A carrier, catalyst and preparation method for hydrodesulfurization

Abstract

The invention discloses a carrier, a catalyst and a preparation method for hydrodesulfurization. The carrier is an auxiliary-containing alumina carrier. The auxiliary-containing alumina carrier includes main alumina and rod-shaped alumina. The main alumina is alumina with micron-scale pores, and at least part of the rod-shaped alumina is distributed in the main body. On the outer surface of the alumina and in the micron-sized pores, the auxiliary agent is phosphorus and / or boron. The preparation method of the carrier is as follows: a physical pore-enlarging agent is adsorbed to a solution containing an auxiliary agent, and then the pseudo-boehmite and the physical pore-enlarging agent of the adsorption auxiliary agent are kneaded and formed, and the molded product is dried and roasted to obtain a carrier intermediate; Then immerse the carrier intermediate in the ammonium bicarbonate solution, and then seal and heat treat the material. After the heat treatment, the material is dried and calcined to obtain the hydrogenation desulfurization catalyst carrier. The hydrodesulfurization catalyst is especially suitable for the hydrodesulfurization treatment process of residual oil, and has the characteristics of good macromolecular diffusion performance, strong metal-accommodating ability, and high desulfurization ability.

Description

technical field

[0001] The invention relates to an alumina carrier, a catalyst and a preparation method thereof, in particular to a catalyst carrier, a catalyst and a preparation method thereof for residual oil hydrodesulfurization. Background technique

[0002] With the increasingly heavy and poor quality of petroleum, it brings more and more difficulties to petroleum processing. Heavy oil residues contain a large amount of sulfur, most of which exist in asphaltene, which is a component that is difficult to remove. As an important process in petroleum refining and synthetic ammonia production using petroleum as raw material, hydrodesulfurization has always been valued by people. However, in recent years, the quality of petroleum has become heavier and worse, while the requirements for product quality have become more stringent, and the requirements for feed materials in subsequent processes have become more and more stringent. In addition, since mankind entered the 21st c...

Examples

Embodiment 1

[0049] Weigh 25 grams of activated carbon with a particle size of 6 microns, spray and impregnate the above-mentioned activated carbon with 7.5 mL of ammonium hydrogen phosphate solution with a mass concentration of 28%, and mix the activated carbon with 260 grams of pseudoboehmite dry rubber powder (Wenzhou Jing Crystal Alumina Co., Ltd.), 8 grams of Squatia powder, mixed evenly, adding an appropriate amount of 1.5% acetic acid aqueous solution, kneaded, extruded, and dried at 100 ° C for 6 hours, and dried at 700 °C in an air atmosphere ℃ for 5 hours to obtain the alumina carrier intermediate ZA1.

[0050] Weigh 100 grams of the above-mentioned alumina carrier intermediate ZA1, place it in 500 grams of ammonium bicarbonate solution, the mass concentration of the ammonium bicarbonate solution is 14% aqueous solution, transfer the mixed material into an autoclave and seal it, and heat it at 15°C Raise the temperature to 100°C at a speed of 10°C / min and keep the temperature for...

Embodiment 2

[0052] Same as Example 1, except that the activated carbon was changed to charcoal with a particle size of 4 microns, and the amount of charcoal added was 29 grams to obtain the alumina carrier intermediate ZA2. The quality of ammonium bicarbonate solution is 600 grams, and the mass concentration of ammonium bicarbonate solution is 17.5%. The sealing pretreatment temperature was 90°C, the treatment time was 2 hours, the heat treatment temperature was 110°C, and the treatment time was 8 hours, and the alumina carrier A2 was prepared. The properties of the carrier are shown in Table 1. P in the alumina carrier A2 2 o 5 The content is 1.5wt%, the length of the rod-shaped alumina in the micron-sized pores is mainly 1-3.5 μm, the length of the rod-shaped alumina on the outer surface of the main alumina is mainly 3-8 μm, and the rod-shaped alumina on the outer surface of the main alumina The coverage rate of alumina accounts for about 78%, and the coverage rate of rod-shaped alumi...

