Preparation method of hydrodemetallization catalyst

Abstract

The invention discloses a method for preparing a hydrodemetallization catalyst, which includes the following contents: (1) Prepare at least two kinds of aqueous solutions of polyols and / or monosaccharides with different concentrations, and spray and immerse them in aluminum oxide in order of concentration from high to low. on the carrier, so that the concentration of polyols and / or monosaccharides forms a gradient distribution from outside to inside, from low to high; (2) Dry the impregnated alumina carrier, and then impregnate it with active components and urea impregnating the above-mentioned alumina carrier with liquid, and performing hydrothermal treatment on the wet agent in a sealed container; (3) drying the material obtained in step (2), and then treating it at high temperature without oxygen to obtain a hydrodemetallization catalyst. The carbon content in the catalyst prepared by the method of the invention presents a gradient distribution, the active component is easy to be completely vulcanized, and the active metal component is evenly distributed on the surface of the carrier, thereby significantly improving the demetallization activity of the catalyst.

Description

Technical field

[0001] The invention belongs to the field of catalyst preparation, and specifically relates to a method for preparing a hydrodemetalization catalyst. Background technique

[0002] At present, the most common hydrogenation catalysts are generally supported catalysts with alumina, silica, etc. as carriers, and metals such as Co, Ni, Mo, and W as active components. The active component is loaded on the carrier by impregnation or kneading, and then dried and calcined to prepare the catalyst. When the wet agent after immersion dries, the active components in the immersion solution will gradually evaporate with the solvent, which will easily form larger particles of active species in the pores of the carrier, causing part of the pores in the carrier to be blocked, and the solvent is evaporating The migration will also cause uneven distribution of active components, and ultimately affect the activity of the catalyst. In addition, during the calcination process, the act...

Examples

Embodiment 1

[0031] Weigh the pore volume to 0.9ml / g, and the specific surface area to be 220m 2 100 grams of γ-phase cylindrical alumina carrier per g is put into the spray rolling pan, and in the rotating state, the carrier in the rolling pan is sprayed and impregnated with 25ml xylitol aqueous solution with a mass concentration of 40% ; Then use 40ml of xylitol aqueous solution with a mass concentration of 20% to continue to spray and impregnate the alumina carrier; finally, use 40ml of xylitol aqueous solution with a mass concentration of 10% to continue to spray and impregnate the alumina carrier. The impregnated alumina support was dried at 110°C for 8 hours. Then use 150ml containing MoO 3 10 g / 100ml (molybdenum source comes from ammonium molybdate), NiO 1.5 g / 100ml (nickel source comes from nickel chloride), urea 26 g / 100ml impregnation solution to impregnate the above carrier for 5 hours, filter out the excess solution, remove the wet agent Transfer to an autoclave and place the au...

Embodiment 2

[0033] Same as Example 1, except that the alumina carrier is in the shape of clover strips. For the first spray dipping, 30ml of sorbitol with a mass concentration of 30% was used. For the second spray dipping, 50ml of sorbitol with a mass concentration of 10% was used. For the alcohol aqueous solution, 20ml of sorbitol aqueous solution with a mass concentration of 5% was used for the third spray dipping. The active component impregnating liquid contains MoO 3 8g / 100ml (molybdenum source comes from ammonium molybdate), NiO1g / 100ml (nickel source comes from nickel chloride), urea 22g / 100ml impregnating the above carrier. During the hydrothermal treatment, firstly, it was sealed and heat-treated at 130° C. for 6 hours, and then heated to 220° C. for 10 hours to prepare the hydrodemetalization catalyst C2 of the present invention. The properties of the catalyst are shown in Table 1.

