Alumina carrier and preparation method thereof

Abstract

The invention discloses an alumina carrier and a preparation method thereof. In the alumina carrier, aluminum hydroxide gel prepared by a molten salt supersolubilizing micelle method is taken as a raw material. After a surfactant and a hydrocarbon component contained in the gel are molded and baked, nano-alumina particles formed by removing water from the polymerized aluminum hydroxide still have a basic rod-shaped structure and are piled up in an unordered way so as to form a frame structure. The alumina carrier has the characteristics of large pore volume, large pore diameter, high porosity, large orifice on the outer surface and high pore canal penetrability. In particular for macromolecules, the alumina carrier prevents catalyst inactivation caused by the blocking of an ink bottle-shaped orifice, so that impurity deposition is increased, and the running period of a catalyst is prolonged. The alumina carrier can be applied to a catalytic reaction which contains a macromolecule reactant or a macromolecule product.

Description

technical field

[0001] The invention relates to an alumina carrier and a preparation method thereof, in particular to a large-capacity mesoporous alumina carrier and a preparation method thereof. Background technique

[0002] With the increasingly heavy and poor quality of petroleum, it brings more and more difficulties to petroleum processing. At the same time, people's awareness of environmental protection is constantly increasing, and environmental protection regulations are becoming more and more stringent. x , SO x And the restrictions on aromatics content are more stringent.

[0003] At present, hydroprocessing is still the most important means to produce high-quality, environment-friendly petroleum products. The core of hydroprocessing technology is the catalyst, and the performance of the carrier is the key to preparing a hydroprocessing catalyst with excellent properties. For the heavy components of petroleum (such as VGO, especially residual oil), the pore size...

Examples

Embodiment 1

[0046] Under stirring conditions, 375g of aluminum nitrate nonahydrate and 90g of urea were mixed and heated to 100°C, and added to a mixture of 32g of polyisobutylene maleate triethanolamine maleate and 88g of 150 HVI neutral oil at the same temperature to form a supersolubilizer group, and then reacted at 100°C for 3 hours to obtain nano-aluminum hydroxide gel. Wash three times with 200ml of distilled water, and dry at 120°C for 10 hours. Nano-aluminum hydroxide gel dry powder and binding agent pseudo-boehmite are mixed uniformly in a weight ratio of 3: 1; 26g dilute nitric acid (mass concentration 17%), 160g water and 10g cosolvent are mixed uniformly, and then added to In the mixture of nano-aluminum hydroxide gel dry powder and binder, stir evenly, mix evenly on a mixer, and then shape it in an extruder, controlling the pressure at 10MPa. The molded product was dried at 100°C for 10 hours, calcined at 240°C for 3 hours, and then calcined at 850°C for 4 hours with a heati...

Embodiment 2

[0048] The alumina carrier A1 obtained in Example 1 is impregnated with active metals, and the resulting residue hydrodemetallization catalyst HDM-1 contains 4% (mass fraction) MoO 3 , 2% (mass fraction) NiO.

[0049] The residual oil hydrodemetallization catalyst HDM-1 was used in the hydrodemetallization experiment of the residual oil raw material (see Table 1 for properties), and the test conditions were as follows: temperature 390°C, hydrogen-to-oil volume ratio 1000, liquid hourly volume space velocity 1.0h -1 , hydrogen partial pressure 15.4MPa, continuous operation for 3000 hours, the pore properties of the catalyst after operation are shown in Table 3. Investigate the diffusion and metal distribution of metal precipitation in the catalyst pores in residual oil, and use JSM-7500F cold field emission scanning electron microscope (FESEM) to measure the metal distribution, cross-cut the catalyst along half of the longitudinal direction, and then measure along the long axis...

