WO2015050832A1 - Methods for estimating resource density using raman spectroscopy of inclusions in shale resource plays - Google Patents
Methods for estimating resource density using raman spectroscopy of inclusions in shale resource plays Download PDFInfo
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- WO2015050832A1 WO2015050832A1 PCT/US2014/058163 US2014058163W WO2015050832A1 WO 2015050832 A1 WO2015050832 A1 WO 2015050832A1 US 2014058163 W US2014058163 W US 2014058163W WO 2015050832 A1 WO2015050832 A1 WO 2015050832A1
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- light hydrocarbon
- inclusion
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- source rock
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- 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
- E21B47/00—Survey of boreholes or wells
- E21B47/06—Measuring temperature or pressure
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/24—Earth materials
- G01N33/241—Earth materials for hydrocarbon content
Definitions
- the present disclosure relates generally to methods for estimating the in situ density of light hydrocarbons. More specifically, in certain embodiments, the present disclosure relates to methods for estimating in situ density of light hydrocarbons in shale source rock vein and matrix minerals using Raman spectroscopy and associated methods.
- One of the objectives of an exploration and appraisal campaign in unconventional shale gas and liquid rich shale plays is to "sweet spot" the acreage in terms of potential estimated ultimate recovery (EUR).
- Sweet spotting is a term used to refer to the identification of the top quartile wells in a given production zone. This is often difficult to do in the absence of reliable production data.
- Estimating EUR in shale gas formations is especially challenging since EUR is a dynamic production metric while all other rock properties being measured are static in-situ properties. The relationship between these different states is not intuitive and presently poorly understood.
- an estimate of the mass of light hydrocarbon per volume of source rock i.e. the in situ density of light hydrocarbon
- the present disclosure relates generally to methods for estimating the in situ density of light hydrocarbons. More specifically, in certain embodiments the present disclosure relates to methods for estimating in situ density of light hydrocarbons in shale source rock vein and matrix minerals using Raman spectroscopy and associated methods.
- the present disclosure provides a method of determining the in situ pressure of a light hydrocarbon in a shale source rock formation comprising: providing an inclusion comprising the light hydrocarbon trapped within the inclusion; using Raman spectroscopy to determine the density and composition of the light hydrocarbon trapped within the inclusion; and calculating a pressure of the light hydrocarbon in the shale source rock formation based upon the density and composition of the light hydrocarbon trapped within the inclusion.
- the present disclosure provides a method of evaluating a shale source rock formation comprising: providing inclusions from the shale source rock formation, wherein each inclusion comprises a light hydrocarbon trapped within the inclusion; determining in situ pressures and densities of the light hydrocarbon within the shale source rock formation utilizing Raman analyses of the light hydrocarbon trapped within inclusions; and producing a map of the spatial and vertical variations of the in situ pressures and densities of the light hydrocarbon in the shale source rock formation.
- the present disclosure provides a method of evaluating a shale source rock formation comprising: providing inclusions from the shale source rock formation, wherein each inclusion comprises a light hydrocarbon trapped within the inclusion; determining in situ pressures and densities of the light hydrocarbon utilizing Raman analyses of the light hydrocarbon trapped within inclusions; producing a map of spatial and vertical variations of proxies for pressure normalized-estimated ultimate recovery; and identifying the areas on the map that correspond to a top quartile for pressure normalized-estimated ultimate recovery.
- Figure 1 is an illustration of the convolution of various aerial distributions of reservoir data to create an aerial distribution of hydrocarbon volume and proxy PN- EUR.
- Figures 2A-2C are charts depicting the relationship between pressure and concentration of light hydrocarbons and Raman peak shift data.
- the present disclosure relates generally to methods for estimating the in situ density of light hydrocarbons. More specifically, in certain embodiments the present disclosure relates to methods for estimating in situ density of light hydrocarbons in shale source rock vein and matrix minerals using Raman spectroscopy and associated methods.