Embodiment 3

[0035] Same as Example 1, except that four times of spray dipping were used. For the first spray dipping, 20ml of mannitol with a mass concentration of 50% was used. For the second spray dipping, 40ml of sorbitol with a mass concentration of 30% was used. In the third spray dipping, 20ml of sorbitol aqueous solution with a mass concentration of 20% was used, and 20ml of sorbitol aqueous solution with a mass concentration of 10% in the fourth spray dipping. The active component impregnating liquid contains MoO 3 12 g / 100ml (molybdenum source comes from ammonium molybdate), NiO2 g / 100ml (nickel source comes from nickel chloride), urea 28 g / 100ml impregnating the above carrier. During the hydrothermal treatment, firstly, sealed and heat-treated at 120° C. for 8 hours, and then heated to 240° C., sealed and heat-treated for 6 hours to prepare the hydrodemetalization catalyst C3 of the present invention. The properties of the catalyst are shown in Table 1.

Technical field

[0001] The invention belongs to the field of catalyst preparation, and specifically relates to a method for preparing a hydrodemetalization catalyst. Background technique

[0002] At present, the most common hydrogenation catalysts are generally supported catalysts with alumina, silica, etc. as carriers, and metals such as Co, Ni, Mo, and W as active components. The active component is loaded on the carrier by impregnation or kneading, and then dried and calcined to prepare the catalyst. When the wet agent after immersion dries, the active components in the immersion solution will gradually evaporate with the solvent, which will easily form larger particles of active species in the pores of the carrier, causing part of the pores in the carrier to be blocked, and the solvent is evaporating The migration will also cause uneven distribution of active components, and ultimately affect the activity of the catalyst. In addition, during the calcination process, the act...

Examples

Embodiment 1

[0031] Weigh the pore volume to 0.9ml / g, and the specific surface area to be 220m 2 100 grams of γ-phase cylindrical alumina carrier per g is put into the spray rolling pan, and in the rotating state, the carrier in the rolling pan is sprayed and impregnated with 25ml xylitol aqueous solution with a mass concentration of 40% ; Then use 40ml of xylitol aqueous solution with a mass concentration of 20% to continue to spray and impregnate the alumina carrier; finally, use 40ml of xylitol aqueous solution with a mass concentration of 10% to continue to spray and impregnate the alumina carrier. The impregnated alumina support was dried at 110°C for 8 hours. Then use 150ml containing MoO 3 10 g / 100ml (molybdenum source comes from ammonium molybdate), NiO 1.5 g / 100ml (nickel source comes from nickel chloride), urea 26 g / 100ml impregnation solution to impregnate the above carrier for 5 hours, filter out the excess solution, remove the wet agent Transfer to an autoclave and place the au...

Embodiment 2

[0033] Same as Example 1, except that the alumina carrier is in the shape of clover strips. For the first spray dipping, 30ml of sorbitol with a mass concentration of 30% was used. For the second spray dipping, 50ml of sorbitol with a mass concentration of 10% was used. For the alcohol aqueous solution, 20ml of sorbitol aqueous solution with a mass concentration of 5% was used for the third spray dipping. The active component impregnating liquid contains MoO 3 8g / 100ml (molybdenum source comes from ammonium molybdate), NiO1g / 100ml (nickel source comes from nickel chloride), urea 22g / 100ml impregnating the above carrier. During the hydrothermal treatment, firstly, it was sealed and heat-treated at 130° C. for 6 hours, and then heated to 220° C. for 10 hours to prepare the hydrodemetalization catalyst C2 of the present invention. The properties of the catalyst are shown in Table 1.

Embodiment 3

[0035] Same as Example 1, except that four times of spray dipping were used. For the first spray dipping, 20ml of mannitol with a mass concentration of 50% was used. For the second spray dipping, 40ml of sorbitol with a mass concentration of 30% was used. In the third spray dipping, 20ml of sorbitol aqueous solution with a mass concentration of 20% was used, and 20ml of sorbitol aqueous solution with a mass concentration of 10% in the fourth spray dipping. The active component impregnating liquid contains MoO 3 12 g / 100ml (molybdenum source comes from ammonium molybdate), NiO2 g / 100ml (nickel source comes from nickel chloride), urea 28 g / 100ml impregnating the above carrier. During the hydrothermal treatment, firstly, sealed and heat-treated at 120° C. for 8 hours, and then heated to 240° C., sealed and heat-treated for 6 hours to prepare the hydrodemetalization catalyst C3 of the present invention. The properties of the catalyst are shown in Table 1.

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