# US 11,442,053 B2 · Process for quantifying the pyritic sulfur and the organic sulfur of a rock sample > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,442,053 B2 - Document ID: US11442053B2 - Status: Granted - Kind: B2 - Application number: 16/457,216 - Filed: 2019-06-28 - Published: 2020-01-02 - Granted: 2022-09-13 - Earliest claimed: 2018-06-29 - Assignees: Ifp Energies Nouvelles - Applicants: IFP Energies nouvelles - Inventors: Anabel Aboussou; Violaine Lamoureux-Var; Daniel Pillot; Isabelle Kowalewski; Bruno Garcia; Thomas Wagner; Christian März - Web page: https://patentgrep.com/patent/US11442053B2 ## CPC - G01N 33/24: Earth materials (G01N33/42 takes precedence) - G01N 33/241: {for hydrocarbon content} - E21B 49/02: by mechanically taking samples of the soil - G01N 25/00: Investigating or analyzing materials by the use of thermal means (G01N3/00 - G01N23/00 take precedence) - G01N 31/12: using combustion (G01N25/20 takes precedence) - G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q) - E21B: EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS ## Abstract A rock sample is subjected to a heating sequence in an inert atmosphere, the effluents resulting from this heating are oxidized, the hydrocarbon-based compounds, the CO, the CO2 and the SO2 released are measured, and a pyrolysis pyritic sulfur content is deduced therefrom. The residue resulting from the heating in an inert atmosphere is then heated in an oxidizing atmosphere and the CO and the CO2 released are measured. The pyritic sulfur content is determined at least from the pyrolysis pyritic sulfur content and from a parameter which is a function of the hydrogen content and of the oxygen content of the organic matter of the sample. It is also possible to determine the organic sulfur content from the pyritic sulfur content and from a measurement of the SO2 during the heating sequence in an oxidizing atmosphere. ## Claims ### Claim 1 A process for quantifying the pyritic sulfur in a sedimentary rock sample, in which at least the following steps are applied: A. the sample is heated in an inert atmosphere, between a first temperature of between 80° C. and 320° C. and a second temperature of between 600° C. and 700° C., while following a first temperature sequence, and an amount of hydrocarbon-based compounds, an amount of CO and an amount of CO2 released during the first temperature sequence are continuously measured; B. at least one portion of the effluents resulting from the heating of the sample in an inert atmosphere is continuously oxidized, an amount of SO2 released by the oxidation of the effluents as a function of the time of the heating in an inert atmosphere is continuously measured, and at least one pyrolysis pyritic sulfur content SPyrolPyrit is determined from the amount of SO2; C. the residue of the sample resulting from the heating in an inert atmosphere is heated in an oxidizing atmosphere between a third temperature of between 280° C. and 320° C. and a fourth temperature of greater than or equal to 800° C., while following a second temperature sequence, and an amount of CO and an amount of CO2 released during the second temperature sequence are continuously measured; wherein at least one pyritic sulfur content SPyrit contained in the sample is determined on the basis of a formula: S Pyrit = S pyrol Pyrit * ( 1 + β 1 - β + γ 1 - γ ) α wherein α is a parameter representing a proportion of the pyrolysis pyritic sulfur relative to the total sulfur, β is a parameter representing an effect of the mineral matrix on the proportion, and γ is a parameter representing an effect of the organic matrix on the proportion, the values of the parameters α and β being predetermined, and the parameter γ being determined from a formula: γ=ƒ(OI,HI) wherein ƒ is a function of at least one oxygen index OI and of a hydrogen index HI, the hydrogen index HI being a function at least of the amount of hydrocarbon-based compounds measured during the heating in an inert atmosphere and the amounts of CO and of CO2 measured during the first and second temperature sequences, and the oxygen index OI being a function at least of the amounts of CO and of CO2 measured during the first and second temperature sequences. ### Claim 2 (depends on 1) A process according to claim 1, in which the function ƒ is a linear combination of the oxygen index OI and of the hydrogen index HI which is expressed according to a formula: γ=a*OI+b*HI+c, wherein a, b and c are predetermined constants. ### Claim 3 (depends on 2) A process according to claim 2, in which the constant a is between 0.28 and 0.46. ### Claim 4 (depends on 2) A process according to claim 2, in which the constant b is between −0.007 and −0.005. ### Claim 5 (depends on 2) A process according to claim 2, in which the constant c is between 4.99 and 6.49. ### Claim 6 (depends on 1) A process according to claim 1, in which the hydrogen index HI is determined according to a formula HI = 100 * S ⁢ ⁢ 2 RC + PC , wherein S2 is an amount of hydrocarbon-based compounds which are cracked during