- Some desirable attributes of the methods discussed herein are that they are more accurately able to predict areas and volumes of organic rich source rocks with favorable estimated ultimate recovery attributes.
- Sweet spotting may be achieved by mapping in two dimensions estimated ultimate recovery data and making a map that then can highlight the most favorable part of a basin/play/prospect for early development based on the spatial distribution of resource density i.e. the density of hydrocarbon per volume of rock.
- this disclosure outlines methods for evaluating the densities of light hydrocarbons generated by organic rich source rock shale. These methods may be based on the association of light hydrocarbon density trapped as inclusions in shale matrix and vein material within an organic rich shale source rock. The density of the light hydrocarbon may be quantified using a Raman spectroscopic method. A strong correlation between the densities of the light hydrocarbon generated by a shale source rock and estimated ultimate recovery, specifically the pressure normalized- estimated ultimate recovery, has been observed.
- the in situ densities and pressures of the light hydrocarbon at various points in the formation may be inferred from an Equation of State model and the measured density, pressure, and temperature of the light hydrocarbons trapped as inclusions.
- the in situ densities and pressures may be recognized proxies for pressure normalized-estimated ultimate recovery data that is normally obtained from production data.
- the present disclosure provides a method for estimating the pressure of a light hydrocarbon in a shale source rock formation comprising: providing an inclusion comprising the light hydrocarbon trapped within the inclusion; using Raman spectroscopy to determine the density and composition of the light hydrocarbon trapped within the inclusion; and calculating a pressure of the light hydrocarbon in the shale source rock formation based upon the density and composition of the light hydrocarbon trapped within the inclusion.
- the light hydrocarbon may be any hydrocarbon which is a gas at standard pressure and temperature conditions. Suitable examples of light hydrocarbons include methane, ethane, propane, butane, pentane, or any combination thereof.
- the shale source rock formation may be a recognized source rock based on its total organic carbon (TOC) content.
- the shale source rock formation may be an organic-rich shale source rock formation comprising a natural gas liquid resource in which a light hydrocarbon may not be the dominant hydrocarbon species.
- the total pressure of the light hydrocarbons at a particular location in the shale source rock formation may be a summation of all of the partial pressures of gas components present and individual species partial pressures at that particular location and thus may still serve as a valid proxy for the pressure normalized-estimated ultimate recovery of any of the component hydrocarbon species present in the formation of interest.
- the inclusion may be an inclusion found in a rotary core or a side wall core from the well bore of the shale source rock formation.
- the inclusion may be disposed in a mineral phase that is amenable to analysis using Raman spectroscopic methods.
- suitable mineral phases include crystals of quartz, calcite, anhydrite, barite, gypsum, albite, and other members of the feldspar group of minerals.
- the inclusion may be single phase containing only light hydrocarbons.
- the inclusion may be multiphase containing liquid water, carbon dioxide, and light hydrocarbon and potentially other species stable within the C-O-H-S-N system generated as products of the maturation of the given organic rich shale source rock.
- the inclusion may also contain different proportions of gas to liquid and also daughter minerals that are stable in the chemical microcosm of the fluid inclusion formed during the burial and uplift history of a given shale source rock formation.
- the inclusions may first be prepared before Raman spectroscopy is performed.
- the inclusions may be prepared by using conventional techniques used in the preparation of fluid inclusion wafers. For example, in certain embodiments, 100 micron thick wafers may be prepared to have a surface polish quality such that the Raman incident laser beam can interact with the trapped hydrocarbon components of the inclusion, return a signal that is then measured as a characteristic peak shift specific to certain types of characteristic vibrational modes of molecular bonds, suitable for quantification relative to a reference peak shift for a specific C bond in a hydrocarbon molecule.
- Raman spectroscopy may be performed by focusing a laser beam into the inclusion in order to excite a reflected photon beam that is captured as a series of spectral lines corresponding to characteristic peak shifts of vibrational modes of different C bonds that may are diagnostic of the hydrocarbons trapped in the inclusions.
