature of said first temperature sequence and a first intermediate temperature of said first temperature sequence between 350 ° C and 450 ° C, and preferably equal to 400 ° C;
    - S3CO is an amount of CO measured between said first temperature of said first temperature sequence and a second intermediate temperature of said first temperature sequence between 500 and 600 ° C, and preferably equal to 550 ° C;
    - S3'CO is a quantity of CO measured between said second intermediate temperature of said first temperature sequence and said second temperature of said first temperature sequence;
    According to an implementation of the invention, said residual carbon content RC of said sample can be determined according to a formula organic type:
    1 r 12 1
    RC (wt%) = [S4CO 2 . -] + | S4CO. - where S4CO and S4CO 2 correspond respectively to an amount of CO and CO 2 measured between said third temperature of said second temperature sequence and an intermediate temperature of said second temperature sequence between 600 ° C and 700 ° C, and being equal préférentiellement650 ° C.
    According to a first alternative of the invention according to which said sample is of the reservoir rock type, said first temperature can be between 100 ° C. and 200 ° C.
    According to a second alternative of the invention according to which said sample is of the conventional source rock or immature non-conventional source rock, said first temperature can be between 280 ° C. and 320 ° C.
    According to a third alternative of the invention according to which said sample can be of unconventional source rock type with oil or gas, said first temperature can be between 80 ° C. and 120 ° C.
    According to an implementation of the invention, said parameter a can be between 0.40 and 0.46, and can preferably be worth 0.43.
    According to an implementation of the invention according to which said rock sample is of the clay type, said parameter β can be between 0.04 and 0.7, and can preferably be worth 0.38.
    According to an implementation of the invention according to which said rock sample is of the marl type, and for which the parameter β can be between 0.7 and 0.9, and may preferably be 0.78.
    According to an implementation of the invention according to which said rock sample is of the limestone type, and for which the parameter β can be between 0.85 and 0.97, and can preferably be equal to 0.9.
    According to an implementation variant of the invention, it is also possible to measure an amount of SO 2 released during said second temperature sequence, it is possible to determine at least one sulfur content of pyrolysis S Pyrol from said amount of SO 2 measured during said first temperature sequence and an oxidation sulfur content S Oxy from said quantity of SO 2 measured during said second temperature sequence, and an organic sulfur content S Ora can be determined from at least said pyritic sulfur content s Pyrit , said pyrolysis sulfur content S Pyrol and said oxidation sulfur content S Oxy .
    According to an implementation of the invention according to which said fourth temperature is between 800 ° C and 900 ° C, one can determine an organic sulfur content S Ora according to the formula: S Ora = S Pyrol + S Oxy - S Pyrit .
    According to an alternative implementation of the invention in which said fourth temperature is higher than 1150 ° C, and is préféreitiellement less than 1250 ° C, one can further determine a sulphate content S ^ sulfurs are from said quantity of SO2 measured during said second temperature sequence, and an organic sulfur content can be deduced therefrom according to the formula: S Ora = SPyrol + S Oxy - s Pyrit -Sg x l J a .
    Other characteristics and advantages of the method according to the invention will appear on reading the following description of nonlimiting examples of embodiments, with reference to the appended figures and described below.
    Brief presentation of the figures
    - Figure 1a shows an example of measurement performed by an SO 2 detector during a heating sequence under an inert atmosphere to which a rock sample is subjected.
    - Figure 1b shows an example of measurement performed by an SO 2 detector during a heating sequence in an oxidizing atmosphere to which a rock sample is subjected.
    - Figure 2 presents curves representative of the quantity of SO2 released by four samples of pure igneous pyrite of distinct masses during a heating sequence under an inert atmosphere.
    - Figure 3a presents a histogram representative of the effect of the mineral matrix, depending on the class of mineral mixtures considered.
    - Figure 3b presents a histogram representative of the average effect of clays, carbonates and intermediate formations on the proportion of sulfur in the pyrite released during pyrolysis according to the class of mineral mixtures considered.
    - Figure 3c shows the evolution of the effect of the mineral matrix as a function of the mineral carbon.
    FIG. 4 presents a comparison between the organic effect obtained by analyzes of mixtures made up of pyrite and of different types of organic matter and the organic effect determined by the process according to the invention,
    - Figure 5a shows the total sulfur content determined by the process according to the invention for samples of different type, depending on the actual total sulfur content of these samples.
    - Figure 5b shows the pyritic sulfur content determined by the method according to the invention for samples of different type, depending on the actual pyritic sulfur content of these samples.
    - Figure 5c shows the organic sulfur content determined by the method according to the invention for samples of different type, depending on the actual organic sulfur content of these samples.
    - Figure 5d shows the pyritic sulfur content determined by a process according to the prior art for samples of different type, as a function of the actual pyritic sulfur content of these samples.
    Figure 5e shows the organic sulfur content determined by a process according to the prior art for samples of different type, as a function of the actual organic sulfur content of these samples.
    Detailed description of the process
    In general, one of the objects of the invention relates to a method for precisely quantifying the pyritic sulfur present in a sample of sedimentary rock. In particular, the present invention makes it possible to quantify pyritic sulfur distinctly from organic sulfur. Advantageously, the method according to the invention makes it possible to quantify the organic sulfur present in a sample of sedimentary rock, in addition to the pyritic sulfur.
    The present invention can be applied to any type of sedimentary rock, containing pyrite and / or sulfur-containing organic matter. In particular, the present invention is suitable for samples of source rocks, reservoir rocks or unconventional source rocks (called "Shale Play" in English).
    In general, the rock sample may for example have been taken by coring in an underground formation of interest or else result from spoils from a borehole. Advantageously, the sample as taken can be prepared (by washing, sieving, sorting, etc.) in order to remove the impurities (drilling mud for example, pollutants etc.), then is ground by hand. or with a mechanical grinder.
    The method according to the invention can be advantageously but not limited to implemented by means of the ROCK-EVAL® device (IFP Energies nouvelles, France), as described in particular in patent EP 2342557 (US 8796035).
    The method according to the invention comprises at least the following steps:
    1. Heating sequence under an inert atmosphere (pyrolysis)
    2. Heating sequence under an oxidizing atmosphere (oxidation)
    3. Quantification of pyritic sulfur
    According to a first variant, the method according to the invention can also comprise, at the end of step 3, a fourth step of quantification of organic sulfur.
    According to a second variant, the method may further comprise a step of calibrating one or more parameters required for the implementation of step 3 below. This calibration step can be carried out either before step 1, or before step 2, or before step 3, or in parallel with one of these steps 1 or 2.
    Steps 1 to 3 of the method according to the invention are described below, as well as the first and second variants of the method according to the invention.
    1. Heating sequence under an inert atmosphere (pyrolysis)
    During this step, the sedimentary rock sample considered is heated under an inert atmosphere (such as under a flow of nitrogen, helium) according to a program of predefined temperatures, variable over time (sub-step 1.1 below ). Simultaneously, at least part of the effluents from this heating in an inert atmosphere are continuously oxidized (sub-step 1.2 below).
    1.1. Heats in an inert atmosphere
    According to the invention, the sample is heated by pyrolysis between a temperature T1 of between 80 ° C and 320 ° C, and a temperature T2 of between 600 ° C and 700 ° C, preferably 650 ° C, according to a predetermined sequence of temperatures .
    According to an implementation of the invention, the temperature sequence for heating in an inert atmosphere can consist of a temperature gradient (or heating rate) of between 0.1 ° C / min and 30 ° C / min, preferably between 20 ° C / min and 30 ° C / min, and very preferably 25 ° C / min. According to another implementation of the invention, the temperature sequence for heating in an inert atmosphere can comprise at least one temperature level (during which the temperature is kept constant) and at least one temperature gradient (or heating rate ), this gradient can be placed before or after the at least one level.
    According to an implementation of the invention according to which the sample analyzed is a reservoir rock, the temperature T1 is between 100 ° and 200 ° C, and is preferably 180 ° C. Reference may be made to patent EP 0691540 B1 concerning the relevance of this range of temperatures for this type of rock sample.
    According to an implementation of the invention according to which the sample analyzed is a conventional source rock or an immature unconventional source rock (such as a bituminous shale, or "black shale" in English), the temperature T1 is understood between 280 ° and 320 ° C, and is preferably 300 ° C. Or refer to the document (Behar et al., 2001) concerning the relevance of this temperature range for this type of rock sample.
