Probing the surface of synthetic opals with the vanadyl-containing crude oil by using EPR and ENDOR techniques

TL;DR

This study uses advanced EPR and ENDOR techniques to investigate how oil asphaltenes interact with synthetic silica opal surfaces, revealing changes in molecular structure and surface interactions relevant for oil recovery.

Contribution

It demonstrates the application of pulsed EPR and ENDOR to characterize oil-silica interactions at the molecular level, highlighting surface effects on asphaltene adsorption.

Findings

1H ENDOR spectra differ before and after adsorption, indicating VO disaggregation.

No significant changes in W band EPR spectra upon adsorption.

Surface proton groups influence asphaltene adsorption properties.

Abstract

Porous silica materials offer wide range of possibilities for enhancement of the productivity of oil reservoirs. However the mechanism of adsorption of polar components of crude oil on silica surface is poorly understood that hinders technological improvement of supports and oil extraction. We have synthesized opal films with the silica microspheres size of about 360 nm, specific surface area of 5.2 m2/g and pore size of 230 nm. We have fractionated and characterized oil and oil asphaltenes from heavy (Ashalchinskoe) oil. By pulsed electron paramagnetic resonance (EPR) and double electron nuclear resonance (ENDOR) in the W band frequency range (microwave frequency of 94 GHz, magnetic field of 3.4 T) we have studied the adsorption of oil asphaltenes on the surface of opal samples using the intrinsic for asphaltenes paramagnetic vanadylporphyrins (VO) complexes. 1H ENDOR spectra are found to be different for initial and the adsorbed samples in their central parts (that is a sign of asphaltenes VO disaggregation) whereas no significant changes in the W band EPR spectra were detected. Contrasting to alumina support, no strong electron proton interaction with the protons on the surface of SiO2 (presumably, silanol groups) was found and infiltration of the oiled opal films with gasoline changes the central part of 1H ENDOR spectra. It shows that the proton containing groups on the surface of amorphous SiO2 sample can significantly change the asphaltene adsorption properties and ENDOR of the intrinsic for oil paramagnetic centers could be used for the characterization of surface state in porous media in situ or operando.