- the Raman spectra may be collected at ambient laboratory conditions during which careful records of temperature and peak shifts may be recorded.
- the Raman spectroscopy may be micro Laser Raman Spectroscopy.
- a laser light source with different wavelengths may be used, depending on the composition of the light hydrocarbons trapped in the inclusion.
- a low energy laser beam may be used to excite different modes of bond vibrations in molecular moieties of the light hydrocarbons trapped in the inclusion.
- the characteristic peak shift of the light hydrocarbon molecule of interest in the inclusion may be obtained.
- This peak shift data may then be compared to prior calibration peak shift data to determine the density of the trapped light hydrocarbons of a particular composition.
- the pressure of the light hydrocarbon in the shale source rock formation may be calculated based upon the density and composition of the light hydrocarbon trapped in the inclusion.
- an Equation of State model may be used to calculate the pressure of the light hydrocarbon at the location from where the inclusion was sampled.
- commercially available PVT simulation software packages may be used to calculate the pressure of the light hydrocarbon based upon the density and composition of the light hydrocarbon trapped in the inclusion.
- a single Equation of State model for that light hydrocarbon may be used to calculate the pressure in the formation at the location where the inclusion was sampled.
- a single Equation of State model for mixtures may be used to calculate the partial pressure of each light hydrocarbon or gas and the overall pressure of the mixture.
- a single Equation of State model may be used for mixtures of gases, requiring only the use of thermodynamically established mixing laws for the different components comprising the gas phase.
- Temperature may be determined from fluid inclusion thermometry and inferences drawn from the homogenization temperatures at which two phase liquid and gas inclusions are observed to homogenize into a single phase on heating under a calibrated micro heating stage.
- Density may be defined as the mass of gas component divided by its volume.
- the inclusion volume may be assumed to remain constant between ambient laboratory conditions at which the Raman data are collected and the temperature at which the original fluid inclusion was trapped.
- the pressure at which the light hydrocarbon was trapped may be solved iteratively.
- the iterative procedure may involve determining the pressure that satisfies density at the fluid inclusion trapping temperature, based on certain assumptions about the average bulk composition of the gaseous phase present at the time of trapping.
- the assumptions about the average bulk composition of the gaseous phase present at the time of trapping may include the particular mole fractions of gas phases present and whether or not the gas phase is water saturated.
- the pressure and density of a light hydrocarbon in a formation at the location where the inclusion was formed may be estimated.
- the present disclosure provides a method of evaluating a shale source rock formation comprising: providing inclusions from the shale source rock formation, wherein each inclusion comprises a light hydrocarbon trapped within the inclusion; determining in situ densities and pressures of the light hydrocarbon within the shale source rock formation utilizing Raman analyses of the light hydrocarbon trapped within inclusions; and producing a map of the spatial and vertical variations of the in situ pressures of the light hydrocarbon in the shale source rock formation.
- inclusions may be obtained from multiple locations within the shale source rock formation and from several different well locations.
- Raman analyses on each of these inclusions may be performed, and estimates for pressures and densities of light hydrocarbons at multiple locations in the shale source rock formation may be made.
- the pressures and densities of the light hydrocarbons at locations not measured may be estimated using conventional interpolation and/or extrapolation techniques. Using these estimates, a map depicting the spatial and vertical variations of the pressures of the light hydrocarbons may be produced.
- a map depicting the spatial and vertical variations of the pressures of the light hydrocarbons may be produced by performing diagnostic formation integrity tests plotting the results of those tests.
- the present disclosure provides a method of evaluating a shale source rock formation comprising: providing inclusions from the shale source rock formation, wherein each inclusion comprises a light hydrocarbon trapped within the inclusion; determining in situ pressures and densities of the light hydrocarbon utilizing a Raman analysis of the light hydrocarbon trapped within inclusions; producing a map of spatial and vertical variations of proxies for pressure normalized-estimated ultimate recovery; and identifying the areas on the map that correspond to a top quartile for pressure normalized-estimated ultimate recovery.