the first temperature sequence, S2 being determined from the amount of hydrocarbon-based compounds released during the heating in an inert atmosphere; TOC is a total organic carbon content of the sample which is written in the form TOC(wt %)=PC+RC, wherein PC is an organic carbon content from pyrolysis of the sample determined from the measurements of CO and CO2 released during the first temperature sequence, and wherein RC is a residual organic carbon content of the sample determined from the measurements of CO and of CO2 released during the second temperature sequence. ### Claim 7 (depends on 1) A process according to claim 1, in which the oxygen index OI is determined according to a formula: OI = [ 100 * S ⁢ ⁢ 3 ⁢ CO 2 TOC ] , wherein: S3CO2 is an amount of CO2 measured between the first temperature of the first temperature sequence and a first intermediate temperature of the first temperature sequence of between 350° C. and 450° C., and preferentially equals 400° C.; and TOC is a total organic carbon content of the sample and is written TOC(wt %)=PC+RC, wherein PC is an organic carbon content from pyrolysis of the sample determined from the measurements of CO and CO2 released during the first temperature sequence, and wherein RC is a residual organic carbon content of the sample determined from the measurements of CO and of CO2 released during the second temperature sequence. ### Claim 8 (depends on 6) A process according to claim 6, in which the pyrolysis organic carbon content PC of the sample is determined according to a formula: PC ⁡ ( wt ⁢ % ) = [ Q * 0.083 ] + [ ( S ⁢ 3 ⁢ CO + 1 2 ⁢ S ⁢ 3 ′ ⁢ CO ) * 12 280 ] + [ S ⁢ 3 ⁢ CO 2 * 12 440 ] , with S3CO2 is an amount of CO2 measured between the first temperature of the first temperature sequence and a first intermediate temperature of the first temperature sequence of between 350° C. and 450° C.; S3′CO is an amount of CO measured between the first temperature of the first temperature sequence and a second intermediate temperature of the first temperature sequence of between 500 and 600° C.; S3′CO is an amount of CO measured between the second intermediate temperature of the first temperature sequence and the second temperature of the first temperature sequence. ### Claim 9 (depends on 6) A process according to claim 6, in which the residual organic carbon content RC of the sample is determined according to a formula: RC ⁡ ( wt ⁢ % ) = [ S ⁢ 4 ⁢ CO 2 * 12 440 ] + [ S ⁢ 4 ⁢ CO * 12 280 ] , wherein S4CO and S4CO2 correspond respectively to an amount of CO and of CO2 measured between the third temperature of the second temperature sequence and an intermediate temperature of the second temperature sequence of between 600° C. and 700° C. ### Claim 10 (depends on 1) A process according to claim 1, in which the sample is a reservoir rock, and in which the first temperature is between 100° C. and 200° C. ### Claim 11 (depends on 1) A process according to claim 1, in which the sample is a source rock or immature shale, and in which the first temperature is between 280° C. and 320° C. ### Claim 12 (depends on 1) A process according to claim 1, in which the sample is a gas-bearing or oil-bearing shale, and in which the first temperature is between 80° C. and 120° C. ### Claim 13 (depends on 1) A process according to claim 1, in which the parameter α is between 0.40 and 0.46. ### Claim 14 (depends on 1) A process according to claim 1, in which the rock sample is a clay, and for which the parameter β is between 0.04 and 0.7. ### Claim 15 (depends on 1) A process according to claim 1, in which the rock sample is a marl, and for which the parameter β is between 0.7 and 0.9. ### Claim 16 (depends on 1) A process according to claim 1, in which the rock sample is a limestone, and for which the parameter β is between 0.85 and 0.97. ### Claim 17 (depends on 1) A process according to claim 1, in which, in addition, an amount of SO2 released during the second temperature sequence is measured, at least one pyrolysis sulfur content SPyrol is determined from the amount of SO2 measured during the first temperature sequence and an oxidation sulfur content SOxy is determined from the amount of SO2 measured during the second temperature sequence, and an organic sulfur content SOrg is determined from at least the pyritic sulfur content SPyrit, from the pyrolysis sulfur content SPyrol and from the oxidation sulfur content SOxy. ### Claim 18 (depends on 17) A process according to claim 17, in which the fourth temperature is between 800° C. and 900° C., and in which an organic sulfur content SOrg is determined according to the formula: SOrg=SPyrol+SOxy−SPyrit. ### Claim 19 (depends on 17) A process according to one claim 17, in which the fourth temperature is greater than 1150° C., and is preferentially less than 1250° C., and in which a sulfate sulfur content SOxySulfa is also determined from the amount of SO2 measured during the second temperature sequence, and an organic sulfur content is deduced therefrom according to the formula: SOrg=SPyrol+SOxy—SPyrit−SOxySulfa.