Method for producing hydrogenation catalyst with fluidized bed

Abstract

The invention discloses a preparation method for fluidized bed hydrotreating catalysts, which is characterized in that alumina fiber is also added with the content of 3wt% to 10wt% in the catalyst besides the conventional hydrogenated catalyst component in the catalyst. The invention has the advantages that alumina fiber is added to increase mechanical strength of the catalyst; service life of thecatalyst is prolonged, and production cost is reduced; the complete mixing kneading method is adopted in the preparation method, wherein the hydrogenated active metallic ions are added into the catalyst in the mode of solution ions rather than granular metal salts, thus the metallic ions are dispersed more evenly, and mechanical strength of the catalyst is enhanced; and the acidic adhesive in themethod is added after the mixture of refractory porous inorganic oxide and alumina fiber is wetted by the active metallic solution, thus strong interaction of acid and refractory porous inorganic oxide as well as alumina fiber is greatly mitigated, and loss of pore volume and specific surface area is reduced.

Description

technical field

[0001] The invention relates to a preparation method of an ebullating bed hydrogenation treatment catalyst, in particular to a preparation method of an ebullation bed hydrogenation treatment catalyst used for the stable hydrogenation of heavy oil products. Background technique

[0002] The catalytic hydrogenation process usually used for heavy oil products is mainly a fixed bed hydrogenation process. Fixed bed reactors are especially suitable for handling lighter and cleaner feeds, such as naphtha, middle distillates, gas oils and ordinary residues. The fixed bed reactor is characterized by smoother operation and easier control. There are the following problems in the hydrotreating of heavy oil products using the fixed bed process: the catalytic reaction conditions will be relatively harsh because the heavy oil products are heavy and contain more mechanical impurities; high-nitrogen raw materials will accelerate catalyst deactivation Very short, the product...

Examples

Embodiment 1

[0041] Preparation of modified alumina G-1

[0042] Take the filter cake after washing the alumina precursor prepared by the carbonization method, measure its dry basis as 30wt%, take 1500 grams of the filter cake, add 2.5 liters of deionized water, make a slurry, heat up to 65 ° C, stir for 1 hour, add 90 gram of 85m% phosphoric acid solution, filtered to obtain a filter cake, added 2.0 liters of deionized water, beating, heated to 70 ° C, and added 86 grams of boric acid, and with a concentration of 10gNH 3 / 100ml of ammonia solution to adjust the pH value of the solution to 6, stir for 1 hour, filter and dry at 110°C for 4 hours, the sample is G-1, and its physical and chemical properties are shown in Table 1.

Embodiment 2

[0044] Preparation of modified alumina G-2.

[0045] Take 800 grams of filter cake after washing the aluminum oxide precursor prepared by the aluminum sulfate method, the dry basis is 30wt%, add 3 liters of deionized water, stir evenly, heat up to 85 ° C, and add 53 grams of 85m% phosphoric acid solution, filter to obtain Cake, add 2.5 liters of deionized water, make a slurry, heat up to 70 ° C, and add 120 grams of boric acid, and use a concentration of 10 g NH 3 Adjust the pH of the solution to 6.5 per 100ml of ammonia solution, stir for 1 hour, continue stirring for 30 minutes, and dry at 110°C for 4 hours. The physical and chemical properties of sample G-2 are shown in Table 1.

[0046] Table 1 Physicochemical properties of samples

[0047] Example number

Embodiment 3

[0049] Preparation of ebullating bed hydrogenation catalyst C-1 for stable hydrogenation of heavy oil products of the present invention.

[0050] With 168 grams of G-1 and 18 grams of alumina fiber powder (length 30 microns, diameter 6 microns, specific surface 183m 2 / g, pore volume 0.08ml / g) is uniformly wetted with 238ml S-1 solution; 19 grams of nano-silica (the pure nano-silica produced by Tianjin Chemical Co., Ltd.) and 193.5 grams of SB powder (pore volume 0.46 ml / g, specific surface area 260m 2 / g) add the adhesive (30wt% on a dry basis, the acid-aluminum mol ratio is 0.3) of peptizing acid preparation, put into the roller compactor, grind to extrudable paste, extrusion, 110 ℃ of drying 4 hours, 550 ℃ for 3 hours to prepare catalyst C-1. The physical and chemical properties of the catalyst are listed in Table 2.

technical field

[0001] The invention relates to a preparation method of an ebullating bed hydrogenation treatment catalyst, in particular to a preparation method of an ebullation bed hydrogenation treatment catalyst used for the stable hydrogenation of heavy oil products. Background technique

[0002] The catalytic hydrogenation process usually used for heavy oil products is mainly a fixed bed hydrogenation process. Fixed bed reactors are especially suitable for handling lighter and cleaner feeds, such as naphtha, middle distillates, gas oils and ordinary residues. The fixed bed reactor is characterized by smoother operation and easier control. There are the following problems in the hydrotreating of heavy oil products using the fixed bed process: the catalytic reaction conditions will be relatively harsh because the heavy oil products are heavy and contain more mechanical impurities; high-nitrogen raw materials will accelerate catalyst deactivation Very short, the product...

Examples

Embodiment 1

[0041] Preparation of modified alumina G-1

[0042] Take the filter cake after washing the alumina precursor prepared by the carbonization method, measure its dry basis as 30wt%, take 1500 grams of the filter cake, add 2.5 liters of deionized water, make a slurry, heat up to 65 ° C, stir for 1 hour, add 90 gram of 85m% phosphoric acid solution, filtered to obtain a filter cake, added 2.0 liters of deionized water, beating, heated to 70 ° C, and added 86 grams of boric acid, and with a concentration of 10gNH 3 / 100ml of ammonia solution to adjust the pH value of the solution to 6, stir for 1 hour, filter and dry at 110°C for 4 hours, the sample is G-1, and its physical and chemical properties are shown in Table 1.

Embodiment 2

[0044] Preparation of modified alumina G-2.

[0045] Take 800 grams of filter cake after washing the aluminum oxide precursor prepared by the aluminum sulfate method, the dry basis is 30wt%, add 3 liters of deionized water, stir evenly, heat up to 85 ° C, and add 53 grams of 85m% phosphoric acid solution, filter to obtain Cake, add 2.5 liters of deionized water, make a slurry, heat up to 70 ° C, and add 120 grams of boric acid, and use a concentration of 10 g NH 3 Adjust the pH of the solution to 6.5 per 100ml of ammonia solution, stir for 1 hour, continue stirring for 30 minutes, and dry at 110°C for 4 hours. The physical and chemical properties of sample G-2 are shown in Table 1.

[0046] Table 1 Physicochemical properties of samples

[0047] Example number

Embodiment 3

[0049] Preparation of ebullating bed hydrogenation catalyst C-1 for stable hydrogenation of heavy oil products of the present invention.

[0050] With 168 grams of G-1 and 18 grams of alumina fiber powder (length 30 microns, diameter 6 microns, specific surface 183m 2 / g, pore volume 0.08ml / g) is uniformly wetted with 238ml S-1 solution; 19 grams of nano-silica (the pure nano-silica produced by Tianjin Chemical Co., Ltd.) and 193.5 grams of SB powder (pore volume 0.46 ml / g, specific surface area 260m 2 / g) add the adhesive (30wt% on a dry basis, the acid-aluminum mol ratio is 0.3) of peptizing acid preparation, put into the roller compactor, grind to extrudable paste, extrusion, 110 ℃ of drying 4 hours, 550 ℃ for 3 hours to prepare catalyst C-1. The physical and chemical properties of the catalyst are listed in Table 2.

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