Vulcanized hydrogenation catalyst, and preparation method and application thereof

Abstract

The invention provides a single-metal vulcanized hydrogenation catalyst and a double-metal vulcanized hydrogenation catalyst, and a preparation method and application thereof. The preparation method for the single-metal vulcanized hydrogenation catalyst comprises the following steps: (1) subjecting a dispersant and a solution A containing group-VIB metal salt and a sulfur source to contacting, wherein the solution A is acidic; the dispersant is a water-soluble organic solvent with a boiling point of 15 DEG to 90 DEG C; and the sulfur source is a sulfur-contained substance capable of hydrolyzing at 50 to 100 DEG C under the condition of acidity; (2) subjecting the product obtained by contacting in the step (1) and a catalyst carrier to contacting at 60 to 150 DEG C under a sealed condition for 5 to 30 hours; and (3) subjecting a solid material obtained by contacting in the step (2) to calcinating in an inert or reducing atmosphere. The invention also provides the single-metal vulcanized hydrogenation catalyst prepared by using the above-mentioned method, and application of the single-metal vulcanized hydrogenation catalyst in hydrodesulfurization and / or hydrodenitrification. Compared with the prior art, the hydrogenation catalyst provided by the invention has the characteristics of high metal activation grade, high active metal dispersity, high activity, etc.

Description

technical field [0001] The invention relates to a preparation method of a sulfurized hydrogenation catalyst, the sulfurized hydrogenation catalyst prepared by the method and its application in hydrodesulfurization and / or hydrodenitrogenation. Background technique [0002] Hydrogenation technology is the most important means of producing clean oil products, among which efficient hydrogenation catalyst is the core technology of hydrogenation technology. The main active component is VIB group metal W or Mo, the VIII group metal Ni or Co is the auxiliary active component, and γ-A1 2 o 3 or modified γ-A1 2 o 3 The supported catalyst is a hydrogenation catalyst widely used in industry at present. The traditional preparation technology mainly uses impregnation to introduce the oxidized precursor of the active component into the pores of the carrier, and then aging, drying, and roasting to obtain the hydrogenation catalyst. Among them, Co, Ni, Mo and W active components exist i...

AI Technical Summary

Problems solved by technology

On the one hand, when the oxidized active component is used as the precursor, no matter in the impregnation aging process or in the dry roasting process, its 2 o 3 The surface often has a strong interaction, which not only easily leads to uneven dispersion of the active component on the surface of the carrier, but also leads to the formation of too many Al-O-Mo chemical bonds, which in turn makes it difficult to completely vulcanize the active component and form too many low-activity type I Active phase, low active metal utilization (see CN103143365A)

In addition, taking the preparation of Mo-based catalysts as an example, the commonly used precursor ion Mo 7 o 24 6- tends to induce Al 2 o 3 Surface dissociation produces Al 3+ , and subsequently react with it to form an Anderson-type heteropolyanion Al(OH) 6 Mo 6 o 18 3- , after calcination, large-grained MoO is difficult to be fully sulfided, which is not conducive to the improvement of catalytic activity. 3 and Al 2 (MoO 4 ) 3 Species (see J.A.Bergwerffetal., Journal of the American Chemical Society 2004, 126:14548; J.A.Bergwerffetal., Catalysis Today 2008, 130:117.), therefore, it is difficult to achieve hydrogenation catalysts with high dispersion of active components and high degree of sulfidation using traditional impregnation techniques , resulting in unsatisfactory catalytic activity

In addition, studies have pointed out that the lower dispersion of active components will also lead to poor additive effect, and it is difficult to form enough Co(Ni)-Mo(W)-S active centers (see Hanetal., Journal of Materials Chemistry 2012, 22: 25340)

[0004] On the other hand, the presulfurization process in the traditional preparation technology adopts the "in-vessel" vulcanization technology, that is, the oxidation state catalyst is first loaded into the hydrogenation reactor, and then hydrogen and hydrogen are introduced into the reactor during the process of continuous heating. Vulcanizing agent for vulcanization, although this technology is still the most widely used technology at present, it still has a series of problems: 1) The vulcanizing time is too long, delaying the start of work; 2) The vulcanizing process is easy to cause corrosion and aging of the device; 3) The vulcanizing agent Flammable, toxic, easy to cause pollution to the environment; 4) higher cost, etc.

The preparation process of this method is relatively simple, and the preparation process does not need inert gas protection, and is easy to form the II type active phase with high catalytic activity at the same time, and the catalyst has high performance. ) acid salt is an active precursor, which ultimately makes the preparation cost of the catalyst very high, and the possibility of application is small

[0010] In summary, the technologies reported in the current literature are basically still in the stage of laboratory exploration. Although the prepared catalysts all exhibit excellent HDS performance, the complexity of the preparation route, poor controllability of the operation process and Higher production costs etc. limit the industrial application of these methods

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