Embodiment 3

[0054] The same as in Example 1, except that the activated carbon was changed to wood chips with a particle size of 7 microns, and the amount of wood chips added was 21 grams to obtain the alumina carrier intermediate ZA3. The quality of ammonium bicarbonate solution is 300 grams, and the mass concentration of ammonium bicarbonate solution is 20%. The heating rate before sealing pretreatment was 11°C / min, the heating rate after sealing pretreatment was 5°C / min, the heat treatment temperature was 150°C, and the treatment time was 4 hours to prepare alumina carrier A3. The properties of the carrier are shown in the table 1. P in the alumina carrier A3 2 o 5 The content is 0.8wt%, the length of the rod-shaped alumina in the micron-sized pores is mainly 2.0-6.0 μm, the length of the rod-shaped alumina on the outer surface of the main alumina is mainly 3-8 μm, and the rod-shaped alumina on the outer surface of the main alumina The coverage rate of alumina accounts for about 83%,...

technical field

[0001] The invention relates to an alumina carrier, a catalyst and a preparation method thereof, in particular to a catalyst carrier, a catalyst and a preparation method thereof for residual oil hydrodesulfurization. Background technique

[0002] With the increasingly heavy and poor quality of petroleum, it brings more and more difficulties to petroleum processing. Heavy oil residues contain a large amount of sulfur, most of which exist in asphaltene, which is a component that is difficult to remove. As an important process in petroleum refining and synthetic ammonia production using petroleum as raw material, hydrodesulfurization has always been valued by people. However, in recent years, the quality of petroleum has become heavier and worse, while the requirements for product quality have become more stringent, and the requirements for feed materials in subsequent processes have become more and more stringent. In addition, since mankind entered the 21st c...

Examples

Embodiment 1

[0049] Weigh 25 grams of activated carbon with a particle size of 6 microns, spray and impregnate the above-mentioned activated carbon with 7.5 mL of ammonium hydrogen phosphate solution with a mass concentration of 28%, and mix the activated carbon with 260 grams of pseudoboehmite dry rubber powder (Wenzhou Jing Crystal Alumina Co., Ltd.), 8 grams of Squatia powder, mixed evenly, adding an appropriate amount of 1.5% acetic acid aqueous solution, kneaded, extruded, and dried at 100 ° C for 6 hours, and dried at 700 °C in an air atmosphere ℃ for 5 hours to obtain the alumina carrier intermediate ZA1.

[0050] Weigh 100 grams of the above-mentioned alumina carrier intermediate ZA1, place it in 500 grams of ammonium bicarbonate solution, the mass concentration of the ammonium bicarbonate solution is 14% aqueous solution, transfer the mixed material into an autoclave and seal it, and heat it at 15°C Raise the temperature to 100°C at a speed of 10°C / min and keep the temperature for...

Embodiment 2

[0052] Same as Example 1, except that the activated carbon was changed to charcoal with a particle size of 4 microns, and the amount of charcoal added was 29 grams to obtain the alumina carrier intermediate ZA2. The quality of ammonium bicarbonate solution is 600 grams, and the mass concentration of ammonium bicarbonate solution is 17.5%. The sealing pretreatment temperature was 90°C, the treatment time was 2 hours, the heat treatment temperature was 110°C, and the treatment time was 8 hours, and the alumina carrier A2 was prepared. The properties of the carrier are shown in Table 1. P in the alumina carrier A2 2 o 5 The content is 1.5wt%, the length of the rod-shaped alumina in the micron-sized pores is mainly 1-3.5 μm, the length of the rod-shaped alumina on the outer surface of the main alumina is mainly 3-8 μm, and the rod-shaped alumina on the outer surface of the main alumina The coverage rate of alumina accounts for about 78%, and the coverage rate of rod-shaped alumi...

Embodiment 3

[0054] The same as in Example 1, except that the activated carbon was changed to wood chips with a particle size of 7 microns, and the amount of wood chips added was 21 grams to obtain the alumina carrier intermediate ZA3. The quality of ammonium bicarbonate solution is 300 grams, and the mass concentration of ammonium bicarbonate solution is 20%. The heating rate before sealing pretreatment was 11°C / min, the heating rate after sealing pretreatment was 5°C / min, the heat treatment temperature was 150°C, and the treatment time was 4 hours to prepare alumina carrier A3. The properties of the carrier are shown in the table 1. P in the alumina carrier A3 2 o 5 The content is 0.8wt%, the length of the rod-shaped alumina in the micron-sized pores is mainly 2.0-6.0 μm, the length of the rod-shaped alumina on the outer surface of the main alumina is mainly 3-8 μm, and the rod-shaped alumina on the outer surface of the main alumina The coverage rate of alumina accounts for about 83%,...

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