    According to an implementation of the invention according to which the sample analyzed is an unconventional source rock for oil (such as an oil shale, or gas shale). gas, or "gas shale" in English), the temperature T1 is between 80 ° and 120 ° C, and is preferably 100 ° C. Reference may be made to patent FR 3021748 (application US 2015/0346179) concerning the relevance of this range of temperatures for this type of rock sample.
    According to the invention, an amount of hydrocarbon compounds, an amount of carbon monoxide CO and an amount of carbon dioxide CO 2 released during the heating sequence in an inert atmosphere are measured. The measurements of hydrocarbon compounds can be carried out using a flame ionization detector or FID ("Flame Ionization Detector") and the CO and CO 2 measurements can be carried out using an infrared spectrophotometer IR (InfraRed ).
    According to a preferred implementation of the invention, from the measurements of carbon monoxide and carbon dioxide carried out during the heating sequence in an inert atmosphere, it can be determined:
    - an amount of carbon monoxide S3CO, of organic origin exclusively: this amount corresponds to the amount of carbon monoxide measured between the temperature T1 of the heating sequence in an inert atmosphere and a first intermediate temperature T1 'of this heating sequence in an inert atmosphere, T1 'being between 500 and 600 ° C, and preferably equal to 533 ° C;
    - an amount of carbon monoxide S3'CO, of both organic and inorganic origin: this amount corresponds to the amount of carbon monoxide measured between the first intermediate temperature T1 'of the heating sequence in an inert atmosphere, and the temperature T2 of the heating sequence in an inert atmosphere;
    an amount of carbon dioxide S3CO 2 from an organic source exclusively, measured between the temperature T1 of the sequence in an inert atmosphere and a second intermediate temperature of the heating sequence in an inert atmosphere, between 350 ° C and 450 ° C, and preferably equal to 400 ° C.
    According to one implementation of the invention, an organic carbon content of PC pyrolysis is determined according to a formula of the type:
    PC (wt%) = [ρ * 0.083] + [(S3CO + ± S3'CO) * + [S3CO 2 * ^].
    where Q is the quantity of hydrocarbon compounds measured during the heating sequence in an inert atmosphere.
    1.2. Oxidation of heating effluents in an inert atmosphere
    According to the invention, at least part of the effluents released during the pyrolysis are oxidized, and this as they are released. The sulfur gases present in the pyrolysis effluents are thus oxidized to SO 2 , as and when they are released. According to an implementation of the invention, this oxidation of the pyrolysis effluents is carried out by means of a combustion chamber, such as an oxidation furnace, in the presence of an oxygenated gas and optionally a catalyst.
    According to the invention, the SO 2 thus generated is continuously measured, as the pyrolysis takes place, by means of a SO2 detector such as an ultraviolet (UV) or infrared spectrophotometer. (IR). This gives a measurement of the SO 2 released during the pyrolysis, as a function of the time and / or of the pyrolysis temperature.
    FIG. 1a presents an example of a curve (denoted C1) for measuring the amount of SO2 (more precisely the amplitude A measured by a SO 2 detector, such as an ultraviolet spectrophotometer) as a function of the pyrolysis time (denoted t), and also presents, in dotted lines, the evolution of the pyrolysis temperature (denoted T) as a function of the pyrolysis time. For this example and for illustrative purposes, the temperature T1 has been chosen equal to 300 ° C, the temperature T2 has been chosen to be equal to 650 ° C, the temperature T3 has been chosen equal to 300 ° C and the temperature T4 has been chosen equal to 1200 ° C. It can be observed that this curve C1 has different peaks. In particular, one can observe on this curve C1 the peak C which corresponds to the release during the pyrolysis of a part of the sulfur contained in the pyrite, said “pyrritic pyritic sulfur” thereafter, and noted Sp ^. Furthermore, the first two peaks A and B of the curve C1 correspond to the sulfur contained in the thermally labile organic compounds, which are respectively vaporizable and thermally crackable.
    According to the invention, the pyritic sulfur content of pyrolysis Sp ^ oi is determined from the quantity of SO 2 measured during this pyrolysis step. According to an implementation of the invention, the pyritic sulfur content of pyrolysis Sp ^ can be determined from the area under the representative peak of pyritic sulfur pyrolysis on the SO 2 measurement curve recorded during the phase of pyrolysis (see pic C in Figure 1a), divided by the mass of the sample analyzed, weighted by a calibration coefficient for pyrolysis sulfur. The pyritic sulfur content of pyrolysis is expressed as a percentage by mass, i.e. by mass of pyritic sulfur of pyrolysis, divided by the mass of the sample and multiplied by 100.
    According to an implementation of the invention, the sulfur content of pyrolysis S Pyrol of the sample analyzed can be determined from the area under the SO 2 measurement curve recorded during the heating sequence by pyrolysis, divided by the mass of the sample analyzed, weighted by a calibration coefficient for pyrolysis sulfur (respectively a calibration coefficient for oxidation sulfur). These contents are expressed as a percentage by mass, ie by mass of pyrolysis sulfur, divided by the mass of the sample and multiplied by 100.
    According to an implementation of the invention, it is possible to determine a calibration coefficient for the pyrolysis sulfur from at least one reference sample of which the sulfur content is known, reference sample which is subjected to a sequence heating by pyrolysis. Then the calibration coefficient of the pyrolysis sulfur is determined from the area under the measurement curve of the SO 2 released by this reference sample during a heating sequence by pyrolysis, itself divided by the mass of the sample. reference. According to an implementation of the invention, the reference sample can be native sulfur for the determination of the calibration coefficient of the pyrolysis sulfur.
    2. Heating sequence in an oxidizing atmosphere (oxidation)
    According to the invention, the sample is heated under an oxidizing atmosphere between a temperature T3 between 280 ° C and 320 ° C, preferably 300 ° C, and a temperature T4 greater than or equal to 800 ° C according to a predetermined temperature sequence.
    According to an implementation of the invention, the temperature sequence for heating in an oxidizing atmosphere may consist of a temperature gradient (or heating rate) of between 0.1 ° C / min and 30 ° C / min, preferably between 20 ° C / min and 30 ° C / min, and very preferably being 25 ° C / mii. According to another implementation of the invention, the temperature sequence for heating in an oxidizing atmosphere can comprise at least one temperature level (during which the temperature is kept constant) and at least one temperature gradient (or heating rate ), this gradient can be placed before or after the at least one level.
    According to an implementation of the invention, this step can be carried out by means of an oxidation furnace, the pyrolysis residue being swept by a flow of air.
    According to the invention, a quantity of carbon monoxide is continuously measured, during the heating sequence under an oxidizing atmosphere. The CO and CO 2 measurements carried out during the oxidative phase can be carried out using an infrared IR spectrophotometer (InfraRed).
    According to the invention, a residual organic carbon content, denoted RC below, is determined as a function of the CO and CO2 measurements carried out during the heating in an oxidizing atmosphere of the residue resulting from the pyrolysis.
    According to an implementation of the invention, on the basis of the CO and CO2 measurements carried out during the heating sequence under an oxidizing atmosphere, it is possible to determine at least: an amount of carbon monoxide, denoted S4CO below, which is exclusively from an organic source: this quantity corresponds to the quantity of carbon monoxide released between the temperature T3 of the heating sequence in an oxidizing atmosphere and an intermediate temperature of the heating sequence in the oxidizing atmosphere, between 600 ° C and 700 ° C, and preferably equal to 650 ° C;
    - a quantity of carbon dioxide, denoted S4CO 2 thereafter, which is exclusively from organic source: this quantity corresponds to the quantity of carbon dioxide measured between the temperature T3 of the heating sequence in an oxidizing atmosphere and an intermediate temperature of the heating sequence in an oxidizing atmosphere, between 600 ° C and 700 ° C, and preferably equal to 650 ° C.
    According to this implementation of the invention, the residual organic carbon content RC is determined according to a formula of the type:
    RC (wt ° / o) =
    1212 S4CO 2 * --- + S4CO * ---2440280
    According to the invention, it is further determined:
    - a hydrogen index, noted HI below, which corresponds to the hydrogen content of the organic matter in the sample. According to the invention, this index is determined from at least the quantity of hydrocarbon compounds measured during the heating sequence in an inert atmosphere and the quantities of CO and CO 2 measured during the heating sequence in an inert atmosphere and during the sequence heating in an oxidizing atmosphere;
    - an oxygen index, denoted 01 thereafter, which corresponds to the oxygen content of the organic matter in the sample. According to the invention, this index is determined from at least the quantities of CO and CO 2 measured during the heating sequence in an inert atmosphere and during the heating sequence in an oxidizing atmosphere.
