WO2014022757A1 - Procédé et appareil d'estimation simultanée de la minéralogie quantitative, de la teneur et de la maturité en kérogène dans les shales gazifères et les shales bitumineux par spectroscopie de vibration - Google Patents

Procédé et appareil d'estimation simultanée de la minéralogie quantitative, de la teneur et de la maturité en kérogène dans les shales gazifères et les shales bitumineux par spectroscopie de vibration Download PDF

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Publication number
WO2014022757A1
WO2014022757A1 PCT/US2013/053391 US2013053391W WO2014022757A1 WO 2014022757 A1 WO2014022757 A1 WO 2014022757A1 US 2013053391 W US2013053391 W US 2013053391W WO 2014022757 A1 WO2014022757 A1 WO 2014022757A1
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WIPO (PCT)
Prior art keywords
spectroscopy
calculating
maturity
sample
kerogen
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Application number
PCT/US2013/053391
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English (en)
Inventor
Andrew E. Pomerantz
Robert L. Kleinberg
Francois M. Auzerais
Original Assignee
Schlumberger Canada Limited
Services Petroliers Schlumberger
Schlumberger Holdings Limited
Schlumberger Technology B.V.
Prad Research And Development Limited
Schlumberger Technology Corporation
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Application filed by Schlumberger Canada Limited, Services Petroliers Schlumberger, Schlumberger Holdings Limited, Schlumberger Technology B.V., Prad Research And Development Limited, Schlumberger Technology Corporation filed Critical Schlumberger Canada Limited
Publication of WO2014022757A1 publication Critical patent/WO2014022757A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B49/00—Testing the nature of borehole walls; Formation testing; Methods or apparatus for obtaining samples of soil or well fluids, specially adapted to earth drilling or wells
    • E21B49/005—Testing the nature of borehole walls or the formation by using drilling mud or cutting data
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor

