Heavy raw oil hydrogenating treatment catalyst and its preparing method

Abstract

The present invention discloses one kind of catalyst for the hydrotreatment of heavy material oil and its preparation. The catalyst consists of fluorine 0.5-15 wt%, assistant M in oxide 1.0-30 wt%, VIB metal oxide 15-35 wt%, VIII metal oxide 2.0-10 wt% and alumina the rest. It features the simultaneous modification of catalyst carrier with both fluorine and assistant M, and this can not only regulate the physical and chemical property of catalyst but also avoid the loss of fluorine in the catalyst, which will lower the activity of the catalyst, corrode the downstream apparatus and pollute environment. The catalyst is used in hydrotreatment of heavy material oil and has excellent hydrodesulfurizing, hydrodenitrifying and arene saturating performance.

Description

1. Technical field

[0001] The invention relates to a hydrogenation treatment catalyst and a preparation method thereof, in particular to a heavy feedstock oil hydrogenation treatment catalyst containing fluorine additives and a preparation method thereof. 2. Background technology

[0002] In recent years, the trend of heavy and inferior crude oil has become increasingly obvious around the world. On the other hand, the requirements for environmental protection have become increasingly stringent. The content is getting lower and lower, forcing the industry to continuously develop and use various high-activity hydrotreating catalysts with better performance and suitable for heavy crude oil.

[0003] Aromatics in heavy crude oil are mainly polycyclic aromatic hydrocarbons, and the hydrogenation saturation reaction of aromatic hydrocarbons is mainly the reaction of hydrogenation and ring opening of polycyclic aromatic hydrocarbons to form single-ring aromatic hydrocarbons or bicy...

Examples

Embodiment 1

[0039] The preparation process of the catalyst carrier is introduced by extruding the method as an example.

[0040] Take 8.5ml of silica sol (SiO 2 30m%), 10g of ammonium fluorosilicate and 80ml of water to prepare a solution; mix 100g of aluminum hydroxide dry powder, 10g of carbon black, and 5.0g of squid powder evenly, add the above solution and knead into a uniform plastic body, and extrude into a 1.2mm The clover-shaped strips were dried at 120°C for 4 hours and calcined at 600°C for 4 hours to obtain the fluorine-containing catalyst carrier A.

[0041] Take 30ml of silica sol, 2.0ml of acetic acid solution (HAc 36%), 8.0g of ammonium fluorosilicate and 75ml of water to prepare a solution; mix 100g of aluminum hydroxide dry powder, 10g of carbon black and 5.0g of scallop powder, add the above solution and knead Synthesize a uniform plastic body, extrude it into a cylindrical strip of 1.5mm, dry it at 110°C for 4 hours, and bake it at 650°C for 4 hours to obtain the flu...

Embodiment 2

[0045] This example describes the preparation of active component solutions and catalyst preparation.

[0046] Get 203g nickel nitrate (Ni(NO 3 ) 2 ·6H 2 O), 320g ammonium metatungstate (containing WO 3 85.2m%), add deionized water, stir and dissolve, and prepare 500ml tungsten-nickel solution.

[0047] Get 40ml of this tungsten-nickel solution and 50g of the carrier A in Example 1 and place it in a drum for spray immersion (saturated impregnation method). The spray immersion time is 30 minutes. After spraying, take it out and dry it at 120°C for 3 hours, then Calcined at 500°C for 3 hours to prepare catalyst A1.

[0048] The carrier C in Example 1 was taken, impregnated with 200 ml of the above-mentioned tungsten-nickel solution (supersaturated impregnation method) for 2 hours, filtered, dried at 110°C for 3 hours, and then calcined at 450°C for 3 hours to obtain catalyst C1.

[0049] Get 56g basic nickel carbonate (containing NiO 44.7m%), 152g ammonium molybdate (contai...

1. Technical field

[0001] The invention relates to a hydrogenation treatment catalyst and a preparation method thereof, in particular to a heavy feedstock oil hydrogenation treatment catalyst containing fluorine additives and a preparation method thereof. 2. Background technology

[0002] In recent years, the trend of heavy and inferior crude oil has become increasingly obvious around the world. On the other hand, the requirements for environmental protection have become increasingly stringent. The content is getting lower and lower, forcing the industry to continuously develop and use various high-activity hydrotreating catalysts with better performance and suitable for heavy crude oil.

[0003] Aromatics in heavy crude oil are mainly polycyclic aromatic hydrocarbons, and the hydrogenation saturation reaction of aromatic hydrocarbons is mainly the reaction of hydrogenation and ring opening of polycyclic aromatic hydrocarbons to form single-ring aromatic hydrocarbons or bicy...

Examples

Embodiment 1

[0039] The preparation process of the catalyst carrier is introduced by extruding the method as an example.

[0040] Take 8.5ml of silica sol (SiO 2 30m%), 10g of ammonium fluorosilicate and 80ml of water to prepare a solution; mix 100g of aluminum hydroxide dry powder, 10g of carbon black, and 5.0g of squid powder evenly, add the above solution and knead into a uniform plastic body, and extrude into a 1.2mm The clover-shaped strips were dried at 120°C for 4 hours and calcined at 600°C for 4 hours to obtain the fluorine-containing catalyst carrier A.

[0041] Take 30ml of silica sol, 2.0ml of acetic acid solution (HAc 36%), 8.0g of ammonium fluorosilicate and 75ml of water to prepare a solution; mix 100g of aluminum hydroxide dry powder, 10g of carbon black and 5.0g of scallop powder, add the above solution and knead Synthesize a uniform plastic body, extrude it into a cylindrical strip of 1.5mm, dry it at 110°C for 4 hours, and bake it at 650°C for 4 hours to obtain the flu...

Embodiment 2

[0045] This example describes the preparation of active component solutions and catalyst preparation.

[0046] Get 203g nickel nitrate (Ni(NO 3 ) 2 ·6H 2 O), 320g ammonium metatungstate (containing WO 3 85.2m%), add deionized water, stir and dissolve, and prepare 500ml tungsten-nickel solution.

[0047] Get 40ml of this tungsten-nickel solution and 50g of the carrier A in Example 1 and place it in a drum for spray immersion (saturated impregnation method). The spray immersion time is 30 minutes. After spraying, take it out and dry it at 120°C for 3 hours, then Calcined at 500°C for 3 hours to prepare catalyst A1.

[0048] The carrier C in Example 1 was taken, impregnated with 200 ml of the above-mentioned tungsten-nickel solution (supersaturated impregnation method) for 2 hours, filtered, dried at 110°C for 3 hours, and then calcined at 450°C for 3 hours to obtain catalyst C1.

[0049] Get 56g basic nickel carbonate (containing NiO 44.7m%), 152g ammonium molybdate (contai...