Proton $T_1$ and $T_2$ Relaxivities for $CH_2$ and $CH_3$ Peaks in Crude Oil Measured by 400 MHz NMR

Year 2021, , 69 - 78, 31.08.2021

İsmail Arsel , Düzgün Kal , Ali Yılmaz

https://doi.org/10.30931/jetas.950416

Abstract

Petroleum fluid has been extensively studied at low magnetic fields by Nuclear Magnetic Resonance (NMR) Spectroscopy, but high field NMR studies are rarely found in this area. The aim of this study is to determine the proton spin-lattice relaxation rate (1/T1), T1 relaxivity (R1), proton spin-spin relaxation rate (1/T2) and T2 relaxivity (R2) of paraffinic CH2 and gamma CH3 peaks. For this purpose, crude oil samples were taken from 3 separate wells in the Batman region. Using these samples, 3 different sets were prepared from a mixture of deuterated chloroform (CDCl3) and crude oil. The total volume of each prepared mixture was 1 mL. The crude oil content in each set was changed from 0.05 mL to 0.20 mL in 0.05 mL steps.. Special care has been taken to ensure the best shimming of the NMR spectrometer operating at 400 MHz. T1 measurements were performed using an inversion recovery (IR) pulse sequence. 1/T2 values were determined from the half-height line widths of CH2 and CH3 peaks. 1/T1 and 1/T2 rates and all relaxivities were found to vary from well to well. This change is due to the fluid composition of the wells. The 1/T2 rates and R2 relaxivities were found to be considerably greater than the 1/T1 rates and R1 relaxivities. R2 relaxivities for CH3 were also 2-5 times greater than for CH2.The higher 1/T2 and R2 relaxivities compared with 1/T1 and R1 were attributed to the additional CDCl3-mediated relaxation mechanisms. In conclusion, available data show that high 1/T2 rates and R2 relaxivities measured in the high field NMR laboratory can be applied to separate crude oil from other fluids in the oil field.