    According to an implementation of the invention, it can be determined:
    - the hydrogen index HI from a formula of the type:
    100 * S2
    Hl - -----,
    TOC 'where S2 corresponds to an amount of hydrocarbon compounds which have been cracked during the heating of the sedimentary rock sample in an inert atmosphere, S2 being determined from the amount of hydrocarbon compounds Q released during the heating in an inert atmosphere , and TOC corresponds to the total organic carbon content, and is defined for this implementation of the invention according to the following formula: TOC (wt ° / o) = PC + RC.
    According to this implementation of the invention, the quantity S2 of hydrocarbon compounds which have been cracked during the heating of the sedimentary rock sample in an inert atmosphere corresponds to the hydrocarbon compounds which are not present in free form in the rock sample considered. The specialist is fully aware of means for determining the quantity S2 of hydrocarbon compounds which have been cracked during the heating of the sedimentary rock sample in an inert atmosphere, from the quantity of hydrocarbon compounds Q released during the heating in atmosphere inert, in particular from a pyrogram representing the evolution of the quantity of hydrocarbon compounds Q released during heating in an inert atmosphere. Indeed, such a pyrogram generally has several peaks: the first peak, often denoted S1, corresponds to the hydrocarbon compounds present in free form in the sample, the following other peak (s) corresponding to the quantity of hydrocarbon compounds which have been cracked at heating of the sedimentary rock sample in an inert atmosphere. It is thus possible to determine the quantity S2 from the surface of the peak (s) of the pyrogram different from the peak S1;
    - the oxygen index Ol from a formula of the type:
    _ rioo * s3co 2 i - L toc J 'where S3CO2 is the quantity of carbon dioxide of organic origin measured during the heating sequence in an inert atmosphere, and TOC is the content of total organic carbon as defined above.
    3- Quantification of pyritic sulfur
    According to the invention, during this step, the pyritic sulfur content S Pyrit contained in the sedimentary rock sample considered is quantified from pyritic pyrolysis sulfur and a weighting function ρ (α, β, γ ) according to the following formula (see below section "Determination of the expression of S Pyrit as a function of S ^ oi" below):
    < i + A + ->
    with, according to the invention, ρζα, β, γ ') = - 1 1 y ,
    S Pyrit being expressed as a percentage by mass, that is to say by mass of pyritic sulfur divided by the mass of the sample and multiplied by 100, and:
    - the parameter a, which represents the proportion of pyritic sulfur released during the pyrolysis phase compared to its total sulfur, and can be seen as a rate of thermal degradation of the pyrite. According to an implementation of the invention, the parameter a is between 0.40 and 0.46, and is preferably 0.43;
    - the parameter β, which represents the impact of the mineral matrix on the proportion of pyritic sulfur released during the pyrolysis phase. Indeed, the mineral matrix reduces the amount of sulfur from the pyrite released during the pyrolysis phase. According to one aspect of the invention, the parameter β can be between 0.04 and 0.97, depending on the type of rock from which the studied sample comes. According to an implementation of the invention in which the rock sample studied is of the clay type, the parameter β can be between 0.04 and 0.7, and is preferably equal to 0.38. According to an implementation of the invention in which the rock sample studied is of the marl type, the parameter β can be between 0.7 and 0.9, and is preferably 0.78. According to an implementation of the invention in which the rock sample studied is of the limestone type, the parameter β can be between 0.85 and 0.97, and is preferably 0.90.
    - the parameter y, which represents the impact of the organic matrix on the proportion of pyritic sulfur released during the pyrolysis phase, and is predetermined from a formula of the type:
    y = where / is a function of at least the oxygen index Ol and the hydrogen index IH, these indices having been determined during step 2 of the process according to the invention.
    According to a preferred implementation of the invention, the function f is a linear combination of the oxygen index Ol and the hydrogen index Hl, a linear combination which can be expressed according to a formula of the type: y = a * 01 + b * HI + c, where a, b and c are predetermined constants. Indeed, analyzes carried out on various samples (see below, section “calibration of the constants a, b and c of the parameter y >>) made it possible to highlight the linear behavior of the effect of the organic matrix compared to the indices of hydrogen and oxygen.
    Advantageously, the constant a is between 0.28 and 0.46, and is preferably worth 0.37 and / or the constant b is between -0.005 and -0.007 and is preferably worth -0.006 and / or the constant c is between 4.99 and 6.49 and is preferably worth 5.74. Indeed, analyzes carried out on various samples (see below, section “calibration of the constants a, b and c of the parameter γ”) made it possible to highlight the linear behavior of the effect of the organic matrix compared to hydrogen and oxygen indices. Advantageously, γ can vary between 0.34 (wt.%) And 74 (wt.%).
    Device for implementing the method according to the invention
    According to an implementation of the invention, steps 1 and 2 described above can be implemented using the ROCK-EVAL® device (IFP Energies nouvelles, France), developed by the applicant, and described in particular in the EP patent 2342557 (US 8796035). Indeed, the ROCK-EVAL® device includes at least:
    a pyrolysis oven in a non-oxidizing atmosphere, means for oxidizing sulfur-containing effluents, pyrolysis means for continuously measuring the amount of SO 2 contained in said effluents after oxidation, such as an ultraviolet (UV) spectrophotometer or infrared (IR), means for transferring pyrolysis residues in an oxidation furnace, an oxidation furnace in an oxidizing atmosphere, means for continuously measuring the amount of SO 2 contained in said part after oxidation, such as '' an ultraviolet (UV) or infrared (IR) spectrophotometer,
    - means for measuring the hydrocarbon compounds released during the pyrolysis, such as a flame ionization detector (FlD),
    - means for measuring carbon monoxide (CO) and carbon dioxide (CO 2 ), such as an infrared spectrophotometer (IR).
    According to an alternative implementation of the method according to the invention, the method can also be implemented by means of a system comprising a single pyrolysis oven, capable of operating in a non-oxidizing atmosphere and in an oxidizing atmosphere, cooperating with means for measuring the quantity of sulfur dioxide (SO 2 ), means for measuring the quantity of hydrocarbon compounds, as well as means for measuring carbon monoxide (CO) and carbon dioxide (CO 2 )
    Variant 1: Quantification of organic sulfur
    A first variant of the process according to the invention is described below, aiming to determine, in addition to the quantity of pyritic sulfur present in the sample considered, the quantity of organic sulfur present in this same sample. To do this, during step 2 of oxidation of the pyrolysis residue described above, the SO 2 generated by the oxidation of the pyrolysis residue and contained in the oxidation effluents is additionally measured. This SO 2 measurement is for example carried out using a UV or IR spectrophotometer. A measurement of the SO 2 released during the oxidation is thus obtained, for example as a function of the time and / or of the oxidation temperature.
    FIG. 1b presents an example of a curve (denoted C2) for measuring the amount of SO2 (more precisely the amplitude A measured by a SO 2 detector, such as an ultraviolet spectrophotometer) as a function of the time of oxidation (denoted t), and also presents the evolution of the oxidation temperature (denoted T) as a function of the oxidation time. For this example and for illustrative purposes, the temperature T1 has been chosen equal to 300 ° C, the temperature T2 has been chosen equal to 650 ° C, the temperature T3 has been chosen equal to 300 ° C and the temperature T4 has been chosen equal to 1200 ° C.
    It can be observed that this curve C2 has different peaks. In particular, we can observe on curve C2 the peak F which corresponds to the release of the sulfur contained in the sulfates (called "sulfur sulfates" thereafter, and noted S ^ a ) during the oxidation. Also, it can be observed that the curve C2 presents two first quasi-confused peaks D and E, which correspond respectively to organic sulfur contained in organic compounds, which are thermally refractory or else which were generated during the pyrolysis phase, and to pyritic sulfur. It can thus be seen that the recording of the SO 2 released during the oxidation phase does not make it possible to distinguish between these two peaks and therefore between organic sulfur and pyritic sulfur.
    According to this first variant of the invention, quantifies the sulfur pyrolysis S Pyrol released during pyrolysis and S oxidation Oxy sulfur released during the oxidation of the pyrolysis residue from the respectively SO2 measurements made during the heating sequence in an inert atmosphere and during the heating sequence in an oxidizing atmosphere. According to this variant of the invention, the total sulfur content, S Total is also determined as the sum of the two contents S Pyrol and S Oxy , ie:
    ^ Total ~ Spyrol + $ Oxy ’expressed as a mass percentage (wt.%), Or by mass of total sulfur divided by the mass of the sample and multiplied by 100.
