Nanomagnetic Cyclodextrin decorated with ionic liquid as green and reversible Demulsifier for breaking of crude oil emulsions

Abstract

Application of the chemical demulsifiers is the best choice for breaking the water in crude oil (W/O) emulsions in the petroleum industry. Here, novel, environmentally friendly, efficient, and easily reusable Fe3O4 nanomagnetic compounds based on imidazolium-decorated cyclodextrin were successfully synthesized and applied to demulsify the water in crude oil (W/O) emulsions. At first, Fe3O4 nanoparticles were decorated with β-cyclodextrin (β-CD) to prepare Fe3O4@β-CD@IL magnetic nanoparticles. Then, imidazole (Im) was separately reacted with 1-bromohexane and 1-bromodecane to prepare [Im-C6][Br] and [Im-C10][Br] ionic liquids, respectively. The prepared imidazolium-based ionic liquids were reacted with N-propyltriethoxysilane to synthesize [ImSi-C6][Br] and [ImSi-C10][Br]. Finally, [ImSi-Cn][Br] was immobilized on Fe3O4@β-CD to obtain nanomagnetic demulsifiers. Structure of the synthesized compounds was confirmed using different methods such as FT-IR, NMR, and elemental analysis. TGA, VSM, and FESEM methods were used to investigate the thermal stability, magnetic properties, and the morphology, respectively. Fe3O4@βCD and Fe3O4@βCD@[ImSi-C10][Br] nanoparticles respectively showed the particle size in the range of 40–70 nm and 50–80 nm. After grafting the imidazolium-based ionic liquid on the surface of support, the magnetization number reduced from 25.6 emu/g for Fe3O4@β-CD to 24.9 emu/g for Fe3O4@β-CD@[ImSi-C10][Br]. Synthesized material employed to break the (10:90 and 30:70 Vol%) W/O emulsions at the concentration range of 1000–5000 ppm. The maximum demulsification efficiency (DE%) of 92 % was obtained using a Fe3O4@β-CD@[ImSi-C10][Br] at 5000 ppm for (30:70 Vol%) W/O emulsion within 24 h. Interfacial tension (IFT) values decreased with increasing the DE%. The Fe3O4@βCD@[ImSi-C10][Br] demulsifier was reused five times with acceptable yields. The cooperation of imidazolium and β-CD in the green nanomagnetic demulsifiers led to the efficient demulsification of the W/O emulsions. The preparation of different ionic liquids or changing the counter anions are our potential future directions for this research. Demulsification at high demulsifier concentration can be considered a limitation of the nanomagnetic cyclodextrin decorated with ionic liquid. But due to the low amount of ionic liquid immobilized in the synthesized demulsifier, the cost of the final demulsifier is lower that other demulsifiers with full ionic liquid backbones, which increases its potential for industrial applications.