Keywords

CH2 and CH3, crude oil, 400 MHz NMR, 1/T1 and 1/T2 rates, R1 and R2 relaxivities

References

• [1] Borgia, G. C., Brown, R. J. S., Fantazzini, P., “Nuclear magnetic resonance relaxivity and surface‐to‐volume ratio in porous media with a wide distribution of pore sizes”, J. Appl. Phys. 79 (1996) : 3656-3664.
• [2] Deflandre, F., and Godefroy, S., “Validity of permeability prediction from NMR measurements”, Comptes Rendus de l'Académie des Sciences - Series IIC - Chemistry 4 (2001) : 869-872.
• [3] Hirasaki, G. J., Lo, S-W., and Zhang, Y., “NMR properties of petroleum reservoir fluids”, Magn. Reson. Imaging 2 (2003) : 269-277.
• [4] Ahmad, A. A., Saidian, M. M., Prasad, M., Carolyn, A., “Measurement of the water droplet size in water-in-oil emulsions using low field nuclear magnetic resonance”, Can. J. Chem. 93 (2015) : 1-7.
• [5] Korb, J. P., Nicot, B., Bryant, S., “Relation and correlation between NMR relaxation times, diffusion coefficient, and viscosity of heavy crude oils”, J. Phys. Chem. 119(43) (2015) : 24439-24446.
• [6] Majod, A. A., Saidian ,M., Prased, M., Koh C. A., “Measurement of the water droplet size in water-in-oil emulsions using low field nuclear magnetic resonance”, Can. J. Chem. 93 (2015) : 1-7.
• [7] Abouelresh, M. O., An integrated characterization of the porosity in qusaiba shale, Saudi Arabia, J. Petrol. Sci. Eng.149 (2017): 75-87
• [8] Alvares, J. O., and Schechter, D.S., “Application of wettability alteration in the exploitation of unconventional liquid resources”, Petrol. Explor. Develop. 43(5) (2016) : 832-840.
• [9] Corbeanu, R., Nasoetion, S., Yang, K., Labiadh, M., Narayanan, R., Mubarak, M., Habib, K., “Reservoir fracture characterization and modeling in a shuaiba reservoir”, International Petroleum Technology Conference, January 19-22, Doha, Qatar (2014).
• [10] Freedman, R., Lo, S., Flaum, M., Hirasaki, G. J., Matteson, A., Sezginer A., “A new NMR method of fluid characterization in reservoir rocks: Experimental confirmation and simulation results”, SPE J 6 (4) (2001) : 452-464.
• [11] Korb, J-P., Godefroy, S., Fleury, M., “Surface nuclear relaxation and dynamics of water and oil in granular packings and rocks”, Magn. Reson. Imaging 21 (3-4) (2003) : 193-9.
• [12] Tan, M., Zou, Y., Zhou, C., “A new inversion method for (T2, D) 2D NMR logging and fluid typing”, Comput. and Geosci. 51 (2013) : 366-380.
• [13] Walsh. D., Turner, P., Grunewald, E., Zhang, H., Butler, J.J., Reboulet, E., Knobbe, S., Christy, T., Lane, J. W. Jr., Johnson, C. D., Munday, T., Fitzpatrick, A., “A small-diameter NMR logging tool for ground water investigations”, Ground Water 51(6) (2013) : 914-926.
• [14] Zheng, Y., Wan, D., Ayaz, M., Ma, C., “Utilizing NMR mud logging technology to measure reservoir fundamental parameters in well site”, EPE 5 (2013) : 1508-1511.
• [15] Kadkhodaie-Ilkhchi A, Golsanami, N., Yousef Sharghi Y, Zeinali M., “Estimating, NMR T2 distribution data from well log data with the use of a committee machine approach: A case study from the Asmari formation in the Zagros basin”, Iran, J. Petrol. Sci. Eng. (2014) : 38-51.
• [16] Rakhmatullin, I., Efimov, S., Varfolomeev, M., Klochkov, V., “High-resolution NMR study of light and heavy crude oils : Structure property” Analysis, IOP Conf. Series: Earth. Environ. Sci. 155 (2018) : 012014
• [17] Edwards, J. C., “Applications of NMR spectroscopy in petroleum chemistry”, Chapter 16 in ‘spectroscopic analysis of petroleum products and lubricants’. Edited by R A Kishore Nadkarni, Publisher: ASTM International-Institute of Physics (2010).
• [18] Krishnan, V. V., Murali N., “Radiation damping in modern NMR experiments: Progress and challenges” Prog. Nucl. Magn. Reson. Spectrosc. 68 (2013) : 41-57.
• [19] Yilmaz, U. N., Yilmaz, B. D., “Shortening of NMR 1/T1 and 1/T2 relaxation rate distribution intervals in D2O containing jaw cysts or abscesses: Separation of cysts fromabscesses”, J . Appl. Spectrosc. 87(5) (2020) : 946-950.
• [20] Koenig, S.H., Baglin, C. M., Brown III, R. D., “Magnetic field dependence of solvent proton relaxation in aqueous solutions of Fe3+ complexes”, Magn. Reson. Med. 2(3) (1985) : 283-288.
