GEOPHYSICAL RESEARCH, 2020, vol. 21, no. 2, pp. 61-77. https://doi.org/10.21455/gr2020.2-5

UDC  550.367

Abstract  References   Full text (in Russian)

QUANTIFICATION OF CO2 HYDRATE IN LABORATORY SAMPLES USING A TWO-NEEDLE PROBE

I.I. Fadeeva(1,2), A.A. Duchkov(1,2), A.Y. Manakov(2,3), D.E. Aunov(1)

(1) Trofimuk Institute of Petroleum Geology and Geophysics SB RAS, Novosibirsk, Russia

(2) Novosibirsk State University, Novosibirsk, Russia

(3) Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk, Russia

Abstract. A new approach to the assessment of hydrate content in the sediments by the geothermal method is proposed. The transition of pore water to gas hydrate significantly reduces the heat capacity of the sediment. The amount of hydrate contained in the pores can determine by measuring the volumetric heat capacity of sediments in two different states: with and without hydrate in the pores (after its complete decomposition, only water remains in the pores). The volumetric heat capacity can calculate as the ratio of thermal conductivity to thermal diffusivity. The thermal conductivity and diffusivity of the sediment in different states can be determined using a two-needle probe according to the method proposed in this work.

The proposed approach in laboratory experiments was tested. The volumetric heat capacity of the sample in its various states is measured. The sample is the sand with synthetic carbon dioxide hydrate formed in a thermostatic high-pressure chamber (the volume of the obtained hydrate-containing sample is about 1000 cm(3)). We used not the standard method of pulsed heating, but the method based on the constant heating of the medium by a linear source. The accuracy of determining the heat capacity of the medium can increase by describing the entire useful interval of the experimental thermogram by using the proposed method. The paper presents an estimate of the content of CO2 hydrate in the art sample. This based on measurements of the thermal properties of the sample in two states: before and after the formation of CO2 hydrate in sample pores. Additionally, an estimate of the amount of CO2 hydrate produced in the sample is given. The estimate obtained from the record of the pressure and temperature of the sample state during hydrate formation. The results confirm the possibility of determining the hydrate content based on measurements of the heat capacity of the medium in two states. The minimum fraction of hydrate that can be fixed in the bottom sediment pores with the accuracy indicated in this work should be approximately 10%.

Keywords: quantitative assessment of hydrate content, laboratory experiment, carbon dioxide hydrate, thermal conductivity, thermal diffusivity, volumetric heat capacity.

References

Assael M.J., Antoniadis K.D., Wakeham W.A., Historical evolution of the transient hot-wire technique, Int. J. Thermophys., 2010, vol. 31, no. 6, pp. 1051-1072.

ASTM D 5334-00, Standard Test Method for Determination of Thermal Conductivity by Thermal Needle Probe Procedure, 2000, 6 p.

Bogorodsky V.V., Gavrilo V.P., Led. Fizicheskie svojstva. Sovremennye metody glyacio-logii. (Ice. Physical properties Modern glaciology methods), Leningrad: Gidrometeoizdat, 1980, 384 p. [in Russian].

Bristow K.L., Kluitenberg G.J., Horton R., Measurement of soil thermal properties with a dual-probe heat-pulse technique January, Soil Science Society of America Journal, 1994, vol. 58, no. 5, pp. 1288-1294.

Campbell G.S., Calissendorff C., Williams J.H., Probe for measuring soil specific heat using a heat-pulse method, Soil Science Society of America Journal, 1991, vol. 55, no. 1, pp. 291-293.

Carslaw H.S., Jaeger J.C., Conduction of heat in solids, Second edition, Oxford University Press, Oxford, UK, 1959, p. 310.

Circone S., Stern L.A., Kirby S.H., Durham W.B., Chakoumakos B.C., Rawn C.J., Rondinone A.J., Ishii Y., CO2 hydrate: synthesis, composition, structure, dissociation behavior, and a comparison to structure I CH4 hydrate, J. Phys. Chem. B, 2003, vol. 107, no. 23, pp. 5529-5539.

de Wilde P., Griffiths R., Goodhew S., Validation of data analysis routines for a thermal probe apparatus using numerical data sets, Build. Simul., Springer-Verlag, 2008, vol. 1, no. 1, pp. 36-45.

Duchkov, A.D., Manakov, A.Yu., Kazantsev, S.A., Permyakov, M.E., Ogienko, A.G., Thermal conductivity measurement of the synthetic samples of bottom sediments containing methane hydrates, Izv. Phys. Solid Earth, 2009, vol. 45, no. 8, pp. 661-669.

Fadeeva I.I., Ayunov D.E., Duchkov A.A., Investigation of the possibilities of developing an unsteady method for determining the thermophysical properties of a linear source, Interekspo GEO-Sibir', 2019, vol. 2, no. 3, pp. 174-180. [in Russian].

