A kind of preparation method of sulfurized hydrogenation catalyst

Abstract

The present invention discloses a preparation method for a vulcanization type hydrogenation catalyst. The preparation method comprises: uniformly mixing a carrier precursor, a thiomolybdate and / or thiotungstate, a nickel salt and / or a cobalt salt, adding a binder to carry out kneading, carrying out molding, and then carrying out drying and calcination in the protection of an inert gas to prepare the catalyst. The method of the present invention has characteristics of simple process and high vulcanization degree, wherein the prepared vulcanization type hydrogenation catalyst has high activity and high selectivity.

Description

technical field [0001] The invention relates to a preparation method of a sulfurized hydrogenation catalyst. Background technique [0002] In recent years, with the decrease of oil reserves, the rising international oil price, and the trend of heavy and inferior crude oil becoming more and more serious, the market demand for high-quality middle distillate products continues to increase. Therefore, it is particularly important to increase the production of middle distillates, increase the ratio of diesel to gasoline, and improve the contradiction between supply and demand. The key to solving this contradiction lies in the development of hydrocracking catalysts with high selectivity for middle distillates. Most of the metal active components of the current industrialized hydrocracking catalysts exist in the form of oxides, but in actual use, the active metal oxides on the catalyst need to be converted into sulfides. Therefore, the catalysts need to be sulfurized or Called pre...

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Problems solved by technology

[0003] Conventional catalyst vulcanization methods use "in-vessel" vulcanization or "in-situ" vulcanization, that is, the catalyst in the oxidized state is first loaded into the hydrogenation reactor, and then hydrogen and sulfurizing agent are introduced into the reactor during the process of continuous heating. Pre-sulfurization, this method brings the following problems: (1) special pre-sulfurization equipment should be set up on the hydrogenation unit; (2) the vulcanizing agent added during the vulcanization process and the water and hydrogen sulfide generated by the reaction can easily cause high pressure Corrosion of reactors and related equipment, resulting in equipment damage and potential safety hazards; (3) The vulcanization process is longer, delaying the start-up time

(4) The vulcanizing agent used is flammable and toxic, and pollutes the environment during the vulcanization process; (5) The cost of pre-vulcanization in the device is relatively high

The above-mentioned methods all carry out pre-sulfurization treatment to the ready-made oxidized catalyst, so there are following deficiencies in the preparation process: the oxide MoO of hydrogenation catalyst active metal Mo, W, Co, Ni 3 、WO 3 , CoO, NiO have a strong interaction with the surface of the support, resulting in difficult and incomplete sulfidation of the active metal component, reducing the hydrogenation activity of the catalyst, and causing serious environmental pollution during the sulfidation process

Since thiomolybdate and thiotungstate are insoluble in water, organic solvents need to be added to the preparation solution, the preparation process is complicated, and it is not suitable for large-scale industrial production

In addition, during the high-temperature treatment process of this method, due to the volatilization of the organic solvent, the interaction between the hydrogenation component and the carrier is strengthened, which affects the sulfuration of the catalyst. The degree of sulfurization is relatively low, and the activity and selectivity of the catalyst decrease.

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