• [21] Yilmaz, A., Ulak, F. S., Batun, M. S., “Proton T1 and T2 relaxivities of serum proteins. Magn”. Reson. Imaging. 22(5) (2004) : 683-689.
• [22] Uh, J., Watson, A. T., “Nuclear magnetic resonance determination of surface relaxivity in permeable media”, Ind. Eng. Chem. Res. 43(12) (2004) : 3023032.
• [23] Sulucarnain, I., Sondergeld, C. H., Rai C. S., “An NMR study of shale wettability and effective surface relaxivity” Paper presented at the SPE Canadian Unconventional Resources Conference, Calgary, Alberta, Canada, October (2012).
• [24] Muhammad, A., de Vasconcellos Azeredo, R. B., “1H NMR spectroscopy and low- field relaxometry for predicting viscosity and API gravity of Brazilian crude oils – A comparative study”, Fuel 130 (2014) : 126-134.
• [25] Saidian, M., Prasad, M., “Effect of mineralogy on nuclear magnetic resonance surface relaxivity: A case study of middle Bakken and three forks formations”, Feul 161 (2015) : 197-206.
• [26] Luo, Z-X, Paulsen, J., Song, Y-Q., “Robust determination of surface relaxivity from nuclear magnetic resonance DT2 measurements”, J. Magn. Reson. 259 (2015) : 146-152.
• [27] Zhang, B., Daigle, H., “Direct determination of surface relaxivity in isolated kerogen by pulsed-field gradient NMR”, Paper presented at the SPE/AAPG/SEG Unconventional Resources Technology Conference, San Antonio, Texas, USA, (2016), Paper Number: URTEC-2460364-MS.
• [28] Lennartz, D, Strehlow, H., “Determination of reaction rate constants and T2 relaxation times using integrated NMR power spectra”, Zeitschrift Fur Physikalische Chemie: Z. Phys.Chem. 220 (2006) : 641-653.
• [29] Chen, K., Tjandra, N., “Direct Measurements of protein backbone 15N spin relaxation rates from peak line-width using a fully-relaxed accordion 3D HNCO experiment”, J. Magn.Reson. 197(1) (2009) : 71-76.
• [30] Wilhelm, M. J., Ong H. H., Wehrli., F. W., “Super-Lorentzian framework for investigation of T2* distribution in myelin”, In Proceedings of the 20th Annual Meeting of ISMRM, Melbourne, Victoria, Australia, (2012) : 2394.
• [31] Ahlner, A., Carlsson, M., Jonsson, B. H., Lundström, P., “PINT-a software for integration of peak volumes and extraction of relaxation rates”, J.Biomol. NMR. 56 (2013) : 191-202.
• [32] Yilmaz A., Zengin, B., “High-field NMR T2 relaxation mechanism in D2O solutions of albümin”, J. Appl. Spectrosc. 80(3) (2013) : 335-340.
• [33] Carrington, A., McLachlan, A. D., “Introduction to magnetic resonance: With applications to chemistry and chemical physics”, Publisher: Harper and Row, London, (1967).
• [34] Washburn, K. E., “Relaxation mechanisms and shales”, Concepts in Magn. Reson. Part A. 43A(3) (2014) : 57-78.
• [35] Mehana, M., El-Monier, I., “Characteristics impact on nuclear magnetic resonance (NMR) fluid typing methods and correlations”, Petroleum 2(2) (2016) : 138-247.
• [36] Mladenov, G., Dimitrov. V. S., “Extraction of T2 from NMR linewidths in simple spin systems by use of reference deconvolution”, Magn. Reson. Chem. 39 (2001) : 672-680.
• [37] Jones, M., Taylor, S. E., “NMR relaxometry and diffusometry in characterizing structural, interfacial and colloidal properties of heavy oils and oil sands”, Advan. Colloid. Interfac. 224 (2015) : 33-45.
• [38] Morgan, V. G., Barbosa, L. L., Lacerda, Jr. V., de Castro, E. V. R., “Evaluation of the physicochemical properties of the post salt crude oil for Low-field NMR”, Ind. Eng. Chem. Res. 53(21) (2014) : 8881-8889.
• [39] Pople, J. A., “The effect of quadrupole relaxation on nuclear magnetic resonance multiplets”, Mol. Phys. 1(2) (1958) : 168-174.
• [40] [Gill, D., Pathania, V., “Chapter ten-The chemistry of monovalent copper in solutions of pureand mixed nonaqueous solvents”, Advan. Inorg. Chem. 68 (2016) : 441-481.
• [41] Chen, K., “A Practical review of NMR Lineshapes for Spin-1/2 and quadrupolar nuclei in disordered materials”, Int. J. Mol. Sci. 21(16) (2020) : 5666.
• [42] Freedman, R., “Advances in NMR logging”, J .Pet. Technol. 58(1) (2006) : 60-66.