Fadeeva I.I., Duchkov A.A., Permyakov M.E., Thermophysical method for quantitative of hydrate content in samples imitating bottom sediments, Russian Geology and Geophysics, 2016, vol. 57, no. 6, pp. 984-992.

Filippov P.I., Prilozhenie teorii teploprovodnosti k teplofizicheskim izmereniyam (Application of the theory of thermal conductivity to thermophysical measurements), Novosibirsk: Nauka, 1973, 62 p. [in Russian].

Gavriliev R.I., Teplofizicheskie svojstva gornyh porod i napochvennyh pokrovov kriolitozony (Thermophysical properties of rocks and ground cover of permafrost zone), Novosibirsk: Publishing House of the SB RAS, 1998, 280 p. [in Russian].

Golubev V.A., Evidence of the presence of gas hydrates in the upper layer of bottom sediments of Lake Baikal: in situ thermal conductivity measurements, Doklady Earth Sciences, 1998, vol. 358, no. 3, pp. 384-388. [in Russian].

Istomin V.A., Yakushev V.S., Gazovye gidraty v prirodnyh usloviyah (Gas hydrates in nature), Мoscow: Nedra, 1992, 231 p. [in Russian].

Kalinin A.N., Sokolova L.S., Duchkov A.D., Cherepanov V.Ya., Studies of a thermal comparator as applied to measurements of thermal conductivity of rocks, Geologiya i geofizika (Geology and geophysics), 1983, no. 3, pp. 116-122. [in Russian].

Kazantsev S.A., Fadeeva I.I., A device for the operational measurement of thermal diffusivity of weakly cemented rocks, Interekspo GEO-Sibir', 2015, vol. 2, no. 2, pp. 82-85. [in Russian].

Kluitenberg G.J., Ham J.M., Bristow K.L., Error analysis of the heat pulse method for measuring soil volumetric heat capacity, Soil Science Society of America Journal, 1993, vol. 57, no. 6, pp. 1444-1451.

Kutas R.I., Kravchuk O.P., Bevzyuk M.I., Diagnostics of gas hydration of the bottom layer of sediments of the Black Sea based on the results of measuring their thermal conductivity in situ, Geofizicheskij zhurnal (Geophysical Journal), 2005, vol. 27, no. 2, pp. 238-244. [in Russian].

Lee T.C., Duchkov A.D., Morozov S.G., Determination of thermal conductivity and formation temperature from cooling history of friction-heated probes, Geophysical Journal International, 2003, vol. 152, no. 2. pp. 433-442.

Lysov V.G., Rykov Yu.G., On the calculation of phase equilibrium in multicomponent filtration problems, Preprinty IPM im. M.V. Keldysha (Preprints of the IPM of M.V. Keldysh), 2014, no. 94, 20 p. [in Russian].

Nikitin D.S., Khutorskoy M.D., Nikitin A.S., Non-contact measurements of the thermophysical properties of rocks at the TS14 installation, Processy v geosredah (Processes in geomedia), 2016, no. 7, pp. 246-254. [in Russian].

Ochsner T.E., Horton R., Ren T., Simultaneous water content, air-filled Porosity, and bulk density measurements with thermo-time domain reflectometry, Soil Science Society of America Journal, 2001, vol. 65, no. 6, pp. 1618-1622.

Permyakov M.E., Effective thermal conductivity of hydrate-containing samples according to the results of laboratory measurements under various PT conditions, Novosibirsk: 2010, 16 p. [in Russian].

Popov Yu.A., Semenov V.G., Korostelev V.M., Berezin V.V., Determination of thermal conductivity of rocks using a movable heat source, Fizika Zemli (Physics of the Earth), 1983, no. 7, pp. 86-93. [in Russian].

Popov Yu., Tertychnyi V., Romushkevich R., Korobkov D., Pohi J., Interrelations between thermal conductivity and other physical properties of rocks: experimental data, Pure and Applied Geophysics, 2003, vol. 160, pp. 1137-1161.

Riedel M., Willoughby E.C., Chopra S., Geophysical characterization of gas hydrates, Tulsa: SEG geophysical developments series, 2010, no. 14, 412 p.

Shashkov A.G., Volokhov G.M., Abramenko T.N., Kozlov V.P., Metody opredeleniya teplopro-vodnosti i temperaturoprovodnosti (Methods for determining thermal conductivity and thermal diffusivity), Moscow: Energy, 1973, 336 p. [in Russian].

Sloan E.D., Koh C.A., Clathrate hydrates of natural gases, Boca Raton, London, New-York, CRC Press, 2008. 752 p.

Suetnova E.I., Accumulation of gas hydrates in pores during compaction of an accumulated rheologically layered inhomogeneous sedimentation medium, Geofizicheskie issledovaniya (Geophysical Research), 2013, vol. 14, pp. 71-78. [in Russian].

Von Herzen R., Maxwell A.E., The measurement of thermal conductivity of deep sea sediments by a needle probe method, Journal of Geophysical Research, 1959, vol. 64, no. 10, pp. 1557-1563.