- the map predicting the spatial and vertical variation of pressure normalized-estimated ultimate recovery may be produced relying solely on the data obtained from any of the methods discussed above.
- the in situ pressures of the light hydrocarbons may then be mapped and the areas with top quartile potential may be identified.
- the best producing intervals of the formation correlate with the pressure normalized-estimated ultimate recovery.
- in situ density and/or pressure may be used as a proxy for pressure normalized-estimated ultimate recovery.
- producing the map of the spatial and vertical variation of proxies for pressure normalized-estimated ultimate recovery may comprise using the calculated partial pressures of various light hydrocarbon components as proxies for pressure normalized-estimated ultimate recovery at each of those locations and preparing a map based upon these proxies.
- these proxies may also be calculated based upon formation properties such as Total Organic Carbon, porosity, gas composition, and pressure, temperature, and volume properties of the light hydrocarbons.
- the formation properties may be determined in a variety of ways. In certain embodiments, a variety of these formation properties, for example, gas composition, pressure, temperature, and/or volume, may be determined using any of the methods described above.
- other formation properties at multiple locations may be calculated using seismic data such as acoustic and elastic impendence of the subsurface formation using an inversion algorithm.
- An example of a seismic inversion algorithm may include the following steps: (1) seed an initial subsurface model with an initial estimate of the subsurface acoustic and elastic impedances, (2) generate a synthetic systemic response based on the initial estimate using a forward modeling algorithm that simulates the dependence of seismic properties on variation in acoustic and elastic impedances, and (3) compare the synthetic data with the actual seismic data. When comparing the synthetic data with the actual seismic data, if the error is acceptably small the initial estimate may be accepted as the final result. This model may then be used to produce the pressure normalized-estimated ultimate recovery maps. On the other hand, if the error is unacceptably large, the subsurface model may be perturbed in a manner that can improve agreement with the measured data and then steps (2) and (3) may be repeated until the error is acceptably small and convergence is obtained.
- the inverted seismic properties may be used to calculate formation properties.
- Several additional calibration steps may be involved to determine formation properties for unconventional reservoirs compared to conventional formations.
- the acoustic properties of the organic matter and kerogen may have to be established by using methods such as nanoindentation of the organic matter in order to estimate mechanical and elastic properties. With these properties established, the inverted acoustic properties may then be used to estimate to volume of organic matter and bulk density of the formation. A map of the thickness of the reservoir interval in the area of interest may then be generated using these results.
- the density of the organic matter and/or kerogen may need to be known.
- the maturity of the kerogen may be determined by using Raman measurement of solid organic matter and then estimating a ratio of the D5/G peak ratio, where D5 and G refer to characteristic Raman peaks of organic components in the solid organic matter, specifically the aliphatic C-C stretch vibrational mode (D5) and the bulk aromatic or grapheme like component (G).
- D5 and G refer to characteristic Raman peaks of organic components in the solid organic matter, specifically the aliphatic C-C stretch vibrational mode (D5) and the bulk aromatic or grapheme like component (G).
- the grain density of the organic matter may then be estimated based on the maturity of the kerogen and a proprietary correlation between maturity and the grain density of solid organic matter.
- the porosity of the formation may then be estimated.
- a map of the average porosity of the reservoir interval in the area of interest may then be generated using these results.
- the maps of the thickness of the reservoir interval and the average porosity of the reservoir interval may then be convolved to generate a map of the distribution of the potential pore space volume of the reservoir interval in the area of interest.
- the map depicting the spatial and vertical variations of the partial pressures of the light hydrocarbons may then be convolved with the map of the distribution of the potential pore space volume to produce a pressure normalized-estimated ultimate recovery map.
- a map that predicts the spatial and vertical variations of estimated ultimate recovery may be produced and the areas on that map may then be identified as having the potential to be top quartile candidates for development.
