Roles of Nanostructured Bimetallic Supported on Alumina-Zeolite (AZ) in Light Cycle Oil (LCO) Upgrading

Light cycle oil (LCO) is one of the major products in Fluid catalytic cracking (FCC) processes, and has drawbacks such as high aromatics, sulfur, and nitrogen contents, and low cetane number (CN). Hydro-upgrading is one of the most typical processes for LCO upgrading, and alumina-zeolite (AZ) is an effective hydrotreating catalyst support. This paper examined the effects of different bimetallic catalysts (CoMo/AZ, NiMo/AZ, and NiW/AZ) supported by AZ on hydro-upgrading of both model compounds and real LCO. CoMo/AZ preferred the direct desulfurization (DDS) route while the NiMo/AZ and NiW/AZ catalysts favored the desulfurization route through hydrogenation (HYD). The presence of nitrogen compounds in the feed introduced a competitive adsorption mechanism and reduced the number of available acid sites. Aromatics were partially hydrogenated into methyltetralines at first, and then further hydrogenated, cracked, and isomerized into methyldecalins, monocyclic, and methyltetralines isomers. CoMo/AZ is the best hydrodesulfurization (HDS) catalyst for the model compounds at low H2 pressure (550 psi) and for LCO at lower temperature (573 K), while NiMo/AZ performs the best for LCO at higher temperature (648 K). NiMo/AZ is the best hydrodenitrogenation (HDN) catalyst for LCO. The hydrodearomatization (HDA) performances of NiMo/AZ and NiW/AZ improved significantly and overwhelmingly higher than that of the CoMo/AZ when the H2 pressure was increased to 1100 psi.

[1]  S. Moreno,et al.  Hydrocracking of 1-methylnaphtalene (1MN) over modified clays-supported NiMoS and NiWS catalyst , 2021, Fuel.

[2]  Mônica A. P. Silva,et al.  Impact of proximity between NiMoS and zeolitic HY sites on cyclohexene hydroconversion: An infrared operando study of sulfide catalysts , 2021, Journal of Catalysis.

[3]  Hui Wang,et al.  Hydro‐upgrading of light cycle oil‐synthesis of NiMo/SiO2-Al2O3-TiO2 porous catalyst , 2021, Journal of porous materials.

[4]  Chunming Xu,et al.  Selective hydrocracking of light cycle oil into high-octane gasoline over bi-functional catalysts , 2021, Journal of Energy Chemistry.

[5]  A. V. Kleimenov,et al.  Influence of zeolite content in NiW/Y-ASA-Al2O3 catalyst for second stage hydrocracking , 2020 .

[6]  Xilong Chen,et al.  Steric Hindrance of Methyl Group on the Reaction Pathway of Hydrodesulfurization in the Presence of Quinoline , 2020, Catalysis Letters.

[7]  P. Merino,et al.  Impact of variables on the naphthalene hydrogenation for the tetralin formation towards BTX production , 2020, International Journal of Oil, Gas and Coal Technology.

[8]  Xuejun Pan,et al.  High Metal–Acid Balance and Selective Hydrogenation Activity Catalysts for Hydrocracking of 1-Methylnaphthalene to Benzene, Toluene, and Xylene , 2020 .

[9]  Xilong Wang,et al.  DFT insights into the direct desulfurization pathways of DBT and 4,6-DMDBT catalyzed by Co-promoted and Ni-promoted MoS2 corner sites , 2019, Chemical Engineering Science.

[10]  Jinsen Gao,et al.  Development of heavy oil upgrading technologies in China , 2019 .

[11]  Zhenmin Cheng,et al.  Upgrading of Light Cycle Oil to High-Octane Gasoline through Selective Hydrocracking over Non-Noble Metal Bifunctional Catalysts , 2019, Energy & Fuels.

[12]  Lixin Zhao,et al.  Characteristics of zeolite‐modified NiMo/Al 2 O 3 catalysts and their hydrotreating performance for light cycled oil , 2018, The Canadian Journal of Chemical Engineering.

[13]  A. Maximov,et al.  Development of micro-mesoporous materials with lamellar structure as the support of NiW catalysts , 2018, Microporous and Mesoporous Materials.

[14]  P. Merino,et al.  Light Cycle Oil Upgrading to High Quality Fuels and Petrochemicals: A Review , 2018 .

[15]  Hongfei Lin,et al.  Hydrotreating of waste cooking oil over supported CoMoS catalyst – Catalyst deactivation mechanism study , 2017 .

[16]  Zhanquan Zhang,et al.  Technical review on flexible processing middle distillate for achieving maximum profit in China , 2017, Applied Petrochemical Research.

[17]  Hongfei Lin,et al.  Integration of catalytic cracking and hydrotreating technology for triglyceride deoxygenation , 2017 .

[18]  L. Du,et al.  Effects of Ga- and P-modified USY-based NiMoS catalysts on ultra-deep hydrodesulfurization for FCC diesels , 2017 .

[19]  Xiangchen Fang,et al.  Commercial analysis of catalytic hydroprocessing technologies in producing diesel and gasoline by light cycle oil , 2016 .

[20]  H. Yang,et al.  The role of nanobeta zeolite in NiMo hydrotreating catalysts , 2012 .

[21]  H. Yang,et al.  Co-promotion of fluorine and boron on NiMo/Al2O3 for hydrotreating light cycle oil , 2012 .

[22]  M. Zheng,et al.  A Novel Route to the Preparation of Carbon Supported Nickel Phosphide Catalysts by a Microwave Heating Process , 2010 .

[23]  H. Yang,et al.  LCO hydrotreating with Mo-Ni and W-Ni supported on nano-and micro-sized zeolite beta , 2009 .

[24]  Zisheng Zhang,et al.  Hydrotreating of light cycle oil using WNi catalysts containing hydrothermally and chemically treated zeolite Y , 2007 .

[25]  Zisheng Zhang,et al.  Hydrotreating of light cycled oil using WNi/Al2O3 catalysts containing zeolite beta and/or chemically treated zeolite Y , 2006 .

[26]  Xianchun Wu Acidity and catalytic activity of zeolite catalysts bound with silica and alumina , 2004 .

[27]  K. Knudsen,et al.  Catalyst and process technologies for ultra low sulfur diesel , 1999 .

[28]  J. W. Ward The nature of active sites on zeolites: VIII. Rare earth Y zeolite , 1969 .

[29]  Louise Olsson,et al.  Hydrotreatment of lignin dimers over NiMoS-USY: effect of silica/alumina ratio , 2021, Sustainable Energy & Fuels.

[30]  Qian,et al.  Hydrodesulfurization , Hydrodenitrogenation and Hydrodearomatization over CoMo / SAPO-11-Al 2 O 3 Catalysts , 2017 .

[31]  Guo,et al.  Development of Light Cycle Oil(LCO) Hydrocracking Technology over a Commercial W-Ni Based Catalyst , 2015 .

[32]  Haiping Zhang Synthesis of highly active unsupported molybdenum sulfide catalysts for hydrosulfurization and hydrodeoxygenation , 2014 .