    According to an implementation of this first variant of the invention, the sulfur content of pyrolysis S Pyrol (respectively the sulfur content of oxidation sulfur S Oxy ) of the sample analyzed can be determined from the area under the SO 2 measurement curve recorded during the pyrolysis heating sequence (respectively during the oxidative heating sequence), divided by the mass of the sample analyzed, weighted by a calibration coefficient for pyrolysis sulfur (respectively a calibration coefficient oxidation sulfur). These contents are expressed as a percentage by mass, that is to say by mass of pyrolysis sulfur (respectively of oxidation), divided by the mass of the sample and multiplied by 100.
    According to this first variant of the invention, the organic sulfur content S Ora contained in the rock sample considered can be determined from at least the difference between the total sulfur content S T otai and the pyritic sulfur content S Pyrit .
    According to a first implementation of this first variant of the invention according to which the end of oxidation temperature T4 is between 800 ° C and 900 ° C, it is possible to determine the content of organic sulfur S Ora contained in said sample according to a formula of the type:
    c Org oc Pyrit J - O Total ù
    According to a second implementation of this first variant of the invention according to which the end of oxidation temperature T4 is between 1150 ° C and 1250 ° C, preferably 1200 ° C, the content of organic sulfur S Ora can be determined contained in the sample as follows:
    quantifying a sulfur sulphate content S ^ l J a from the area under the representative peak of sulfur sulphates of the SO 2 measurement curve recorded during the oxidation phase, divided by the mass of the sample analyzed , and weighted by a calibration coefficient of oxidation sulfur (see step 3 above for the determination of this calibration coefficient);
    the organic sulfur content S Ora is determined according to a formula of the type:
    cOrg _ q çPyrtt ç Sulfa ύ Total ~ ύ ~ ^ 0xy
    Indeed, for this implementation alternative, one can distinguish the peak S ^ l J (cf. peak F in Figure 1a) which corresponds to the release during the oxidation of the sulfur in the sulphate, occurring for high temperatures. The determination of the organic sulfur content is more precise according to this second embodiment of the invention.
    Variant 2: Calibration of parameters a, β and γ
    According to an implementation of the invention, the parameters a and / or β and / or γ as defined above can be calibrated before the implementation of the method according to the invention, or else during the implementation implementing the method according to the invention, for example prior to step 1, to step 2 or to step 3 described above, or also in parallel with steps 1 and / or 2.
    • calibration of parameter a
    According to an implementation of the invention, the parameter a can be calibrated by estimating the proportion of the pyritic sulfur released during the pyrolysis phase relative to the total sulfur from at least one sample of pure igneous pyrite. According to an implementation of the invention, a so-called pure pyrite can be obtained by cleaning a natural pyrite from these impurities by chemical attacks.
    An example of calibration of the parameter a is described below. Four samples from a single sample of pure igneous pyrite (noted respectively E1, E2, E3, E4), of different masses (respectively 2mg, 3mg, 4mg and 8mg) are each subjected to a pyrolysis using the ROCK-EVAL device. ® (IFP Energies nouvelles, France). In particular, for this example of calibration of parameter a, each sample was placed in the pyrolysis oven of the ROCK-EVAL® device, then the sample was heated between 300 ° C and 650 ° C, with a temperature ramp of 25 ° C / min and under a nitrogen flow at 150ml / min. Then, the sulfur effluents released by each sample of pure igneous pyrite considered were entrained by the flow of nitrogen towards the combustion chamber (oxidation furnace) of the ROCK-EVAL® device, where they were transformed into SO 2 into continuous flow, then the SO 2 was driven to an SO 2 detector where it was continuously quantified using the SO 2 detector of the ROCK-EVAL® device. The solid residue from each sample of igneous pyrite, obtained at the end of the pyrolysis sequence, was then placed in the oxidation oven of the ROCK-EVAL® device and then the sample was heated to 300 ° C and 850 ° C, with a temperature ramp of 20 ° C / min and under an air flow at 100ml / min. The released SO 2 effluents were led to a SO 2 detector where they were continuously quantified using the SO 2 detector of the ROCK-EVAL® device.
    FIG. 2 shows the recording in time t of the quantity of SO 2 (more precisely the amplitude released by the samples E1, E2, E3, and E4 during the pyrolysis phase as described above. The curve T also presented in this figure 2 corresponds to the evolution of the temperature to which each of the samples considered is subjected during this same pyrolysis phase.We can notably observe in this figure the presence of peaks, representative of the thermal degradation of pyrite to different masses analyzed during the pyrolysis phase. The pyrolysis sulfur content of the igneous pyrite sample (pyrolysis pyritic sulfur content) was calculated by multiplying by the sulfur content of the reference sample the area under each of the curves E1, E2, E3 and E4, divided by the mass of the sample, and brought back to the area under the measurement curve of SO 2 released by a reference sample (such as native sulfur) during the heating sequence by pyrolysis, itself divided by the mass of the reference sample. The ratio between this pyrolysis pyritic sulfur content and the total sulfur content of the pyrite is calculated. The results show that, whatever the mass analyzed, the mass proportion of the pyritic sulfur which is released during the pyrolysis is 0.43 ± 0.03% wt. The remaining proportion of pyritic sulfur at the end of the pyrolysis (0.57 ± 0.03% wt) is then released during the oxidation phase.
    Thus, the calibration as described above makes it possible to determine that the parameter a is between 0.40 and 0.46, and is worth 0.43 on average.
    • calibration of the parameter β
    According to an implementation of the invention, the parameter β which represents the impact of the mineral matrix on the quantity of the pyrite sulfur released during the pyrolysis phase can be calibrated from at least one mixture of pyrite and at least one type of mineral, this mixture being representative of the rock sample to be studied by the method according to the invention.
    An example of calibration of the parameter β for different types of minerals is described below. For this example of calibration of the parameter β, mixtures were produced from the following two major groups of minerals:
    - clay / silicate minerals, such as
    Silica (Sable de Fontainebleau, France) the mixture produced with silica is the reference mixture because silica is known to be non-reactive;
    Kaolinite (Reference: CMS KGa 1b);
    Smectite (Reference: Mx80);
    Illite (Argile du Velay, France): this sample naturally containing carbonates, it was decarbonated with hydrochloric acid.
    - carbonated minerals, such as:
    Calcite (France);
    Dolomite (Euguy, Spain);
    Siderite (Peru).
    The following mixtures are then produced:
    - 2 mg of pyrite + 98 mg of each clay mineral / silicate;
    - 2 mg of pyrite + 58 mg of each carbonate mineral;
    - 2mg of pyrite + 98mg of clays (all clay minerals / silicates in equal parts%;%;%;%));
    - 2 mg of pyrite + 58 mg of carbonates (all carbonate minerals in equal parts 1/3; 1/3; 1/3);
    - 2 mg of pyrite + 58 mg of clays and carbonates in different proportions, i.e.
    93% clays and 7% carbonates;
    69% clays and 31% carbonates;
    51% clays and 49% carbonates;
    26% clays and 74% carbonates.
    These different samples are then subjected to steps 1 and 2 as described above using the ROCK-EVAL® device (IFP Energies nouvelles, France). More precisely, each sample is placed in the pyrolysis oven of the ROCKEVAL® device, then the sample is heated between 300 ° C and 650 ° C, with a temperature ramp of 25 ° C / min and under a flow nitrogen at 150ml / min. According to one implementation of the invention, the sulfur effluents released by each sample are entrained by a flow of nitrogen towards the combustion chamber (oxidation furnace) of the ROCK-EVAL® device where they are transformed into SO 2 into continuous flow, then the SO 2 is driven to the SO 2 detector of the ROCK-EVAL® device where it is quantified continuously. The solid residue from each sample obtained at the end of the pyrolysis sequence is then placed in the oxidation furnace of the ROCK-EVAL® device, then the sample is heated to 300 ° C and 850 ° C, with a temperature ramp of 20'C / min and under an air flow of 100ml / min. The released SO 2 effluents are led to a SO 2 detector where they are continuously quantified by means of the SO 2 detector of the ROCK-EVAL® device.