- Figure 1 provides an illustration of the convolution of these maps. As can be seen in Figure 1, the lighter colored areas of each map correspond to higher values of thickness, porosity, pore space, partial pressure, hydrocarbon density, and estimated ultimate recovery.
- Fluid inclusion sections were prepared from pieces of vein and core material containing calcite, quartz, barite, and anhydrite. Fluid inclusion wafers were prepared using standard industry methods, resulting in polished thin sections suitable for petrographic examination and characterization of fluid inclusion types.
- Figure 2A shows the sensitivity of the characteristic Raman peak shift of CH 4 as a function of temperature, at a constant pressure of 30.58 MPa.
- Figure 2B shows the relationship between methane pressure and D (cm 1 ) at room temperature, where D is the Delta between the measured peak shift of methane trapped in the inclusion and an "intercept" value, based on a calibration of the methane peak shift at zero pressure for the Raman instrument configuration used to measure the Raman peak shifts in inclusions.
- Figure 2C shows the model relationships between Raman peak shift, D (cm 1 ) and density of the vapor phase, as a function of temperature.
- in situ methane density may be calculated using an Equation of State. Table 1 below illustrates the result of such calculations.
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Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201480054444.1A CN105659084A (en) | 2013-10-01 | 2014-09-30 | Methods for estimating resource density using raman spectroscopy of inclusions in shale resource plays |
| RU2016117165A RU2016117165A (en) | 2013-10-01 | 2014-09-30 | METHODS FOR ASSESSING DENSITY OF RESOURCES USING RAMANOVSKAYA SPECTROSCOPY OF INCLUSIONS AT SHALE DEPOSITS |
| DE112014004526.8T DE112014004526T5 (en) | 2013-10-01 | 2014-09-30 | Method for estimating resource density using Raman spectroscopy of inclusions in shale resource areas |
| AU2014329845A AU2014329845B2 (en) | 2013-10-01 | 2014-09-30 | Methods for estimating resource density using raman spectroscopy of inclusions in shale resource plays |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201361885070P | 2013-10-01 | 2013-10-01 | |
| US61/885,070 | 2013-10-01 |
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| WO2015050832A1 true WO2015050832A1 (en) | 2015-04-09 |
| WO2015050832A9 WO2015050832A9 (en) | 2015-07-09 |
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| PCT/US2014/058163 Ceased WO2015050832A1 (en) | 2013-10-01 | 2014-09-30 | Methods for estimating resource density using raman spectroscopy of inclusions in shale resource plays |
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| US (1) | US9909409B2 (en) |
| CN (1) | CN105659084A (en) |
| AR (1) | AR097834A1 (en) |
| AU (1) | AU2014329845B2 (en) |
| DE (1) | DE112014004526T5 (en) |
| RU (1) | RU2016117165A (en) |
| WO (1) | WO2015050832A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3555422A4 (en) * | 2016-12-14 | 2020-09-02 | Michael Smith | METHODS AND DEVICES FOR EVALUATING THE CONTENTS OF MATERIALS |
| US11927571B2 (en) | 2016-12-14 | 2024-03-12 | Michael P. Smith | Methods and devices for evaluating the contents of materials |
| US12055534B2 (en) | 2019-01-13 | 2024-08-06 | Michael P. Smith | Analysis of release-resistant water in materials and related devices and methods |
| US12105076B2 (en) | 2018-09-05 | 2024-10-01 | Michael P. Smith | Carbonate grain coarseness analysis and related methods |
| US12188920B2 (en) | 2019-10-13 | 2025-01-07 | Michael P. Smith | Determining properties of materials through conditionally releasable material-associated liquids |
