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Preparation method of hydrotreatment catalyst

A hydrogenation treatment and catalyst technology, applied in physical/chemical process catalysts, chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, etc., can solve the limitation of catalyst activity improvement and affect the dispersion of active metals , Catalyst activity reduction and other issues, to achieve the effect of enhancing the promotion effect, facilitating dispersion, and reducing the rate of activity loss

Active Publication Date: 2012-10-17
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Adding an organic complexing agent in this method improves the stability of boron, but due to simultaneous impregnation with active metals, boron and active metals compete with the carrier for adsorption, which affects the dispersion of active metals on the carrier.
At the same time, the promotion effect of boron on the conversion of type I active phase to type II active phase with higher activity is bound to be weakened, which limits the improvement of the activity of this type of catalyst.
In addition, since boron is introduced after the alumina carrier is formed, it has little effect on the pore structure and channel of the alumina carrier, and does not play a role in pore expansion; the acid center type of the carrier is not adjusted before loading the active metal; It does not weaken the strong interaction between the active metal and the support, which reduces the activity of the catalyst

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] will contain Al 2 o 3 5g / 100mL AlCl 3 Solution 2000mL with NH 3 10g / 100mL of ammonia water was added dropwise into the gelling reaction tank stirred at a temperature of 60°C, and the pH value was maintained at 7.6, and the reaction contact time was 40min. Aging was performed at a temperature of 70°C and a pH of 8.0. The aging time is 1h. The product was filtered, and then washed with deionized water with a solid-to-liquid volume ratio of 1:20 at a washing temperature of 80°C for 3 times. The obtained filter cake was dried at 120° C. for 3 h to obtain aluminum hydroxide.

[0034] Take 100g of the above-mentioned aluminum hydroxide, mix it with 110g of SB alumina powder peptized by nitric acid, knead for 20min, make a plastic paste, and extrude it through a clover orifice plate with a diameter of 1.4mm. After the wet strip was dried at 130°C for 8h, it was calcined at 520°C for 4h to obtain alumina carrier S-1.

Embodiment 2

[0036] After the gelation of Example 1, dropwise add the SiO-containing 2 2g / 100mL simethicone oil 100mL, aged at 70°C for 80min, then added 2 o 3 3g / 100mL organic compound solution 100mL, the boron-containing organic compound solution is prepared by dissolving boric acid in water, and the molar ratio of boric acid to mannitol is 1:1. Others are the same as in Example 1, and aluminum hydroxide containing silicon and boron is obtained. .

[0037] Take 120g of the above-mentioned aluminum hydroxide containing silicon and boron, mix it with 126g of SB alumina powder peptized by nitric acid and an aqueous solution containing molybdenum and cobalt, and knead for 20 minutes to make a plastic paste, and squeeze it through a clover orifice of φ1.4mm strip. The wet strips were dried at 130°C for 3 hours, then calcined at a constant temperature of 210°C for 2 hours, at a constant temperature of 320°C for 1.0 hours, and at a constant temperature of 530°C for 3.0 hours to obtain a ca...

Embodiment 3

[0039] After the gelation of Example 1, dropwise add the SiO-containing 2 2g / 100mL methyl silicone oil 100mL, aging at 70°C for 80min, then add B 2 o 3 100mL of 3g / 100mL organic compound solution, the boron-containing organic compound solution is prepared by dissolving boric acid in water, and the molar ratio of boric acid to ethylene glycol is 1.0:1.5, and then aging at 70°C for 80min, and the other same implementation Example 1, obtain the aluminum hydroxide containing silicon and boron.

[0040] Take 110g of the above-mentioned aluminum borohydroxide containing silicon and borohydroxide, mix it with 118g of SB alumina powder peptized by nitric acid and an aqueous solution containing molybdenum and phosphorus, and knead for 20 minutes to make a plastic paste, and extrude it through a clover orifice plate with a diameter of φ1.4mm . The wet bar was dried at 140°C for 3h, then calcined at 190°C for 0.5h, at 350°C for 2.0h, and at 530°C for 2.0h to obtain the catalyst C-3 ...

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Abstract

The invention discloses a preparation method of a hydrotreatment catalyst, comprising the following steps of: introducing silicon and boron additives in the way that an organic silicon source is added after aluminium hydroxide gel forming and then a boron-containing organic compound solution is added, so as to obtain silicon and boron containing aluminium hydroxide, mixing parts of an active metal component with boron-containing aluminium hydroxide by a kneading method, carrying out three-stage roasting to obtain a catalyst intermediate, loading residual part of the active metal onto the catalyst intermediate by dipping, and drying to obtain the hydrotreatment catalyst. By the adoption of the method provided by the invention, the silicon and boron additives and the active metal component are uniformly distributed on the surface of the catalyst. In addition, the active metal component has different existing forms in the catalyst when introduced in the two modes, loss rate of the catalyst activity is reduced by mutual cooperation, and running period of a device is prolonged. The catalyst has large pore volume, large specific surface area, appropriate pore structure and acidity, and is especially suitable for hydrodenitrogenation process of heavy hydrocarbon.

Description

technical field [0001] The invention relates to a preparation method of a hydrogenation treatment catalyst, in particular to a preparation method of a hydrogenation treatment catalyst with large pore volume and large specific surface area. Background technique [0002] At present, countries all over the world have increasingly stringent requirements on vehicle fuels, especially the content of sulfur, nitrogen and aromatics. However, as the amount of oil extracted increases, it becomes heavier and worse day by day, and the human demand for vehicle fuel continues to increase, which makes it more and more difficult for refineries to process oil. Among them, hydrogenation technology is one of the important technologies for producing qualified fuels. Under the above-mentioned background, the raw materials processed by this technology are also deteriorating and becoming heavier, which constantly puts forward new requirements for hydrogenation catalysts. [0003] Hydrogenation cat...

Claims

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Application Information

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IPC IPC(8): B01J23/882B01J27/19B01J23/889C10G45/08
Inventor 王敏汤涛凌凤香孙万付王少军马涛刘丽华
Owner CHINA PETROLEUM & CHEM CORP
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