Electron paramagnetic resonance studies of asphaltenes complexes in heavy oils and bitumen

Authors: M.A.Volodin, M.R. Gafurov, G.V. Mamin, S.B. Orlinskii (Kazan (Volga Region) Federal University, RF, Kazan) V.M. Murzakaev (TNG-Group LLC, RF, Bugulma), T.N. Yusupova (Arbuzov Institute of Organic and Physical Chemistry, RF, Kazan)
Key words: electron paramagnetic resonance (EPR), dynamic nuclear polarization (DNP), asphaltenes, vanadyl
The present paper is focused on the application of some of the multifrequency (9.5 and 94 GHz) continuous wave and pulsed EPR techniques to study the dynamics and structure of asphaltenes and vanadyl complexes from the crude oils and bitumen at near room temperature. The features of the observation of EPR in these systems at high frequencies are pointed out. Longitudinal and transverse relaxation times of asphaltenes and vanadyl complexes are measured. Usage of the data obtained for DNP of protons of crude oils and bitumen is discussed.

References

1. Il'yasov A.V., Khimiya i tekhnologiya topliv i masel - Chemistry and Technology

of Fuels and Oils, 1962, V. 59, pp. 63-67.

2. Chang H.-L., Wong G.K., Lin J.R., Yen T., Electron spin resonance study of bituminous

substances and asphaltenes, Asphaltenes and Asphalts, Part 2. Developments

in Petroleum Science, 40B, NY.: Elsevier, 2000, Ch. 9, pp. 229-280.

3. Abdel-Raouf M., Crude oil emulsions – composition stability and characterization,

Croatia: InTechOpen, 2012, 230 p.

4. Bogomolova A.I., Sovremennye metody issledovaniya neftey (Modern

methods of study oils), Leningrad: Nedra Publ., 1984, 432 p.

5. Tojima M., Suhara S., Imamura M., Furuta A., Effect of heavy asphaltene on

stability of residual oil, Catalysis Today, 1998, V. 43, pp. 347-351.

6. Pool C.P., Jr., Electron Spin Resonance. Comprehensive treatise on experimental

techniques, J. Wiley & Sons, New York, London, Sydney 1967.

7. Salikhov K.M., Semenov A.G., Tsvetkov Yu.D., Elektronnoe spinovoe ekho i

ego primenenie (Electron spin echo and its application), Novosibirsk: Nauka

Publ., 1976, 342 p.

8. Stoll S., Schweiger A., EasySpin, a comprehensive software package for

spectral simulation and analysis in EPR, J. Magn. Reson., 2006, V. 178,

pp. 42–55.

9. Klauder J.R., Anderson P.W., Spectral diffusion decay in spin resonance experiments,

Phys. Rev.,1963, V. 125, no. 3, pp. 912-932.

10. Mamin G.V., Sitdikov D.T., Volodin M.A. et al., High-frequency EPR study of

the oil asphaltenes, Magnetic Resonance in Solids, Electronic journal, 2013,

V. 15, pp. 13105.

11. Gafurov M., Denysenkov V., Prandolini M.J., Prisner T., Temperature dependence

of the proton overhauser DNP enhancements on aqueous solutions of

Fremy‘s salt measured in a magnetic field of 9.2 T, Applied Magnetic Resonance,

2012, V. 43, no. 1-2, pp. 119-128.

12. Gafurov M.R., TEMPOL as a polarizing agent for dynamic nuclear polarization

of aqueous solutions, Magnetic Resonance in Solids, Electronic journal,

2013, V. 15, pp. 13103.

13. Baranov P.G., Orlinskii S.B., de Mello Donega C., Schmidt J., High-frequency

EPR and ENDOR Spectroscopy on Semiconductor Quantum Dots, Applied

Magnetic Resonance, 2010, V. 39, no. 1, pp. 151-183.

14. Mullins C., The modified Yen model, Energy Fuels, 2010, V. 24,

pp. 2179–2207.

Key words: electron paramagnetic resonance (EPR), dynamic nuclear polarization (DNP), asphaltenes, vanadyl
The present paper is focused on the application of some of the multifrequency (9.5 and 94 GHz) continuous wave and pulsed EPR techniques to study the dynamics and structure of asphaltenes and vanadyl complexes from the crude oils and bitumen at near room temperature. The features of the observation of EPR in these systems at high frequencies are pointed out. Longitudinal and transverse relaxation times of asphaltenes and vanadyl complexes are measured. Usage of the data obtained for DNP of protons of crude oils and bitumen is discussed.

References

1. Il'yasov A.V., Khimiya i tekhnologiya topliv i masel - Chemistry and Technology

of Fuels and Oils, 1962, V. 59, pp. 63-67.

2. Chang H.-L., Wong G.K., Lin J.R., Yen T., Electron spin resonance study of bituminous

substances and asphaltenes, Asphaltenes and Asphalts, Part 2. Developments

in Petroleum Science, 40B, NY.: Elsevier, 2000, Ch. 9, pp. 229-280.

3. Abdel-Raouf M., Crude oil emulsions – composition stability and characterization,

Croatia: InTechOpen, 2012, 230 p.

4. Bogomolova A.I., Sovremennye metody issledovaniya neftey (Modern

methods of study oils), Leningrad: Nedra Publ., 1984, 432 p.

5. Tojima M., Suhara S., Imamura M., Furuta A., Effect of heavy asphaltene on

stability of residual oil, Catalysis Today, 1998, V. 43, pp. 347-351.

6. Pool C.P., Jr., Electron Spin Resonance. Comprehensive treatise on experimental

techniques, J. Wiley & Sons, New York, London, Sydney 1967.

7. Salikhov K.M., Semenov A.G., Tsvetkov Yu.D., Elektronnoe spinovoe ekho i

ego primenenie (Electron spin echo and its application), Novosibirsk: Nauka

Publ., 1976, 342 p.

8. Stoll S., Schweiger A., EasySpin, a comprehensive software package for

spectral simulation and analysis in EPR, J. Magn. Reson., 2006, V. 178,

pp. 42–55.

9. Klauder J.R., Anderson P.W., Spectral diffusion decay in spin resonance experiments,

Phys. Rev.,1963, V. 125, no. 3, pp. 912-932.

10. Mamin G.V., Sitdikov D.T., Volodin M.A. et al., High-frequency EPR study of

the oil asphaltenes, Magnetic Resonance in Solids, Electronic journal, 2013,

V. 15, pp. 13105.

11. Gafurov M., Denysenkov V., Prandolini M.J., Prisner T., Temperature dependence

of the proton overhauser DNP enhancements on aqueous solutions of

Fremy‘s salt measured in a magnetic field of 9.2 T, Applied Magnetic Resonance,

2012, V. 43, no. 1-2, pp. 119-128.

12. Gafurov M.R., TEMPOL as a polarizing agent for dynamic nuclear polarization

of aqueous solutions, Magnetic Resonance in Solids, Electronic journal,

2013, V. 15, pp. 13103.

13. Baranov P.G., Orlinskii S.B., de Mello Donega C., Schmidt J., High-frequency

EPR and ENDOR Spectroscopy on Semiconductor Quantum Dots, Applied

Magnetic Resonance, 2010, V. 39, no. 1, pp. 151-183.

14. Mullins C., The modified Yen model, Energy Fuels, 2010, V. 24,

pp. 2179–2207.



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