Vulcanized hydrogenation catalyst, and preparation method and application thereof

A hydrogenation catalyst and vulcanization-type technology, applied in the direction of physical/chemical process catalysts, chemical instruments and methods, chemical/physical processes, etc., can solve the problems of uneven dispersion of active components, long vulcanization time, toxicity, etc., to avoid Formation of chemical bonds, saving start-up time, and simple technical operation

Inactive Publication Date: 2016-04-27
CHINA PETROLEUM & CHEM CORP +1
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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 H

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  • Vulcanized hydrogenation catalyst, and preparation method and application thereof
  • Vulcanized hydrogenation catalyst, and preparation method and application thereof
  • Vulcanized hydrogenation catalyst, and preparation method and application thereof

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preparation example Construction

[0022] The present invention provides a kind of preparation method of single metal vulcanization type hydrogenation catalyst, and this method comprises the following steps:

[0023] (1) The dispersant is contacted with solution A containing a VIB group metal salt and a sulfur source, the solution A is acidic, the dispersant is a water-soluble organic solvent with a boiling point of 15-90° C., and the sulfur source can be Sulfur-containing substances hydrolyzed under acidic conditions at 50-100°C;

[0024] (2) Contacting the product obtained in step (1) with the catalyst carrier at 60-150° C. for 5-30 hours under airtight conditions;

[0025] (3) Calcining the solid material obtained after contacting in step (2) in an inert or reducing atmosphere.

[0026] According to the present invention, preferably, the VIB group metal is molybdenum or tungsten, the VIB group metal salt is sodium molybdate and / or sodium tungstate, and the concentration of the VIB group metal salt in soluti...

Embodiment 1

[0063] Prepare 40 mL of a solution containing 0.15 mol / L sodium molybdate and 0.45 mol / L thioacetamide, and add 4.0 mL of 2.4 mol / L hydrochloric acid dropwise during stirring to obtain solution A with a pH value of 5.0;

[0064] Measure 20mL of absolute ethanol, and add the absolute ethanol dropwise to solution A at a rate of 1mL / min while stirring continuously to form solution B;

[0065] Transfer solution B to 4.0g of γ-Al with a diameter of 2-5mm 2 o 3 Then put the autoclave into a rotary oven (100rpm rotating speed) and contact it at 85°C for 24h, then filter the suspension, wash it with water, dry it at room temperature, and put it under H2O at 500°C. 2 Calcined in the atmosphere for 4h to obtain the single metal sulfide catalyst MoS 2 / γ-Al 2 o 3 .

[0066] Prepare a nickel nitrate solution containing 2.6g of nickel nitrate and about 15mL, and take 4.5mL of it to impregnate the above-mentioned sulfurized catalyst MoS 2 / γ-Al 2 o 3 , air-dried at room temperature,...

Embodiment 2

[0069] Prepare 30 mL of a solution containing 0.20 mol / L sodium tungstate and 0.60 mol / L thioacetamide, and add 4.5 mL of 2.4 mol / L hydrochloric acid dropwise during stirring to obtain solution A with a pH value of 4.5;

[0070] Then measure 30 mL of absolute ethanol, and add the absolute ethanol dropwise to solution A at a rate of 1 mL / min while stirring continuously to form solution B;

[0071] Transfer solution B to 4.0g of γ-Al with a diameter of 2-5mm 2 o 3 granules in an autoclave, and then placed the autoclave in a rotary oven (rotating speed: 80rpm) for 24 hours at 85°C, then filtered the suspension, washed it with water, and vacuum-dried it, and placed it at 500°C in H 2 Calcined in the atmosphere for 4h, the monometallic sulfurized catalyst WS was obtained 2 / γ-Al 2 o 3 .

[0072] Prepare about 15mL of nickel acetate solution containing 1.6g of nickel acetate, and take 4.0mL of it for impregnating the above vulcanized catalyst WS 2 / γ-Al 2 o 3 , air-dried at ...

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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...

Claims

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Application Information

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IPC IPC(8): B01J27/051B01J27/047B01J27/049C10G45/08
Inventor 韩伟龙湘云张乐刘学芬李明丰杨清河聂红李大东
Owner CHINA PETROLEUM & CHEM CORP
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