Ferrocene-based catalysts for in-situ hydrothermal upgrading of heavy crude oil: Synthesis and application

Anastasia N Mikhailova,Ameen A Al-Muntaser,Muneer A Suwaid,Rustem R Zairov,Ibrahim T Kadhim,Richard Djimasbe,Alexey Dovzhenko,Ilya A Bezkishko,Almaz Zinnatullin,Dmitrii A Emelianov,Reyimkulyyeva S Umarkulyevna,Farit G Vagizov,Chengdong Yuan,Mikhail A Varfolomeev

doi:10.1016/j.fuel.2023.128585

Anastasia N Mikhailova, Ameen A Al-Muntaser + Show 12 more

https://doi.org/10.1016/j.fuel.2023.128585

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Abstract

In this work, the effect of synthesized Ferrocene-based ligand catalysts, including Mono-, Di- and Tri-Ferrocene, as additives for promoting the catalytic in-situ hydrothermal upgrading of Tatarstan (Russia) heavy crude oil was studied. In addition, the changes in composition of upgraded oil samples as well as the in-situ transformation and characteristics of used catalysts were evaluated in detail using comprehensive analyzing techniques. All of the catalytic and non-catalytic hydrothermal upgrading experiments were carried out under the steam stimulation conditions at 300 °C, 72 bar (1044.27 psi) and 24 h of reaction time. The results show that introducing Ferrocene-based ligand catalysts to the upgrading system promotes the in-situ upgrading of heavy crude oil and improves the physical and chemical properties of upgraded oil samples. The maximum viscosity reduction was observed in presence Tri-Ferrocene and reached around 40% compared to non-catalytic hydrothermal upgrading. In addition, the upgrading performance also reflects in increase of H/C ratio, reduction of sulfur content, increase of saturates and aromatics, and decrease of the content of resins and asphaltenes as well as a noticeable change (increase) in the light fractions of C10-C20 are observed for all upgraded oil samples. Mono-Ferrocene as an oil-soluble catalyst mainly transformed to the particles of Fe3O4 (Magnetite) and FeS, which can act as active forms of catalysts and accelerate the hydrothermal conversion of heavy crude oil and its heavy fractions including resins and asphaltenes. These transformations were confirmed using XRD, SEM-EDX and Mössbauer analyzing techniques. Generally, the good catalytic performance of used ferrocene-based ligand catalysts as well as their low cost and commercial availability makes them great potential catalysts for improving the efficiency of steam injection for heavy oil production and in-situ upgrading.

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