TY - JOUR

T1 - Investigation on halloysite nanotube catalysts for heavy oil hydrotreatment

AU - Vorobyeva, E. E.

AU - Khoreshkova, A. A.

AU - Polukhin, A. V.

AU - Vdovichenko, V. A.

AU - Metalnikova, V. M.

AU - Lysikov, A. I.

AU - Selezneva, D. A.

AU - Parkhomchuk, E. V.

N1 - The study was supported by Ministry of Science and Higher Education of the Russian Federation (project FWUR-2024-0036). The Raman equipment was provided by REC «MDEST» NSU. The authors thank the Department of Solid State Chemistry of NSU for the provided Raman equipment and S.S. Sharaya for the Raman spectra recording. The authors thank Mikhail Kanin for providing of the HNT-containing natural materials.

PY - 2025/12/1

Y1 - 2025/12/1

N2 - Within the present study, halloysite nanotube-containing clay (Raw clay) and commercial product (Commercial clay) obtained by treatment the Raw clay from the same mine were investigated in the hydrodesulfurization of heavy oil. Two catalysts with approximately the same HNT content were synthesized: CoMoNi/Clay and CoMoNi/Composite. The former contained a Raw clay mineral as a source of HNT, while the latter − a Commercial clay and a binder (Al2O3). CoMoNi/Al2O3 was synthesized and used as a reference catalyst. The catalysts were characterized by XRD, N2-sorption, Hg-porosimetry, FTIR, and Raman spectroscopy. It has been found that catalysts from natural clays have heterogeneity of the phase composition (significant variation in phase composition from one sample to another) and are capable of forming macroporosity by sintering of nonporous phases. In turn, β-CoMoO4 has been preferably formed on HNT-containing catalyst surface. Catalytic test on hydrotreatment (HT) of a real oil feedstock was performed at 390 and 400 °C, hydrogen pressure at 7 MPa, a product collected after the three-stage HT of atmospheric residue was used as the feedstock. Catalytic tests showed the initial specific activity of the HNT-catalysts was higher compared with traditional catalysts but changed due to high density of the acidic sites and undeveloped texture formed by nonporous phases.

AB - Within the present study, halloysite nanotube-containing clay (Raw clay) and commercial product (Commercial clay) obtained by treatment the Raw clay from the same mine were investigated in the hydrodesulfurization of heavy oil. Two catalysts with approximately the same HNT content were synthesized: CoMoNi/Clay and CoMoNi/Composite. The former contained a Raw clay mineral as a source of HNT, while the latter − a Commercial clay and a binder (Al2O3). CoMoNi/Al2O3 was synthesized and used as a reference catalyst. The catalysts were characterized by XRD, N2-sorption, Hg-porosimetry, FTIR, and Raman spectroscopy. It has been found that catalysts from natural clays have heterogeneity of the phase composition (significant variation in phase composition from one sample to another) and are capable of forming macroporosity by sintering of nonporous phases. In turn, β-CoMoO4 has been preferably formed on HNT-containing catalyst surface. Catalytic test on hydrotreatment (HT) of a real oil feedstock was performed at 390 and 400 °C, hydrogen pressure at 7 MPa, a product collected after the three-stage HT of atmospheric residue was used as the feedstock. Catalytic tests showed the initial specific activity of the HNT-catalysts was higher compared with traditional catalysts but changed due to high density of the acidic sites and undeveloped texture formed by nonporous phases.

KW - CoMoNi-catalysts

KW - Deactivation

KW - Halloysite nanotubes

KW - Hydrodesulfurization

KW - Hydrotreatment

UR - https://www.mendeley.com/catalogue/14a92da6-97b3-352d-873d-d0a9cf87cb06/

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-105007159473&origin=inward&txGid=a1f43c2aa0c57424ed973fc2b10a38e4

U2 - 10.1016/j.fuel.2025.135563

DO - 10.1016/j.fuel.2025.135563

M3 - Article

VL - 401

JO - Fuel

JF - Fuel

SN - 0016-2361

M1 - 135563

ER -