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Titanium-based catalyst for diesel oil hydrofining and preparation method thereof

A technology for hydrorefining and catalysts, used in chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, etc.

Inactive Publication Date: 2012-08-15
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0012] There are following two disadvantages in the prior art diesel hydrotreating catalyst with TiO2 as carrier: one, the acidity of the catalyst is relatively Weak, not conducive to the desulfurization of fused ring sterically hindered sulfides through the isomerization pathway, and also unfavorable for direct desulfurization
Second, after the TiO2 carrier is calcined, its specific surface area and pore volume decrease, resulting in a low loading of active components of the catalyst, which cannot reach the level of Al2O3 The amount of load that can be achieved on the carrier

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] (1) Using the impregnation method, the specific surface area of ​​100 g is 250 m 2 / g, the pore volume is 0.5 cm 3 / g, titanium dioxide powder with anatase crystal structure and 50 g solution containing 17 g ammonium metatungstate and 2 g oxalic acid were contacted, dried at 120 °C for 5 h, and then calcined at 500 °C for 4 h to obtain WO 3 / TiO 2 Powder.

[0047] (2) Dissolve 4 g of gelatin in 70 g of a solution containing 25 g of nickel nitrate and 27 g of ammonium molybdate at a temperature of 85 °C, add 1 g of nitric acid during cooling, and stir well until a gel is formed.

[0048] (3) The WO of step (1) 3 / TiO 2 The powder, 6 g of pseudo-boehmite powder and the gel of step (2) are mixed, kneaded evenly, and extruded to obtain a catalyst precursor.

[0049] (4) The catalyst precursor in step (3) was dried at 120 °C for 5 h and calcined at 500 °C for 4 h to obtain a titanium-based catalyst for diesel hydrotreating.

[0050] The mass percent of each component ...

Embodiment 2

[0052] (1) Using the impregnation method, the specific surface area of ​​100 g is 250 m 2 / g, the pore volume is 0.5 cm 3 / g, titanium dioxide powder with anatase crystal structure and 50 g solution containing 17 g ammonium tungstate and 2 g lactic acid were contacted, dried at 120 °C for 5 h, and then calcined at 500 °C for 4 h to obtain WO 3 / TiO 2 Powder.

[0053] (2) Dissolve 4 g of methyl cellulose in 70 g of a solution containing 25 g of nickel chloride and 27 g of ammonium molybdate at a temperature of 85 °C, add 1 g of formic acid during the cooling process, and stir well until a gelatinous mixture is formed. glue.

[0054] (3) The WO of step (1) 3 / TiO 2 The powder, 6 g of pseudo-boehmite powder and the gel of step (2) are mixed, kneaded evenly, and extruded to obtain a catalyst precursor.

[0055] (4) The catalyst precursor in step (3) was dried at 120 °C for 5 h and calcined at 500 °C for 4 h to obtain a titanium-based catalyst for diesel hydrotreating.

[00...

Embodiment 3

[0058] (1) Using the impregnation method, the specific surface area of ​​100 g is 300 m 2 / g, the pore volume is 0.3 cm 3 / g, metatitanic acid powder with crystal structure of anatase contacted with 50 g of a solution containing 15 g of ammonium paratungstate and 2 g of malonic acid, dried at 120 °C for 5 h, and then calcined at 500 °C for 4 h. get WO 3 / TiO 2 Powder.

[0059] (2) Dissolve 3 g of hydroxyethyl cellulose in 70 g of a solution containing 25 g of nickel sulfate and 27 g of ammonium molybdate at a temperature of 50 °C, add 1 g of acetic acid during the cooling process, and stir well until a gelatinous mixture is formed. glue.

[0060] (3) The WO of step (1) 3 / TiO 2 The powder, 5 g of pseudo-boehmite powder and the gel of step (2) are mixed, kneaded evenly, and extruded to obtain a catalyst precursor.

[0061] (4) The catalyst precursor in step (3) was dried at 120 °C for 5 h and calcined at 500 °C for 4 h to obtain a titanium-based catalyst for diesel hydro...

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Abstract

The invention provides a titanium-based catalyst for diesel oil hydrofining and a preparation method of the titanium-based catalyst. Compared with the prior art, the titanium-based catalyst has the advantages that WO3 / TiO2 powder is taken as a carrier of the titanium-based catalyst for diesel oil hydrofining, so that the aim of the free adjustment of the acid quantity and the acid strength of the WO3 / TiO2 powder can be achieved by controlling the charge number and the roasting temperature of WO3; metallic ions of active components are fixed in gel grids of high-molecular compound with a three-dimensional structure, and the metallic ions are jointly molded in an extruding way with the WO3 / TiO2 powder, so that the charge number of the active components can be greatly improved; and an isolating layer is formed between the active components and the WO3 / TiO2 powder by the high-molecular compound, so that the mutual effect between the metallic oxide and the WO3 / TiO2 carrier can be weakened, the precursors of the active components under the oxidation state are easy to vulcanize, and the hydrodesulfurization and hydrodenitrogeneration capability of the catalyst can be remarkably improved.

Description

technical field [0001] The invention relates to a preparation method of a titanium-based catalyst for diesel hydrotreating, which can be used to catalyze the hydrodesulfurization and denitrogenation processes of any one of diesel oil, coked diesel oil, straight-run diesel oil, atmospheric and vacuum diesel oil or a combination thereof . Background technique [0002] In recent years, due to the increasing weight and deterioration of oil quality and stricter environmental protection legislation, the hydrorefining technology of diesel oil is developing in the direction of processing high-sulfur crude oil and producing ultra-low-sulfur clean petroleum fuel. Although there is room for cleanliness in the design and construction of diesel hydrotreating units in my country, most of the units still do not fully consider the rapid development of environmental improvement requirements, and it is difficult to adapt to the continuous improvement of oil quality requirements in the proces...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/888C10G45/08
Inventor 王继元樊继利钱中坚堵文斌陈韶辉杨爱武柏基业卞伯同许建文
Owner CHINA PETROLEUM & CHEM CORP