    Subsequently, the effect of the mineral matrix is called the quantity expressed according to a formula of the type:
    çPyrit.ref _ ^ Pyrit, Matrix r · _ b Pyrol ï'pyrol _______ '-'Min ~ Pyrit.ref 1 ^ Pyrol where SpyJ ^ ref is the pyritic sulfur of pyrolysis released by a reference sample (consisting of pure igneous pyrite and silica) and SpyJ 0 ^ Matrix is the pyritic pyrolysis sulfur released by a considered mixture (pure igneous pyrite plus a mineral or a mixture of minerals). To evaluate this quantity, the pyrritic sulfur content of pyrolysis is determined, for a reference sample Sp ^ ' ref and for a mixture considered çPyrtt, Matrix ^ Pyrol
    FIG. 3a presents a histogram representative of the effect E M i n of the mineral matrix as a function of the class of mixtures considered in the case of clay minerals / silicates and carbonates, more precisely for the following classes of mixtures:
    - M1: mixtures consisting of pyrite and quartz (reference sample);
    - M2: mixtures of pyrite and kaolinite;
    - M3: mixtures of pyrite and illite;
    - M4: mixtures of pyrite and smectite;
    - M5: mixtures of pyrite and calcite;
    - M6: mixtures of pyrite and dolomite;
    - M7: mixtures of pyrite and siderite.
    FIG. 3b presents a histogram representative of the effect E M in mean of clays, carbonates and intermediate formations on the proportion of sulfur of the pyrite released during pyrolysis for the following mixtures:
    - M8: mixtures made of 100% clay;
    - M9: mixtures made up of 93% clays and 7% carbonates;
    - M10: mixtures consisting of 69% clays and 31% carbonates;
    - M11: mixtures made up of 51% clays and 49% carbonates;
    - M12: mixtures made up of 26% clays and 74% carbonates;
    - M13: mixtures made of 100% carbonates.
    Figures 3a and 3b also show the error bars for each histogram bar. These error bars were obtained by estimating a standard deviation established from a repetition of the analyzes as described above.
    Thus, the results obtained by the implementation of the method for calibrating the parameter β as described above for the various mixtures described above highlight the fact that the mineral matrix can reduce the proportion of sulfur in pyrite released during the pyrolysis phase. However, this effect is very variable depending on the type of mineral present. The relative reduction in the proportion of sulfur released by pyrite during pyrolysis varies between 0% and 40% in the presence of clay / silicate minerals and between 60% and 98% in the presence of carbonate minerals (see Figure 3a). The average effect of clays is 6% while that of carbonates reaches 93% (see Figure 3b). Between these two poles we observe an increasing evolution of the effect of the mineral matrix E M as a function of the share of clays and carbonates in the mixture (cf. Figure 3b).
    FIG. 3c shows the evolution of the effect E M i n of the mineral matrix as a function of the mineral carbon (noted MinC below), which is a parameter which can be measured for example with the ROCK-EVAL® device (IFP Energies nouvelles, France), which is an indicator of the carbonate content of the mixtures. We can observe in this figure that the MinC varies over a range between 0wt% and 12wt%, which corresponds to a calcite equivalent between 0wt% and 100wt%. Thanks to this parameter, we can define three types of lithologies: clays, marls and limestones. The zone (A) of FIG. 3c represents the zone of clays, which have carbonate-equivalent calcite contents between
    0wt% and 30wt% (0 <MinC clays <3.6wt%). In this zone of clay formations, the effect of the matrix on the quantity of sulfur of the pyrite released during the pyrolysis phase varies between 6% and 70%, with an average of 38%. The zone (B) of FIG. 3c represents the zone of the marls, which have carbonate-equivalent calcite contents of between 30% and 70% (3.6 <MinC marls <8.4wt%). In this area of marl formations, the average value of the effect of the matrix on the quantity of sulfur from the pyrite released during the pyrolysis phase varies between 70% and 87%, with an average of 78%. The zone (C) in FIG. 3c represents the zone of limestones which have carbonate-equivalent calcite contents of between 70% and 100% (8.4wt% <MinC limestones <12wt%). In this zone of limestone formations, the average value of the effect of the matrix on the quantity of sulfur from the pyrite released during the pyrolysis phase varies between 87% and 94%, with an average of 90%.
    Thus, the parameter β varies between 0.06 and 0.94 depending on the type of sedimentary formations, and more precisely, in the case of:
    - Clays: the parameter β is on average 0.38;
    - Marnes: the parameter β is worth on average 0.78;
    - Limestones: the parameter β is worth on average 0.90.
    • calibration of the constants a, b, and c of the parameter y
    This step can be implemented in the context of the preferred implementation of the method according to the invention, according to which the parameter y is written in the form:
    y = a * OI + b * HI + c, where a, b and c are predetermined constants.
    According to an implementation of the invention comprising a step of calibrating the constants a, b, c of the parameter y, it is possible to produce mixtures consisting of pyrite and of different types of organic matter conventionally noted:
    - Type I: lake organic matter, such as "green river shales" (Eocene, USA);
    - Type II: marine organic matter, such as the “cardboard shales” of the Paris Basin (Toarcien, France);
    - Type II: marine organic matter from well ODP 959 (ConiacienSantonian, Ivory Coast-Ghana);
    - Type II oxidized: marine organic matter, such as the “cardboard shales” of the Paris Basin (Toarcien, France), artificially oxidized according to the method described in the document (Landais etal., 1991).
    - Type IIS: marine organic matter rich in organic sulfur, such as the "Phosphoria Formation" (Permien, USA);
    - Type III: terrestrial organic matter, such as the “Calvert bluff Formation” (Paleocene, USA);
    - Type III: terrestrial organic matter, such as the “Calvert bluff Formation” (Paleocene, USA);
    - Type III oxidized: terrestrial organic matter, such as "Calvert bluff Formation" (Paleocene, USA), artificially oxidized according to the method described in the document (Landais etal., 1991).
    - Mixtures of types II and III: mixtures of marine organic matter, such as the "cardboard shales" of the Paris Basin (Toarcien, France) and terrestrial organic matter, such as the "Calvert bluff Formation" (Paleocene, USA );
    Subsequently, the "expression of the organic matrix" is called the quantity expressed according to the ^ Pyrit + MO obtained _ $ Pyrit + MO expected following formula: E Org = Pyr ° l Pyrit + M0 P atten du --- ---- x 100, ^ Pyrol where 5ρ ^ + Μ0 obtained is the pyritic sulfur of pyrolysis obtained after the analysis of the mixture formed of pyrite and organic matter (as described in step 1 above) and S pyroi + M ° expected is the expected value of pyritic sulfur for pyrolysis of the mixture. This theoretical reference value is calculated as follows:
    - each sample of organic material is analyzed alone, using the ROCK-EVAL® device (IFP Energies nouvelles, France), to quantify its content of pyrolytic pyritic sulfur (as described in step 1 above);
    - the pyrite alone is analyzed, using the ROCK-EVAL® device (IFP Energies nouvelles, France), to quantify its content of pyrolytic pyritic sulfur (as described in step 1 above);
    - the pyritic sulfur from pyrolysis of the pyrite and the pyritic sulfur from the pyrolysis of the organic matter are added proportionally, as a function of the pyrite / organic matter ratio.
    Furthermore, the hydrogen index HI and the oxygen index 01 are determined for each of the samples described above, as described in step 2 above, using the ROCK-EVAL® device ( IFP Energies nouvelles, France). In particular, we determine to do this
    - the organic carbon content of PC pyrolysis according to the formula:
    PC (wt%) = [Q * 0.083] + S3CO * + the residual organic carbon content RC according to the formula:
    RC (wt ° / o) =
    the oxygen index 01 is determined according to the formula: 01 = the hydrogen index IH is determined according to the formula: HI =
    RC + PC
    RC + PC
    Then performing a multivariate regression on the effect of the organic matrix E Org according to the index 01 of oxygen and hydrogen index HI and the constants determining a, b, and c of the parameter γ as defined above and expressed in the form: γ = a * 01 + b * HI + c. The linear regression thus described makes it possible to obtain the following formula for the parameter γ representing the effect of the organic matrix:
    γ = 0.37 + 01 - 0.006 * HI + 5.74
    FIG. 4 presents the comparison between the value of y thus determined by regression (continuous line) and the values determined by measurements on the different samples (diamonds) as described above. We can observe a good correlation between the values taken by γ and the values of E Org determined by measurements (the linear regression coefficient R2 is 0.77), which shows that we can reliably predict the effect of the organic matter from the oxygen index 01 and the hydrogen index HI. Furthermore, from these experiments carried out on different types of sample, the following error bars are defined for each of the constants:
    - a = 0.37 ± 0.09
    - b = -0.006 ± 0.001
    - c = 5.74 ± 0.75
    Furthermore, knowing that generally 0 <IH (mgHC / gTOC) <900 and 0 <IO (mgCO 2 / gTOC) <200, y can vary between 0.34 wt.% (IH = 900; 10 = 0) and 74wt.% (1H = 0; 10 = 200).
