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Preparation method of hydrotreating 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 problems, to achieve the effect of easy operation, improved dispersion and increased pore volume

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

[0031] Will contain Al 2 O 3 5g / 100mL AlCl 3 Solution 2000mL and containing NH 3 10g / 100mL ammonia water was added dropwise to the gelling reaction tank with stirring at a temperature of 60°C, keeping the pH value at 7.6, the reaction contact time was 40min, and aging was carried out at a temperature of 70°C and a pH value of 8.0. The aging time was 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 and washing times for 3 times. The resulting filter cake was dried at 120°C for 3 hours to obtain aluminum hydroxide.

[0032] Take 100g of the above aluminum hydroxide, mix with 110g of SB alumina powder peptized by nitric acid, knead for 20 minutes, make a plastic paste, and extrude it through a 1.4mm clover orifice plate. After drying the wet bar at 130°C for 8 hours, it was calcined at 520°C for 4 hours to obtain alumina carrier S-1.

Embodiment 2

[0034] After the gelation of Example 1, add SiO 2 2g / 100mL Dimethicone 100mL, aging at 70℃ 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 at a molar ratio of boric acid to mannitol of 1:1. Others are the same as in Example 1, to obtain silicon and boron-containing aluminum hydroxide .

[0035] Take 120g of the above-mentioned silicon and boron-containing aluminum hydroxide, mix 130g of SB alumina powder peptized by nitric acid and an aqueous solution containing molybdenum and cobalt, knead it for 20 minutes, make a plastic paste, and squeeze it through a 1.4mm clover orifice plate Article. The wet bar was dried at 130°C for 3 hours, then calcined at 220°C for 1 hour, at 310°C for 2.0 hours, and at 540°C for 3.0 hours to obtain catalyst C-2. In this catalyst, MoO 3 The weight content of CoO is 11.9%, and the weight content of CoO is 3.0%.

Embodiment 3

[0037] After the gelation of Example 1, add SiO 2 2g / 100mL methyl silicone oil 100mL, aging at 70℃ 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 at a molar ratio of boric acid to ethylene glycol of 1.0:1.5, and then aging at 70°C. The aging time is 80min. Others are the same. In Example 1, aluminum hydroxide containing silicon and boron was obtained.

[0038] Take 110g of the above-mentioned silicon and aluminum borohydride, mix 116g of SB alumina powder peptized by nitric acid and an aqueous solution containing molybdenum, nickel and phosphorus, kneading for 20 minutes, make a plastic paste, and pass it through a 1.4mm clover orifice plate Squeeze. The wet bar was dried at 140°C for 2h, then calcined at 220°C for 1h, at 330°C for 1.0h, and at 540°C for 3.0h to obtain catalyst C-3. In this catalyst, MoO 3 The weight content of NiO is 23.8%, the weight content ...

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Abstract

The invention discloses a preparation method of a hydrotreating 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 an active metal component with silicon and boron containing aluminium hydroxide by a kneading method, and carrying out three-stage roasting to obtain the hydrotreating catalyst. The method provided by the invention is beneficial to uniform distribution of the silicon and boron additives and the active metal component in the catalyst and enhances the positive effect of the boron additive on active phase transition. In addition, the obtained catalyst has advantages of large pore volume, large specific surface area and appropriate pore structure and acidity. The preparation method is used to raise activity and stability of the catalyst and is especially suitable for hydro-denitrification of heavier hydrocarbons.

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): B01J23/882B01J27/19B01J23/888C10G45/08
Inventor 王敏刘丽华凌凤香孙万付王少军汤涛
Owner CHINA PETROLEUM & CHEM CORP
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