Definitions

  • the subject disclosure generally relates to formation evaluation. More particularly, the subject disclosure relates to formation evaluation in gas shale and oil-bearing shale reservoirs.
  • Raman spectroscopy on earth materials has been described in academic papers.
  • one reference describes the use of Raman on metamorphic rocks (metamorphic rocks have been exposed to higher pressure and temperature than the sedimentary rocks of interest to the petroleum industry).
  • the Raman data are used to estimate mineralogy, organic content (conceptually similar to kerogen content), and a "metamorphic temperature,” which is conceptually similar to maturity (maximum temperature experienced by the organic matter).
  • Another reference describes the use of Raman on gas shales, again deriving a metamorphic temperature. None of these publications mentions potential application to cuttings analysis. Nor do they mention how that information would be used to estimate reservoir quality or completion quality or to selectively stage hydraulic fractures.
  • Figure 1 is a plot of absorbance as a function of wavenumbers for artificially matured kerogen samples collected via FTIR spectroscopy.
  • Figure 2 is a plot of fluorescence and Raman intensity as a function of wavelength for four formation samples with varied maturity.
  • Embodiments herein relate to apparatus for and a method of analyzing a sample of a subterranean formation including preparing the sample, measuring the sample using vibrational spectroscopy, and calculating a mineralogy, kerogen content, and kerogen maturity using the spectroscopy results.
  • the vibrational spectroscopy is infrared and Raman spectroscopy.
  • Formation evaluation in gas shale and oil-bearing shale reservoirs involves estimation of quantities such as mineralogy, kerogen content (kerogen is solid, insoluble organic matter in sedimentary rocks), and thermal maturity (reflecting the extent of alteration of the kerogen due to thermal processes). These quantities are important for estimating the reservoir quality and completion quality of the formation, and measurement of these quantities as a function of depth is desirable in nearly every well in shale plays.
  • vibrational spectroscopy that includes infrared absorption and Raman scattering spectroscopies.
  • the infrared spectroscopy and Raman spectroscopy are performed simultaneously or within 30 minutes of each other.
  • the information may be used to estimate reservoir quality and/or completion quality. Some embodiments may then use the information to selectively stage hydraulic fractures.
  • Some embodiments benefit from vibrational spectroscopy including comparing the Raman and IR results. If IR results indicate a mature kerogen and low kerogen content while Raman shows a mature kerogen and high kerogen content, then this sample data likely suffers from low IR sensitivity at high maturity so the IR should be discarded and Raman retained. If Raman results indicate an immature kerogen and low kerogen content while IR shows immature and high content, then this probably suffers from low Raman sensitivity at low maturities so only the IR should be retained. If they both show moderate maturity and the same kerogen content, both sets of results indicate a likely valid result with low probability of error.
  • the region is probably not economical.
  • the sample may be appropriate for analysis by both infrared absorption and Raman scattering.
  • the kerogen content and maturity from infrared absorption and Raman scattering are expected to agree. Disagreement may indicate potential low data quality.
  • the mineralogy estimates from infrared absorption and Raman scattering are likely to agree.
  • mineralogy disagreement may indicate low data quality.
  • the infrared spectroscopy results and Raman spectroscopy are evaluated in real time, for accuracy, and the more accurate spectroscopy measurement is used to calculate kerogen content and maturity and the other spectroscopy measurement is used to calculate mineralogy retained while the less accurate measurement omitted.
  • calculating the mineralogy, kerogen content, and kerogen maturity includes Raman spectroscopy results and the calculating does not use infrared spectroscopy results when both infrared spectroscopy and Raman spectroscopy indicate high maturity and the kerogen content estimated from infrared spectroscopy is lower than the kerogen content estimated from Raman spectroscopy.
  • Calculating the mineralogy, kerogen content, and kerogen maturity includes infrared spectroscopy results and the calculating does not use Raman spectroscopy results when the infrared spectroscopy and Raman spectroscopy indicate low maturity and the kerogen content estimated from infrared spectroscopy is higher than the kerogen content estimated from Raman spectroscopy in some embodiments.
  • Some embodiments may use Raman spectroscopy results for the kerogen content and maturity are taken from Raman spectroscopy and use infrared spectroscopy results for the mineralogy. Conversely, some embodiments may use infrared spectroscopy results for the kerogen content and maturity and use Raman spectroscopy for the mineralogy.
  • this procedure can be completed using infrared absorption spectroscopy, such as Fourier Transform Infrared Spectroscopy (FTIR), Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), or attenuated total reflectance (ATR).
  • FTIR Fourier Transform Infrared Spectroscopy
  • DRIFTS Diffuse Reflectance Infrared Fourier Transform Spectroscopy
  • ATR attenuated total reflectance
  • the method comprises collecting a sample of a formation including a rock which may be core or cuttings. If the sample is cuttings from a well drilled with an oil- based mud, the cuttings are cleaned using similar techniques to the techniques disclosed in United States Patent Application Serial No. 13/446,985 filed April 13, 2012, entitled, "Method and apparatus to prepare drill cuttings for petrophysical analysis by infrared spectroscopy and gas sorption," which is herein incorporated by reference. Some cleaning embodiments expose the sample to a cleaning fluid. In some embodiments, the cleaning fluid comprises a surfactant. Some embodiments may benefit from crushing the sample to a diameter of about 10-100 micron. Some embodiments will not include exposing the sample to acid. Some embodiments may benefit when demineralizing does not occur.