    Determination of the expression of the weighting function
    The weighting function p (a, /, y) of the method according to the invention is different from that of patent application FR 17/59447 (filing number). The justification for the expression of the weighting function of the method according to the invention is detailed below.
    s pyroi re P re feel a pyritic sulfur content of pyrolysis has been reduced by the presence of the mineral matrix and of the organic matrix. It is therefore appropriate in a first step to correct the pyritic sulfur content of pyrolysis Sp ^ of the mineral effect and the organic effect. This then makes it possible to quantify the pyritic sulfur of total pyrolysis s total pyrot and then to deduce the total pyritic sulfur S Pyrit .
    Correction of the mineral effect CorrB:
    The mineral effect β represents the proportion of pyritic pyrolysis sulfur which is retained in the mineral matrix. Thus, knowing the effect of the mineral matrix β, we can find the pyritic sulfur of pyrolysis without this effect of the mineral matrix Sp y ^ t l withoutEmm · 15 The formula of the mineral effect can be written as follows :
    çPyrit without Emin _ çPyrit β _ ^ Pyrol Spyrol
    F çPyrit without Emin b Pyrol çPyrit β - γ__Spyrol
    F çPyrit without Emin ^ Pyrol çPyrit
    Hyrol _ β çPyrit without Emin F ^ Pyrol çPyrit çPyrit without Emin _Spyrol b Pyrol ~ 1 - β
    We then define Βοννβ, which represents the quantity of pyritic pyrolysis sulfur which has been retained in the mineral matrix, according to the following formula:
    r 'n çPyrit without Emin çPyrit
    Οοννβ = S p y yrol -Sp y rol çPyrit
    CorrB = pyr ° l - s Pyrit currp γ-β pyroi € θΓΓβ = S P ^ (^ - 1)
    Correction of the organic effect CorrE ,,,. ,,
    The organic effectγ represents the proportion of pyritic pyrolysis sulfur which is retained in the organic matrix. Thus, knowing the effect of the organic matrix y, we can find the pyritic sulfur of pyrolysis without this effect of the organic matrix Spyroi sansE ° r9 The formula of the organic effect can be written as follows:
    çPyrtt without Eorg _ çPyrit _ ^ Pyrol ^ pyrol f çPyrit without Eorg b Pyrol çPyrlt ^ pyrol 'çPyrit without Eorg b Pyrol rPyrit pyroi = i _ çPyrit without Eorg' ^ Pyrol çPyrit çPyrit without Eorg _ pyroi ^ Pyrol - 1 _
    CorrE org is then defined, which represents the quantity of pyritic pyrolysis sulfur which has been retained in the organic matrix, according to the following formula:
    n Pyrtt without Eorq n Pyrtt
    Corry = S p y rol ~ S p y rol çPyrit d pyroi r Pyrtt Corr y = ____ Sp y roi
    Corry = -1)
    Corry =
    Pyritic sulfur calculation of total total pyrolysis
    The total pyrolysis sulfur Ε ρ ^ total is then obtained from the sum between (the pyrolysis sulfur content reduced by the presence of the mineral matrix and the organic matrix), Corrf (the quantity of the pyrritic sulfur pyrolysis which was retained in the mineral matrix) and Corry (the quantity of pyrolysis pyritic sulfur which was retained in the organic matrix) as follows:
    S total pyrol = S pyrol + Corr P + Corr Y rPyrit _ ç.Pyrit, ç.Pyrlt (@ , çPyrit z Y Spyrol total Spyrol _ β) 'pyroL' - ^ _ y çPyrtt _ çPyrlt ^. β Y Spyrol total ~ '-'pyrol' · '^ _β' ^ _ γ /
    Calculation of total pyritic sulfur s Pyrit
    The total pyritic sulfur s Pyrit is calculated from pyritic sulfur of total pyrolysis S Py total and of the parameter a (the proportion of pyritic sulfur of total pyrolysis s total pyroi P ar compared to total pyritic sulfur S Pyrit ):
    çPyrtt çPyrtt _ Total spyrol a fl -I — β | Y) çPyrtt _ çPyrtt 1 ~ β 1 ~ Y d - Spyrol * n
    S Pyrit = p (a, M * S ^
    We therefore deduce the following expression for the weighting function used to determine the total pyritic sulfur s Pyrit from the pyritic pyrolysis sulfur S Py ^ measured:
    ρ (α, β, γ) il -I --—-- 1 --—— 1 a
    Application examples
    The example of application below aims to assess the quality of the results obtained by the implementation of the method according to the invention. To do this, various mixtures formed from nine samples of sedimentary rock containing only organic sulfur are formed, in known quantity, to which known masses of pyrite are added. The rock samples come from three different formations ("Orbagnous >>," Phosphoria >> and "Limagne >>) and were taken from different levels of these formations. The characteristics of these nine samples of sedimentary rock are summarized in the first nine lines of Tables 1a and 1b below. Different masses of pyrite were added to these nine samples, according to the characteristics summarized in lines 10 and 11 of Tables 1a and 1b below. In this way, 14 mixes of the “pyrite + Orbagnoux” type are produced (type noted EXA below), 6 mixes of the “pyrite + Phosphoria” type (type noted EXB below), and 8 mixes of the “ pyrite + Limagne ”(type noted EXC below).
    Then, the pyritic sulfur and organic sulfur contents of each of these mixtures are determined by the method according to the invention on the one hand, and on the other hand by the method according to the prior art described in the application for Patent FR.17 / 59.447.
    The method according to the invention is implemented by means of the ROCK-EVAL® device (IFP Energies nouvelles, France). More precisely, each mixture is placed in the pyrolysis oven of the ROCK-EVAL® device and then the mixture is heated between 300 ° C and 650 ° C, with a temperature ramp of 25Ό / ιηίη and under a flow of nitrogen at 150ml / min. According to an implementation of the invention, the sulfur effluents released by each sample are entrained by a flow of nitrogen towards a combustion chamber (also called oxidation furnace) of the ROCK-EVAL® device where they are transformed into SO 2 in continuous flow, then the SO 2 is driven to the SO 2 detector of the ROCK-EVAL® device where they are quantified continuously. At the end of the pyrolysis, each residue of the mixture is transferred from the pyrolysis oven to the oxidation oven of the ROCK-EVAL® device and then the sample is heated to 300 ° C and 850 ° C or 1200 ° C depending on the implementation, with a temperature ramp of 20 ° C / min and under an air flow of 100ml / min. The SO 2 effluents released by this oxidation are entrained up to the SO 2 detector of the ROCK-EVAL® device where they are continuously quantified. The total sulfur, pyritic sulfur and organic sulfur contents of each mixture are determined by implementing the method according to the invention as described above.
    FIGS. 5a, 5b, and 5c respectively present the evolution of the contents of total sulfur (INV TS), pyritic sulfur (INV S pyr it) and organic sulfur (INV S org ) obtained by the process according to the invention, as a function of the reference contents respectively in total sulfur (VR TS), in pyritic sulfur (VR S pyri t) and in organic sulfur (VR S org ) for each of the mixtures of the EXA type (ie 14 mixtures "pyrite + Orbagnoux") , for each of the mixtures of the EXB type (ie 6 mixtures "pyrite + Phosphoria") and for each of the mixtures of the EXC type (or 8 mixtures "pyrite + Limagne").
    One can observe in FIGS. 5a, 5b, and 5c a very good correlation between the contents of total sulfur, of pyritic sulfur and of organic sulfur determined from the process according to the invention and the reference contents of total sulfur, of sulfur pyritic and organic sulfur (correlation with a slope close to 1). This confirms the accuracy of the determination of the pyritic sulfur and organic sulfur content of a sample by the method according to the invention.
    FIGS. 5d and 5e respectively show the evolution of the contents of pyritic sulfur (AA S pyri t) and of organic sulfur (AA S org ) obtained by the process according to the prior art as a function of the reference contents respectively of pyritic sulfur (VR S pyri t) and in organic sulfur (VR S org ) for each of the EXA type mixtures (ie 14 "pyrite + Orbagnoux" mixtures), for each of the EXB type mixtures (ie 6 "pyrite + Phosphoria" mixtures) and for each of the EXC type mixtures (ie 8 “pyrite + Limagne” mixtures).