| US12540529B2 (en) | 2020-03-20 | 2026-02-03 | Michael Smith | Subsurface carbon dioxide analysis methods |
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| CN105403585B (en) * | 2015-10-28 | 2018-03-13 | 中国石油天然气股份有限公司 | Method for Determining Lower Limit of Abundance of Dispersed Liquid Hydrocarbons in Source Rocks |
| WO2018156527A1 (en) * | 2017-02-27 | 2018-08-30 | Schlumberger Technology Corporation | Wellsite kerogen maturity determination utilizing raman spectroscopy |
| US10801963B2 (en) | 2018-08-22 | 2020-10-13 | Paul Bartholomew | Raman spectroscopy for minerals identification |
| US11530611B2 (en) * | 2018-05-14 | 2022-12-20 | Schlumberger Technology Corporation | Method for performing Raman spectroscopy within a logging while drilling instrument |
| US10663345B2 (en) | 2018-08-22 | 2020-05-26 | Paul Bartholomew | Raman spectroscopy for minerals identification |
| CN111007233B (en) * | 2019-12-25 | 2022-03-11 | 西南石油大学 | A method for analyzing methane-carbon dioxide movement behavior in microscopic pores of shale |
| CN111175278B (en) * | 2020-01-19 | 2023-05-23 | 北京缔科新技术研究院(有限合伙) | Single photon humidity measuring function sighting telescope |
| US12253508B2 (en) * | 2020-04-24 | 2025-03-18 | Schlumberger Technology Corporation | Methods and systems for estimating properties of organic matter in geological rock formations |
| CN116124755A (en) * | 2022-07-28 | 2023-05-16 | 四川省科源工程技术测试中心有限责任公司 | Sea mud shale maturity testing method based on Raman spectrum |
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- 2014-09-29 AR ARP140103601A patent/AR097834A1/en unknown
- 2014-09-30 US US14/501,363 patent/US9909409B2/en active Active
- 2014-09-30 DE DE112014004526.8T patent/DE112014004526T5/en not_active Withdrawn
- 2014-09-30 AU AU2014329845A patent/AU2014329845B2/en active Active
- 2014-09-30 WO PCT/US2014/058163 patent/WO2015050832A1/en not_active Ceased
- 2014-09-30 CN CN201480054444.1A patent/CN105659084A/en active Pending
- 2014-09-30 RU RU2016117165A patent/RU2016117165A/en not_active Application Discontinuation
Non-Patent Citations (5)
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3555422A4 (en) * | 2016-12-14 | 2020-09-02 | Michael Smith | METHODS AND DEVICES FOR EVALUATING THE CONTENTS OF MATERIALS |
| US11280186B2 (en) | 2016-12-14 | 2022-03-22 | Michael Smith | Methods and devices for evaluating the contents of materials |
| US11927571B2 (en) | 2016-12-14 | 2024-03-12 | Michael P. Smith | Methods and devices for evaluating the contents of materials |
| US12247954B2 (en) | 2016-12-14 | 2025-03-11 | Michael P. Smith | Methods and devices for evaluating the contents of materials |
| US12105076B2 (en) | 2018-09-05 | 2024-10-01 | Michael P. Smith | Carbonate grain coarseness analysis and related methods |
| US12055534B2 (en) | 2019-01-13 | 2024-08-06 | Michael P. Smith | Analysis of release-resistant water in materials and related devices and methods |
| US12449412B2 (en) | 2019-01-13 | 2025-10-21 | Michael Smith | Analysis of release-resistant water in materials and related devices and methods |
| US12188920B2 (en) | 2019-10-13 | 2025-01-07 | Michael P. Smith | Determining properties of materials through conditionally releasable material-associated liquids |
| US12540529B2 (en) | 2020-03-20 | 2026-02-03 | Michael Smith | Subsurface carbon dioxide analysis methods |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2014329845A1 (en) | 2016-03-24 |
| US20150090443A1 (en) | 2015-04-02 |
| US9909409B2 (en) | 2018-03-06 |
| CN105659084A (en) | 2016-06-08 |
| AR097834A1 (en) | 2016-04-20 |
| AU2014329845B2 (en) | 2017-02-23 |
| DE112014004526T5 (en) | 2016-06-23 |
| RU2016117165A (en) | 2017-11-10 |
| WO2015050832A9 (en) | 2015-07-09 |
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