  • Cuttings samples may include a solid collected from a drilling operation.
  • the measurements and characterization of a sample may occur within 1 mile of a wellbore from which the sample is collected. Some embodiments may occur in less than 24 hours.
  • the calculation of the sample properties may occur before recovering hydrocarbons begins, after producing hydrocarbons begins, during reservoir characterization during production, while drilling the formation or at multiple times during the life of a reservoir traversed by a wellbore.
  • Embodiments of the method also include measuring the infrared absorption spectrum of the rock using techniques disclosed in co-owned, United States Patent Application Serial No. 13/446975 filed April 13, 2012, entitled, "Method and apparatus for simultaneous estimation of quantitative mineralogy, kerogen content and maturity in gas shale and oil-bearing shale", the contents of which are herein incorporated by reference.
  • the kerogen content is estimated from the area under the 2,800 - 3,000 cm "1 peak and the kerogen maturity is estimated from the ratio of the area under CH 2 peaks (centered near 2849 and 2923 cm 1 ) to the area under the CH 3 peaks (centered near 2864 and 2956 cm “1 ).
  • using the peak height provides similar information as using the area under the peaks.
  • Figure 1 illustrates the FTIR spectra for artificially matured kerogen. This shows that as the kerogen maturity increases, FTIR may not provide an accurate estimate.
  • the kerogen content is estimated from the area under the 1 , 100-1 ,700 cm "1 peak.
  • the kerogen maturity is determined using the vitrinite reflectance. Some embodiments may select a Raman shift of about 100 - 1200 cm "1 for calculating mineralogy.
  • the fitting procedure includes two components: a Lorentzian (L) profile for the D-band and weak substructures, if any, and a Breit-Wigner-Fano (BWF) profile for the G- band.
  • spectral parameters include the peak position COD,G, the peak intensity I D ,G, the integrated intensity AD,G, an d the full width at half maximum FWHM-D,G.
  • the spectral parameters derived from the LBWF fit (FWHM-D, G, COD, COG, ID/IG and A D /[A D +AG]) are plotted versus VR.
  • the spectral parameters that correlate with VR include the following.
  • the kerogen maturity is estimated from the lineshape in the region 1,100 - 1,700cm "1 .
  • the region contains multiple peaks including the graphitic band (G) at 1,600 cm “1 , and defect bands D1-D5 occurring near 1350, 1600, 1500, 1175, and 1250cm "1 respectively.
  • the maturity of the kerogen can be estimated from the G/Dl ratio, the D1/(G+D1+D2) ratio, or the D5/G ratio.
  • Figure 2 illustrates that most mature kerogen has a relatively reliable lineshape for estimating kerogen properties.
  • the kerogen content is then estimated from both the estimated kerogen content from the infrared absorption spectrum and the estimated kerogen content from the Raman scattering spectrum. If both estimates of kerogen content are low (less than one percent), the sample is unlikely to represent an economically viable prospect.
  • the kerogen content estimate from infrared absorption is low (less than one weight percent) and the kerogen content estimate from Raman scattering is high (more than one weight percent), one may calculate a maturity estimate from infrared absorption. If the maturity estimate from infrared absorption is high (CH 2 :CH 3 ratio ⁇ 2), the sample is likely to mature for accurate analysis by infrared absorption. In this situation, the kerogen content and maturity is discarded from infrared absorption and the kerogen content and maturity from Raman scattering is retained.
  • the mineralogy, kerogen content, and maturity determined may be used to estimate reservoir quality and completion quality and therefore to selectively stage hydraulic fractures, as disclosed in United States Patent Application Serial No. 13/447109 filed April 13, 2012, and entitled, "Reservoir and completion quality assessment in unconventional (shale gas) wells without logs or core,” the contents of which are herein incorporated by reference.
  • the workflow for simultaneously and accurately estimating mineralogy, kerogen content, and maturity in a gas shale or oil-bearing shale from Raman spectroscopy is as follows:
  • [0029] Collect a sample of rock.
  • the sample can be either core or cuttings. If the sample is cuttings from a well drilled with oil-based muds, the cuttings need to be cleaned similar to United States Patent Application Serial Number 13/446,985.
  • [0030] Measure the Raman spectrum of the rock.
  • the specifics of the spectral acquisition are known in the references. Briefly, the sample is excited (for example by laser) and the Raman scattered radiation is dispersed (for example with a grating) and detected (for example with a charge coupled device).
  • the Raman shift range should be approximately 100 - 2,000 cm 1 . This measurement can be performed in the laboratory or at the well-site.
  • [0035] 7. Use the lineshape in the region 1,100 - 1,700 cm-1 to estimate the maturity.
  • the region contains multiple peaks including the graphitic band (G) at 1 ,600 cm-1 , and defect bands Dl - D5 occurring near 1350, 1600, 1500, 1175, and 1250 cm-1 respectively.
  • the intensity of these peaks can be used in the following equations: _ 4.4G
  • G + DI + D2 where L is the size of aromatic units, T is the highest temperature the kerogen has been exposed to, and G and D# are the intensities of the labeled peaks.
  • maturities metrics both L and T increase with maturity.
  • these quantities can be related to more familiar maturity metrics such as vitrinite reflectance and/or T max (from Rock-Eval). That is, alternatively or in parallel, some embodiments may also benefit from using the vitrinite reflectance methods described in more detail above.
  • step 5 Use the mineralogy (step 5), kerogen content (step 6), and maturity (step 7) determined here to estimate reservoir quality / completion quality and therefore to selectively stage hydraulic fractures, as described in United States Patent Application Serial Number 13/447109, filed April 13, 2012, which is incorporated by reference herein.
  • Some additional patent applications relate to this technology.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Environmental & Geological Engineering (AREA)
  • Fluid Mechanics (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