Embodiment 3

[0059] Mix 90g minus three-line dewaxed oil and 70g SP-80, heat to dissolve at 80°C, and mix well; heat 620g of aluminum nitrate nonahydrate to 80°C to melt, slowly add to the above mixture, and mix for 20 minutes to form a uniform supersolubilized colloid. 220 g of saturated ammonia water at 20° C. was added dropwise and aged for 3 hours to obtain a nano-aluminum hydroxide gel. Wash three times with 200ml of distilled water, and dry at 120°C for 10 hours. Nano-aluminum hydroxide gel dry powder and binder pseudo-boehmite are mixed uniformly in a weight ratio of 3: 1; 32g dilute nitric acid (mass concentration 17%), 150g water and 32g cosolvent ethanol are mixed uniformly, and then add Put it into the mixture of nano-aluminum hydroxide gel dry powder and binder, stir evenly, mix evenly on a mixer, and then shape it in an extruder, controlling the pressure at 23MPa. The molded product was dried at 100°C for 10 hours, calcined at 240°C for 3 hours, and then calcined at 850°C for...

technical field

[0001] The invention relates to an alumina carrier and a preparation method thereof, in particular to a large-capacity mesoporous alumina carrier and a preparation method thereof. Background technique

[0002] With the increasingly heavy and poor quality of petroleum, it brings more and more difficulties to petroleum processing. At the same time, people's awareness of environmental protection is constantly increasing, and environmental protection regulations are becoming more and more stringent. x , SO x And the restrictions on aromatics content are more stringent.

[0003] At present, hydroprocessing is still the most important means to produce high-quality, environment-friendly petroleum products. The core of hydroprocessing technology is the catalyst, and the performance of the carrier is the key to preparing a hydroprocessing catalyst with excellent properties. For the heavy components of petroleum (such as VGO, especially residual oil), the pore size...

Examples

Embodiment 1

[0046] Under stirring conditions, 375g of aluminum nitrate nonahydrate and 90g of urea were mixed and heated to 100°C, and added to a mixture of 32g of polyisobutylene maleate triethanolamine maleate and 88g of 150 HVI neutral oil at the same temperature to form a supersolubilizer group, and then reacted at 100°C for 3 hours to obtain nano-aluminum hydroxide gel. Wash three times with 200ml of distilled water, and dry at 120°C for 10 hours. Nano-aluminum hydroxide gel dry powder and binding agent pseudo-boehmite are mixed uniformly in a weight ratio of 3: 1; 26g dilute nitric acid (mass concentration 17%), 160g water and 10g cosolvent are mixed uniformly, and then added to In the mixture of nano-aluminum hydroxide gel dry powder and binder, stir evenly, mix evenly on a mixer, and then shape it in an extruder, controlling the pressure at 10MPa. The molded product was dried at 100°C for 10 hours, calcined at 240°C for 3 hours, and then calcined at 850°C for 4 hours with a heati...

Embodiment 2

[0048] The alumina carrier A1 obtained in Example 1 is impregnated with active metals, and the resulting residue hydrodemetallization catalyst HDM-1 contains 4% (mass fraction) MoO 3 , 2% (mass fraction) NiO.

[0049] The residual oil hydrodemetallization catalyst HDM-1 was used in the hydrodemetallization experiment of the residual oil raw material (see Table 1 for properties), and the test conditions were as follows: temperature 390°C, hydrogen-to-oil volume ratio 1000, liquid hourly volume space velocity 1.0h -1 , hydrogen partial pressure 15.4MPa, continuous operation for 3000 hours, the pore properties of the catalyst after operation are shown in Table 3. Investigate the diffusion and metal distribution of metal precipitation in the catalyst pores in residual oil, and use JSM-7500F cold field emission scanning electron microscope (FESEM) to measure the metal distribution, cross-cut the catalyst along half of the longitudinal direction, and then measure along the long axis...

Embodiment 3

[0059] Mix 90g minus three-line dewaxed oil and 70g SP-80, heat to dissolve at 80°C, and mix well; heat 620g of aluminum nitrate nonahydrate to 80°C to melt, slowly add to the above mixture, and mix for 20 minutes to form a uniform supersolubilized colloid. 220 g of saturated ammonia water at 20° C. was added dropwise and aged for 3 hours to obtain a nano-aluminum hydroxide gel. Wash three times with 200ml of distilled water, and dry at 120°C for 10 hours. Nano-aluminum hydroxide gel dry powder and binder pseudo-boehmite are mixed uniformly in a weight ratio of 3: 1; 32g dilute nitric acid (mass concentration 17%), 150g water and 32g cosolvent ethanol are mixed uniformly, and then add Put it into the mixture of nano-aluminum hydroxide gel dry powder and binder, stir evenly, mix evenly on a mixer, and then shape it in an extruder, controlling the pressure at 23MPa. The molded product was dried at 100°C for 10 hours, calcined at 240°C for 3 hours, and then calcined at 850°C for...

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