    We can observe in Figures 5d and 5e a poorer correlation between the pyritic sulfur and organic sulfur contents determined from the process according to the prior art and the reference contents of pyritic sulfur and organic sulfur.
    Thus, the present invention makes it possible to significantly improve the accuracy of the determination of the content of pyritic sulfur contained in a sample of sedimentary rock, and consequently the accuracy of the determination of the content of organic sulfur contained in a sample of sedimentary rock.
    Table 1a
    formations Orbagnoux Phosphoria ages Kimmeridgien Permian Country France United States Samples O-9m O-9ka O-9cb O-9ca P-55 P- 43 IO(MgCOVgCOT) 40.0 25.6 11.6 24.0 127.5 61.3 IH(MGHC / GCOT) 964.6 969.6 811.8 887.5 134.5 372.5 Mineral carbon content (wt.%) 11.2 10.8 0.8 10.7 0.3 0.4 Rock mass (mg) 60 + 0.02 60 ± 0.02 60 + 0.02 30 + 0.02 60 + 0.02 30 + 0.02 Organic sulfur content (wt.%) 0.3 + 0.03 0.7 ± 0.03 0.7 + 0.03 1.21 + 0.03 0.6 + 0.03 1.8 + 0.03 Mass of pyrite (mg) 1; 2; 3; 4+0.02 1; 2; 3; 4+0.02 1; 2; 3; 4+0.02 1, 2+0.02 1; 2; 3; 4+0.02 1; 2 + 0.02 Pyritic sulfur content (wt.%) 53 + 2 53 + 2 53 + 2 53 + 2 53 + 2 53 + 2
    Table lb
    formations Limagne ages Eocene-Oligocene Country France Samples L-S18-2 L-S02-5 L-S05-2
    ΙΟ(MgCOVgCOT) 39.0 31.5 30.5 ΙΗ(MGHC / GCOT) 549.0 660.0 691.5 Mineral carbon content (wt.%) 0.1 0.2 0.2 Rock mass (mg) 60 + 0.02 30 + 0.02 30 + 0.02 Organic sulfur content (wt.%) 0.4 + 0.03 2.2 + 0.03 1.5 + 0.03 Mass of pyrite (mg) 1; 2; 3; 4+0.02 1; 2 + 0.02 1; 2 + 0.02 Pyritic sulfur content (wt.%) 53 + 2 53 + 2 53 + 2
    权利要求:
    Claims (18)
    [1" id="c-fr-0001]
    1) Method for quantifying pyritic sulfur in a sample of sedimentary rock, in which at least the following steps are applied:
    A. heating said sample in an inert atmosphere, between a first temperature between 80 ° C and 320 ° C and a tenth temperature between 600 ° C and 700 ° C, following a first sequence of temperatures, and measuring continuously an amount of hydrocarbon compounds, an amount of CO and an amount of CO 2 released during said first temperature sequence;
    B. at least part of the effluents from said heating in an inert atmosphere of said sample are continuously oxidized, a quantity of SO 2 released by said oxidation of said effluents is continuously measured as a function of the time of said heating in an inert atmosphere, and determines at least one pyritic sulfur content of pyrolysis Sp ^ i from said quantity of SO 2 ;
    C. the residue of said sample from said heating in an inert atmosphere is heated in an oxidizing atmosphere between a third temperature between 280 ° C and 320 ° C and a fourth temperature above or equal to 800 ° C, by following a second sequence of temperatures , and continuously measuring an amount of CO and an amount of CO 2 released during said second temperature sequence;
    characterized in that at least one content of pyritic sulfur S Pyri £ contained in said sample is determined from a formula of the type:
    ^ Pyrit Pyrit ^ + 1-β + 1-γ ) pyrol * ™ where a is a parameter representing a proportion of said pyrolysis pyritic sulfur relative to said total sulfur, β is a parameter representing an effect of the mineral matrix on said proportion, y is a parameter representing an effect of the organic matrix on said proportion, the values of said parameters a and β being predetermined, and said parameter γ being determined from a formula of the type:
    where fest is a function of at least one oxygen index 01 and a hydrogen index HI, said hydrogen index HI being a function of at least said quantity of hydrocarbon compounds measured during said heating in an inert atmosphere and said quantities of CO and CO 2 measured during said first and second temperature sequences, and said oxygen index 01 being a function at least of said quantities of CO and C0 2 measured during said first and second temperature sequences.
    [2" id="c-fr-0002]
    2) Method according to claim 1, wherein said function f is a linear combination of said oxygen index Ol and said hydrogen index HI expressed according to a formula of the type: γ = a * 01 + b * HI + c , where a, b and c are predetermined constants.
    [3" id="c-fr-0003]
    3) Method according to claim 2, wherein said constant a is between 0.28 and 0.46, and is preferably 0.37.
    [4" id="c-fr-0004]
    4) Method according to one of claims 2 to 3, wherein said constant b is between -0.007 and -0.005 and is preferably equal to -0.006.
    [5" id="c-fr-0005]
    5) Method according to one of claims 2 to 4, wherein said constant c is between 4.99 and 6.49 and is preferably 5.74.
    [6" id="c-fr-0006]
    6) Method according to one of the preceding claims, wherein said hydrogen index HI is determined according to a formula of the type:
    100 * 52
    H1 -.
    TOC where
    S2 is an amount of hydrocarbon compounds which are cracked during said first temperature sequence, S2 being determined from said amount of hydrocarbon compounds released during said heating in an inert atmosphere,
    - TOC is a total organic carbon content of said sample written in the form T0C (wt%) = PC + RC, where PC is an organic carbon content of pyrolysis of said sample determined from said measurements of CO and CO 2 released during said first temperature sequence, and where RC is a residual organic carbon content of said sample determined from said CO and CO 2 measurements released during said second temperature sequence.
    [7" id="c-fr-0007]
    7) Method according to one of the preceding claims, wherein in which said oxygen index 01 is determined according to a formula of the type:
    _ rioo * s3co;, j - L toc J 'where:
    - S3CO 2 is an amount of C0 2 measured between said first temperature of said first temperature sequence and a first intermediate temperature of said first temperature sequence between 350 ° C and 450 ° C, and preferably equal to 400 ° C;
    - TOC is a total organic carbon content of said sample and is written TOC (wt ° / o) = PC + RC, where PC is an organic carbon content of pyrolysis of said sample determined from said CO and CO2 measurements released during said first temperature sequence, and where RC is a residual organic carbon content of said sample determined from said measurements of CO and CO2 released during said second temperature sequence.
    [8" id="c-fr-0008]
    8) Method according to one of claims 6 or 7, wherein said organic carbon content of PC pyrolysis of said sample is determined according to a formula of the type:
    PC (wt%) = [Q * 0.083] + [(S3CO + ± S3'CO) * ^] + [S3CO 2 * ^], with
    - S3CO2 is an amount of CO 2 measured between said first temperature of said first temperature sequence and a first intermediate temperature of said first temperature sequence between 350 ° C and 450 ° C, and preferably equal to 400 ° C;
    - S3CO is an amount of CO measured between said first temperature of said first temperature sequence and a second intermediate temperature of said first temperature sequence between 500 and 600 ° C, and preferably equal to 550 ° C;
    - S3'CO is a quantity of CO measured between said second intermediate temperature of said first temperature sequence and said second temperature of said first temperature sequence;
    [9" id="c-fr-0009]
    9) Method according to one of claims 6 to 8, wherein said residual organic carbon content RC of said sample is determined according to a formula of the type:
    12 S4CO 2 * - 2440.
    and S4CO 2 correspond respectively to an amount of between said third temperature of said second temperature and an intermediate temperature of said second temperature between 600 ° C and 700 ° C, and was preferably 650 ° C.
    RC (wt ° / o) =
    η 12 + S4CO * -280
    where S4CO measured
    CO and CO 2 sequence sequence
    [10" id="c-fr-0010]
    10) Method according to one of the preceding claims, in which said sample is of the reservoir rock type, and in which said first temperature is between 100 ° C and 200 ° C.
    [11" id="c-fr-0011]
    11) Method according to one of the preceding claims, in which said sample is of the conventional source rock or immature unconventional source rock, and in which said first temperature is between 280 ° C and 320 ° C.
    [12" id="c-fr-0012]
    12) Method according to one of the preceding claims, wherein said sample is of unconventional gas or oil source rock type, and wherein said first temperature is between 80 ° C and 120 ° C.
    12) Method according to one of the preceding claims, wherein said parameter a is between 0.40 and 0.46, and is preferably 0.43.