Cette invention concerne un procédé permettant d'analyser un échantillon d'une formation souterraine, ledit procédé consistant à préparer l'échantillon, à mesurer l'échantillon par spectroscopie de vibration, et à calculer la minéralogie, la teneur en kérogène et la maturité en kérogène en utilisant les résultats de spectroscopie. Dans certains modes de réalisation, la spectroscopie de vibration est la spectroscopie infrarouge et la spectroscopie de Raman.
PCT/US2013/053391 2012-08-02 2013-08-02 Procédé et appareil d'estimation simultanée de la minéralogie quantitative, de la teneur et de la maturité en kérogène dans les shales gazifères et les shales bitumineux par spectroscopie de vibration WO2014022757A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201261678957P 2012-08-02 2012-08-02
US61/678,957 2012-08-02
US201261711483P 2012-10-09 2012-10-09
US61/711,483 2012-10-09

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017197346A1 (fr) * 2016-05-13 2017-11-16 Gas Sensing Technology Corp. Minéralogie brute et pétrologie utilisant la spectroscopie raman
WO2018129002A1 (fr) * 2017-01-04 2018-07-12 Schlumberger Technology Corporation Procédé d'estimation d'une valeur d'une propriété de kérogène dans des formations souterraines
CN109916937A (zh) * 2019-03-28 2019-06-21 中国地质调查局油气资源调查中心 一种页岩有机质成熟度的分析方法
US10613250B2 (en) 2014-08-04 2020-04-07 Schlumberger Technology Corporation In situ stress properties
CN112014345A (zh) * 2020-08-31 2020-12-01 重庆科技学院 一种基于ftir分析的干酪根类型划分方法
CN113640275A (zh) * 2021-08-02 2021-11-12 中国科学院南海海洋研究所 一种基于表面增强拉曼光谱的有机质拉曼检测方法
US20230118696A1 (en) * 2020-04-24 2023-04-20 Schlumberger Technology Corporation Methods and systems for estimating properties of organic matter in geological rock formations

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US4839516A (en) * 1987-11-06 1989-06-13 Western Atlas International, Inc. Method for quantitative analysis of core samples
US5161409A (en) * 1989-10-28 1992-11-10 Schlumberger Technology Corporation Analysis of drilling solids samples
US5306909A (en) * 1991-04-04 1994-04-26 Schlumberger Technology Corporation Analysis of drilling fluids

Non-Patent Citations (1)

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Title
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10613250B2 (en) 2014-08-04 2020-04-07 Schlumberger Technology Corporation In situ stress properties
WO2017197346A1 (fr) * 2016-05-13 2017-11-16 Gas Sensing Technology Corp. Minéralogie brute et pétrologie utilisant la spectroscopie raman
US10534107B2 (en) 2016-05-13 2020-01-14 Gas Sensing Technology Corp. Gross mineralogy and petrology using Raman spectroscopy
WO2018129002A1 (fr) * 2017-01-04 2018-07-12 Schlumberger Technology Corporation Procédé d'estimation d'une valeur d'une propriété de kérogène dans des formations souterraines
US10215690B2 (en) 2017-01-04 2019-02-26 Schlumberger Technology Corporation Method for estimating a value of a kerogen property in subsurface formations
CN109916937A (zh) * 2019-03-28 2019-06-21 中国地质调查局油气资源调查中心 一种页岩有机质成熟度的分析方法
US20230118696A1 (en) * 2020-04-24 2023-04-20 Schlumberger Technology Corporation Methods and systems for estimating properties of organic matter in geological rock formations
CN112014345A (zh) * 2020-08-31 2020-12-01 重庆科技学院 一种基于ftir分析的干酪根类型划分方法
CN113640275A (zh) * 2021-08-02 2021-11-12 中国科学院南海海洋研究所 一种基于表面增强拉曼光谱的有机质拉曼检测方法

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