K. A. Leonova

Bimetallic Co-Mo-complexes with optimal localization on the support surface: A way for highly active hydrodesulfurization catalysts preparation for different petroleum distillates

Abstract The preparation method of the catalyst for the deep hydrotreatment of vacuum gas oil and gasoline is described. The method is based on vacuum impregnation of the carrier with required average pore diameter with the solution of bimetallic CoMo complexes. It was shown that the use of Co-Mo complexes, containing chelating ligands and having different molecule size, allows to obtain catalysts with the uniform distribution of the surface species, containing supported metals only in the form of Co-Mo-S phase type II that is located inside of the pores exposed to all reacting heteroatomic molecules of the feedstock.

A new catalyst for the deep hydrotreatment of vacuum gas oil, a catalytic cracking feedstock

A new CoNiMo/Al2O3 deep vacuum gas oil hydrotreatment catalyst designed for the production of catalytic cracking feedstocks containing 200–500 ppm of sulfur is developed. The method for its preparation includes the following stages: the preparation of a support with specified textural, strength, and granulometric characteristics; the synthesis of bimetallic (Co-Mo and Ni-Mo) complex compounds in solution; and their deposition and drying. The new sample is compared to current domestic and imported industrial analogs according to their physicochemical (texture, morphology, active phase structure) and catalytic characteristics and analyzed. It is shown that the catalyst allows hydrotreatment at temperatures 5–20°C lower and target fraction yields 4–13% higher than all the reference samples. The high activity of the new catalyst is due to the formation of one-layer trimetallic Co(Ni)MoS phase particles at the stage of its sulfidation. The catalyst preparation technique is ready for industrial use (OOO Sintez, Barnaul, 1000 t/yr), and the principal technological regimes of the hydrotreatment of vacuum gas oil on the developed catalyst are determined.

Hydrocracking of vacuum gas oil in the presence of catalysts NiMo/Al2O3–amorphous aluminosilicates and NiW/Al2O3–amorphous aluminosilicates

Supported nickel–molybdenum and nickel–tungsten hydrocracking catalysts prepared using a support that consists of 70% Al2O3 and 30% amorphous aluminosilicate were characterized by nitrogen and mercury porosimetry, IR spectroscopy of adsorbed CO, and high-resolution electron microscopy. The catalytic tests in hydrocracking of vacuum gas oil containing 3.39% sulfur showed that the nature of the hydrogenating component (NiMo or NiW) only slightly influences the vacuum gas oil conversion and the diesel fraction yield, but noticeable influences the properties of the diesel fraction obtained. The catalyst NiMo/Al2O3–amorphous aluminosilicates, compared to NiW/Al2O3–amorphous aluminosilicates, ensures lower sulfur content in the diesel fraction obtained, whereas the catalyst NiW/Al2O3–amorphous aluminosilicates allows obtaining a diesel fraction with lower content of polyaromatic compounds.

Silica-alumina based nickel-molybdenum catalysts for vacuum gas oil hydrocracking aimed at a higher diesel fraction yield

Nickel-molybdenum hydrocracking catalysts based on amorphous silica-aluminas (ASAs) with Si/Al = 0.3–1.5 have been prepared using chemicals and methods available for catalyst plants. The acidic properties of the ASA surface have been investigated by IR spectroscopy of adsorbed CO, and it has been demonstrated that the Si/Al ratio has an effect on the concentration and strength of Brønsted and Lewis acid sites in the ASA. The catalysts have been characterized by low-temperature nitrogen adsorption and transmission electron microscopy, and it was found that the Si/Al ratio in the ASA has a considerable effect on the textural properties of the catalysts and only a slight effect on the particle size of the sulfide active component. The catalysts have been tested in vacuum gas oil hydrocracking in a laboratory-scale high-pressure flow reactor under typical industrial hydrocracking conditions. The highest diesel fraction yield (>60 wt % at 400°C) has been obtained with the catalyst based on the Si/Al = 0.9 ASA, which has the strongest Brønsted acid sites. With the catalysts based on the Si/Al = 0.3 and 1.5 ASAs, the diesel fraction yield is much lower. This may be due to the lower concentration and strength of acid sites in these catalysts and their smaller specific surface area. The NiMo catalyst based on Si/Al ≈ 0.9 ASA is recommended for industrial use in refineries aimed at obtaining the maximum possible yield of low-sulfur, high-cetane, diesel fuels.

Hydrocracking of vacuum gas oil in the presence of catalysts NiMo/Al2

Supported nickel–molybdenum and nickel–tungsten hydrocracking catalysts prepared using a support that consists of 70% Al2O3 and 30% amorphous aluminosilicate were characterized by nitrogen and mercury porosimetry, IR spectroscopy of adsorbed CO, and high-resolution electron microscopy. The catalytic tests in hydrocracking of vacuum gas oil containing 3.39% sulfur showed that the nature of the hydrogenating component (NiMo or NiW) only slightly influences the vacuum gas oil conversion and the diesel fraction yield, but noticeable influences the properties of the diesel fraction obtained. The catalyst NiMo/Al2O3–amorphous aluminosilicates, compared to NiW/Al2O3–amorphous aluminosilicates, ensures lower sulfur content in the diesel fraction obtained, whereas the catalyst NiW/Al2O3–amorphous aluminosilicates allows obtaining a diesel fraction with lower content of polyaromatic compounds.

Hydrocracking of vacuum gas oil in the presence of catalysts NiMo/Al 2 O 3 –amorphous aluminosilicates and NiW/Al 2 O 3 –amorphous aluminosilicates

Supported nickel–molybdenum and nickel–tungsten hydrocracking catalysts prepared using a support that consists of 70% Al2O3 and 30% amorphous aluminosilicate were characterized by nitrogen and mercury porosimetry, IR spectroscopy of adsorbed CO, and high-resolution electron microscopy. The catalytic tests in hydrocracking of vacuum gas oil containing 3.39% sulfur showed that the nature of the hydrogenating component (NiMo or NiW) only slightly influences the vacuum gas oil conversion and the diesel fraction yield, but noticeable influences the properties of the diesel fraction obtained. The catalyst NiMo/Al2O3–amorphous aluminosilicates, compared to NiW/Al2O3–amorphous aluminosilicates, ensures lower sulfur content in the diesel fraction obtained, whereas the catalyst NiW/Al2O3–amorphous aluminosilicates allows obtaining a diesel fraction with lower content of polyaromatic compounds.

Vacuum gasoil hydrocracking over three-layered packages consisting of supported sulfide NiMo and NiW catalysts

A method for vacuum gas oil hydrocracking using a three-layered package of catalysts is proposed, in which the top layer is NiMo/Al2O3, the middle is NiM/AAS-Al2O3 and the bottom is NiM/Y-Al2O3, where M is molybdenum or tungsten, AAS-Al2O3 is a support with 70% amorphous aluminosilicate (AAS) and 30% aluminum oxide, and Y is an Al2O3 support with 30% zeolite Y and 70% alumina. The acidic properties of the catalysts are studied via the IR spectroscopy of adsorbed CO. The morphology of sulfide particles on a catalyst’s surface is studied by means of transmission electron microscopy. Textural characteristics of the supports and catalysts are studied via nitrogen porosimetry. Packages containing NiMo and NiW catalysts in different combinations are tested in the hydrocracking of vacuum gas oil. It is shown that replacing NiMo/AAS-Al2O3 with NiW/AAS-Al2O3 in a catalyst package containing only NiMo considerably raises the yield of the diesel fraction.