Ni–Mo sulfide nanosized catalysts from water-soluble precursors for hydrogenation of aromatics under water gas shift conditions

Author:

Vutolkina Anna1,Glotov Aleksandr12,Baygildin Ilnur1,Akopyan Argam1,Talanova Marta1,Terenina Maria1,Maximov Anton13,Karakhanov Eduard1

Affiliation:

1. Faculty of Chemistry, Department of Petroleum Chemistry and Organic Catalysis , Lomonosov Moscow State University , GSP-1, 1-3 Leninskiye Gory, 119991 , Moscow , Russia

2. Faculty of Chemical and Environmental Engineering, Department of Physical and Colloid Chemistry , Gubkin Russian State University of Oil and Gas (NRU) , 65 Leninsky Prospekt, 119991 , Moscow , Russia

3. A.V. Topchiev Institute of Petrochemical Synthesis, RAS , GSP-1, 29 Leninsky Prospekt, 119991 , Moscow , Russia

Abstract

Abstract The unsupported catalysts were obtained during hydrogenation by in situ high-temperature decomposition (above 300 °C) of water-soluble metal precursors (ammonium molybdate and nickel nitrate) in water-in-oil (W/O) emulsions stabilized by surfactant (SPAN-80) using elemental sulfur as sulfiding agent. These self-assembly Ni–Mo sulfide nanosized catalysts were tested in hydrogenation of aromatics under CO pressure in water-containing media for hydrogen generation through a water gas shift reaction (WGSR). The composition of the catalysts was determined by XRF and active sulfide phase was revealed by XRD, TEM and XPS techniques. The calculations based on TEM and XPS data showed that the catalysts are highly dispersed. The surfactant was found to affect both dispersion and metal distribution for Ni and Mo species, providing shorter slab length in terms of sulfide particle formation and stacking within high content of NiMoS phase. Catalytic evaluation in hydrogenation of aromatics was performed in a high-pressure batch reactor at T = 380–420 °С, p(CO) = 5 MPa with water content of 20 wt.% and CO/H2O molar ratio of 1.8 for 4–8 h. As shown experimentally with unsupported Ni–Mo sulfide catalysts, the activity of aromatic rings depends on the substituent therein and decreases as follows: anthracene>>1-methylnaphthalene≈2-methylnaphthalene>1,8-dimethylnaphthale-ne>>1,3-di-methylnaphthalene>2,6-dimethylnaphthalene≈2,3-dimethylnaphthalene>2-ethyl-naphthalene. The anthracene conversion reaches up to 97–100% for 4 h over the whole temperature range, while for 1MN and 2MN it doesn’t exceed 92 and 86% respectively even at 420 °С for 8 h. Among dimethyl-substituted aromatics the higher conversion of 45% was achieved for 1,8-dimethylnaphthalene with 100% selectivity to tetralines at 400 °С for 6 h. Similar to 1- and 2-methylnaphtalenes, the hydrogenation of asymmetric dimethyl-substituted substrate carries out through the unsubstituted aromatic ring indicating that steric factors influence on the sorption mechanism over active metal sites. The catalysts were found to be reused for at least six cycles when the hydrogenation is sulfur-assisted preventing metal oxide formation. It was established, that at the first 2–3 h known as the induction period, the oxide catalyst precursors formed slowly by metal salt decomposition, which reveals that it is the rate-determining step. The sulfidation is rather fast based on high catalytic activity data on 2MN conversion retaining at 93–95% upon recycling.

Funder

Russian Science Foundation

Publisher

Walter de Gruyter GmbH

Subject

General Chemical Engineering,General Chemistry

Reference61 articles.

1. H. Luik, L. Luik, I. Johannes, L. Tiikma, N. Vink, V. Palu, M. Bitjukov, H. Tamvelius, J. Krasulina, K. Kruusement, I. Nechaev. Fuel Process. Technol.124, 115 (2014).

2. A. Marafi, H. Albazzaz, M. S. Rana. Catal. Today329, 125 (2019).

3. R. Mythili, P. Venkatachalam, P. Subramanian, D. Uma. Bioresour. Technol.138, 71 (2013).

4. A. Alvarez-Majmutov, R. Gieleciak, J. Chen. Fuel. 241, 744 (2019).

5. P. C. S. Zorzenão, R. M. Mariath, F. E. Pinto, L. V. Tose, W. Romão, A. F. Santos, A. P. Scheer, S. Simon, J. Sjöblom, C. I. Yamamoto. J. Petrol. Sci. Eng.160, 1 (2018).

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