    [13" id="c-fr-0013]
    13) Method one of the preceding claims, in which said rock sample is of the clay type, and for which said parameter β is between 0.04 and 0.7, and is preferably equal to 0.38.
    [14" id="c-fr-0014]
    14) Method according to one of claims 1 to 12, wherein said rock sample is of the marl type, and for which said parameter β is between 0.7 and 0.9, and is preferably 0.78.
    [15" id="c-fr-0015]
    15) Method according to one of claims 1 to 12, wherein said rock sample is of limestone type, and for which the parameter β is between 0.85 and 0.97, and is preferably 0.9.
    [16" id="c-fr-0016]
    16) Method according to one of the preceding claims, in which a quantity of SO 2 released during said second temperature sequence is also measured, at least a sulfur content of pyrolysis S Pyrol is determined from said quantity of SO 2 measured during said first temperature sequence and an oxidation sulfur content S Oxy from said quantity of SO 2 measured during said second temperature sequence, and an organic sulfur content S Ora is determined from at least said content in pyritic sulfur s Pyrit , said pyrolysis sulfur content Spyroi and said oxidation sulfur content S Oxy .
    [17" id="c-fr-0017]
    17) The method of claim 16, wherein said fourth temperature is between 800 ° C and 900 ° C, and wherein, ^ ^ terminates an organic sulfur content S Ora according to the formula: S Ora = S Pyrol + S Oxy - S Pyrit .
    [18" id="c-fr-0018]
    18) Method according to one of claims 16, wherein said fourth temperature is greater than 1150 ° C, and is preferably lower than 1250 ° C, and wherein, it further determines a sulfur content sulfates $ o xy a from said amount of SO2 measured during said second sequence of temperatures, and we deduce an organic sulfur content according to the formula: s = Ora SPyrol Oxy + s - s Pyrit -S ^ l y a.
    类似技术:
    公开号 | 公开日 | 专利标题
    Sebag et al.2006|Monitoring organic matter dynamics in soil profiles by ‘Rock‐Eval pyrolysis’: bulk characterization and quantification of degradation
    Espitalié et al.1977|Source rock characterization method for petroleum exploration
    EP3588083A1|2020-01-01|Method for quantifying the pyritic sulphur and organic sulphur of a rock sample
    FR3072173B1|2019-09-27|METHOD FOR ESTIMATING THE QUANTITY OF FREE HYDROCARBONS IN A SEDIMENTARY ROCK SAMPLE
    Graz et al.2010|Quantitative palynofacies analysis as a new tool to study transfers of fossil organic matter in recent terrestrial environments
    Pinti et al.2009|Isotopic fractionation of nitrogen and carbon in Paleoarchean cherts from Pilbara craton, Western Australia: origin of 15N-depleted nitrogen
    Meyers et al.1999|Effects of extreme heating on the elemental and isotopic compositions of an Upper Cretaceous coal
    Andò et al.2020|Integrating heavy-mineral, geochemical and biomarker analyses of Plio-Pleistocene sandy and silty turbidites: a novel approach for provenance studies |
    EP3454061B1|2020-03-11|Method for quantifying the pyritic sulphur and organic sulphur of a rock sample
    di‐Giovanni et al.1998|Geochemical characterization of soil organic matter and variability of a postglacial detrital organic supply |
    EP0691540B1|2003-02-26|Improved method for the rapid determination of at least one petrological characteristic of a sample of rock and its application to strata containing heavy oil
    Silva et al.2017|A new TOC, Rock-Eval, and carbon isotope record of Lower Jurassic source rocks from the Slyne Basin, offshore Ireland
    Hetényi et al.2005|Stepwise Rock-Eval pyrolysis as a tool for typing heterogeneous organic matter in soils
    Kontorovich et al.2019|Geochemistry and catagenetic transformations of kerogen from the Bazhenov horizon
    Zaputlyaeva et al.2020|Recent magmatism drives hydrocarbon generation in north-east Java, Indonesia
    Larina et al.2021|Ecosystem change and carbon cycle perturbation preceded the end-Triassic mass extinction
    Díaz-Somoano et al.2007|Lead isotope ratios in Spanish coals of different characteristics and origin
    Poirier et al.2006|Dynamics and origin of the non‐hydrolysable organic fraction in a forest and a cultivated temperate soil, as determined by isotopic and microscopic studies
    Hetényi et al.2006|Heterogeneous organic matter from the surface horizon of a temperate zone marsh
    Machado et al.2019|Organic matter and soil fertility in different successional stages of seasonal semidecidual forest
    Czirbus et al.2016|Investigation of the effect of soil mineral composition on soil organic matter stability
    Borisova et al.2022|Regular Trends in Variation of the Asphaltene Composition and Structure in Dia-and Catagenesis
    Osterhout et al.2019|Preservation of carbon isotopes in kerogen from thermally altered Mesoproterozoic lacustrine microbialites
    Mitra-Kirtley et al.2007|Sulfur chemical moieties in carbonaceous materials
    Ahmed et al.2004|Techniques and Methods of Organic Geochemistry as Applied to Petroleum Exploration
    同族专利:
    公开号 | 公开日
    BR102019013141A2|2020-02-18|
    US20200003750A1|2020-01-02|
    CA3047571A1|2019-12-29|
    EP3588083A1|2020-01-01|
    FR3083316B1|2020-06-12|
    RU2019119596A|2020-12-25|
    CN110658322A|2020-01-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2937737A1|2008-10-29|2010-04-30|Inst Francais Du Petrole|METHOD AND DEVICE FOR RAPID CHARACTERIZATION AND QUANTIFICATION OF SULFUR IN SEDIMENTARY ROCKS AND PETROLEUM PRODUCTS|
    FR2722296B1|1994-07-05|1996-08-30|Inst Francais Du Petrole|IMPROVED METHOD FOR THE RAPID ASSESSMENT OF AT LEAST ONE OIL CHARACTERISTIC OF A ROCK SAMPLE APPLICATION TO A DEPOSIT COMPRISING HEAVY OILS|
    FR3021748B1|2014-06-03|2016-09-02|Ifp Energies Now|METHOD FOR EVALUATING AT LEAST ONE PETROLEUM CHARACTERISTIC OF A ROCK SAMPLE|US10942098B2|2017-08-25|2021-03-09|Schlumberger Technology Corporation|Method and system for analyzing at least a rock sample extracted from a geological formation|
    FR3071063B1|2017-09-12|2019-09-13|IFP Energies Nouvelles|PROCESS FOR THE QUANTIFICATION OF PYRITIC SULFUR AND ORGANIC SULFUR OF A ROCK SAMPLE|
    法律状态:
    2019-06-25| PLFP| Fee payment|Year of fee payment: 2 |
    2020-01-03| PLSC| Search report ready|Effective date: 20200103 |
    2020-06-26| PLFP| Fee payment|Year of fee payment: 3 |
    2021-06-25| PLFP| Fee payment|Year of fee payment: 4 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1856042|2018-06-29|
    FR1856042A|FR3083316B1|2018-06-29|2018-06-29|PROCESS FOR THE QUANTIFICATION OF PYRITIC SULFUR AND ORGANIC SULFUR FROM A SAMPLE OF ROCK|FR1856042A| FR3083316B1|2018-06-29|2018-06-29|PROCESS FOR THE QUANTIFICATION OF PYRITIC SULFUR AND ORGANIC SULFUR FROM A SAMPLE OF ROCK|
    EP19179110.2A| EP3588083A1|2018-06-29|2019-06-07|Method for quantifying the pyritic sulphur and organic sulphur of a rock sample|
    CA3047571A| CA3047571A1|2018-06-29|2019-06-20|Process for the quantification of pyrite sulphur and organic sulphur from a rock sample|
    RU2019119596A| RU2019119596A|2018-06-29|2019-06-24|METHOD FOR DETERMINING THE QUANTITY OF PYRITE SULFUR AND ORGANIC SULFUR IN A BREED SAMPLE|
    BR102019013141-1A| BR102019013141A2|2018-06-29|2019-06-25|PROCESS FOR THE QUANTITATIVE EVALUATION OF PYRITIC SULFUR AND ORGANIC SULFUR FROM A ROCK SAMPLE|
    US16/457,216| US20200003750A1|2018-06-29|2019-06-28|Process for quantifying the pyritic sulfur and the organic sulfur of a rock sample|
    CN201910575148.0A| CN110658322A|2018-06-29|2019-06-28|Method for quantifying pyrite sulfur and organic sulfur in rock samples|
    [返回顶部]