A multi-metal bulk catalyst for ultra-deep desulfurization and denitrification, its preparation method and application

Abstract

The invention relates to a hydrofining multi-metal bulk catalyst for ultra-deep desulfurization and denitrogenation and a preparation method thereof. The multi-metal bulk catalyst is composed of a Group VIII metal, a Group IVB metal and two Group VIB metals. Mixed metal oxides composed of metals, wherein the catalyst contains 1-60wt% of Group VIII metals, 1-50wt% of Group IVB metals, and 5-60wt% of two types of Group VIB based on oxides and catalysts Metal. The invention also discloses the preparation method and application of the above-mentioned catalyst. The invention is applied in the hydrofining reaction of fuel oil containing sulfur and nitrogen. The reaction conditions are: temperature 280-400°C, hydrogen pressure 1-20MPa, hydrogen and the The volume ratio of sulfur-containing and nitrogen-containing fuel is 50-1000, and the volume space velocity of the material is 0.1-10h-1. During the reaction, the catalyst can remove sulfur and nitrogen in the diesel fraction from 500ppm to below 10ppm respectively, realizing diesel oil Ultra-deep hydrodesulfurization and ultra-deep hydrodenitrogenation.

Description

technical field [0001] The invention belongs to the field of petrochemical industry, and in particular relates to a hydrorefining multi-metal body catalyst for ultra-deep desulfurization and denitrification, a preparation method thereof and an application in ultra-deep hydrodesulfurization and hydrodenitrogenation reactions of diesel oil. Background technique [0002] At present, due to the decline of the world's oil reserves, the problem of heavy and inferior oil is becoming more and more serious, and the environmental legislation of various countries in the world has increasingly stringent restrictions on the sulfur content of fuel oil and the emission of nitrogen oxides from vehicle exhaust. Therefore, the development of The ultra-deep hydrodesulfurization and denitrification catalyst with higher performance has received more and more attention in the petrochemical industry. The nitrogen-containing compounds and sulfur-containing compounds in fuel oil are the main culprit...

AI Technical Summary

Problems solved by technology

This synthetic method has the following disadvantages: the strong ammonia water used in the synthetic process can pollute the environment; Ni 2+ The complex formed with ammonia is stable and difficult to decompose, resulting in residual Ni ammonium complex ions in the final mother liquor, resulting in pollution and waste; the prepared catalyst specific surface area and pore volume are less (respectively less than 120m 2 / g and 0.2ml / g), which is not conducive to the diffusion of reactants in the catalyst; when used in diesel hydrodesulfurization reaction, it can only show excellent hydrodesulfurization activity under a high pressure higher than 6MPa, so that the catalyst has no effect on the reaction device. Higher requirements are not conducive to industrial applications

[0009] (1) The specific surface area and pore volume of the catalyst are small, and the activity needs to be improved;

[0010] (2) The raw materials used for synthesis are unfriendly to the environment;

[0011] (3) The preparation cost of catalyst is higher;

[0012] (4) Only attention is paid to the hydrodesulfurization activity of the catalyst, and little attention is paid to the hydrodenitrogenation activity of the catalyst

Previously, our group reported the synthesis method of NiMoW bulk catalysts in Chinese patents CN101733120A and CN103657672A. Using environmentally friendly raw materials, the specific surface area (~140m 2 / g) and larger pore volume (~0.4ml / g), can achieve ultra-deep hydrodesulfurization of diesel under relatively mild conditions, but the hydrodenitrogenation activity of the catalyst has not yet been paid attention to

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