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Preparation method of hydrofining catalyst composition

A technology for hydrorefining and catalysts, applied in chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, etc. The problem of low density of active centers, etc., can improve the performance of ultra-deep hydrodesulfurization, improve the interaction, and increase the density of active sites.

Active Publication Date: 2016-12-07
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0010] The bulk phase hydrogenation catalyst disclosed by CN102049265A adds ammonium bicarbonate during the coprecipitation process, and the bulk phase hydrogenation catalyst disclosed by CN102451703A adds carbon dioxide during the coprecipitation process to generate carbonate or bicarbonate. It releases a certain amount of gas during the roasting process. Under the impact of the gas, the pore volume and specific surface area of ​​the catalyst are increased, so that more metal active sites are exposed on the surface of the catalyst, but this method will cause some pores to collapse. , the pore distribution is dispersed, the mechanical strength is reduced, and the active metal is locally aggregated, and the exposed metal active sites are limited
The co-precipitation method adopted above will make the distribution of different hydrogenation active metals difficult to control, thereby affecting the distribution of different hydrogenation active metals and reducing the interaction between active metals. At the same time, the content of surface active metals in the catalyst is relatively low. Small and low active center density, which ultimately affects the ultra-deep hydrodesulfurization performance of the catalyst

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Dissolve nickel chloride and aluminum chloride solutions in clean water respectively, add polyethylene glycol with a molecular weight of 6000 that accounts for 25wt% of nickel and aluminum in the solution based on the weight of nickel oxide and aluminum oxide, and prepare mixed solution A, mixed solution The weight concentration of NiO in A is 19g / L, Al 2 o 3 The weight concentration is 13g / L. Dissolve ammonium metatungstate, ammonium molybdate and aluminum chloride solution in clean water respectively to prepare mixed solution B, and in mixed solution B, WO 3 The weight concentration is 39g / L, MoO 3 The weight concentration is 16g / L, Al 2 o 3 The weight concentration is 13g / L. The temperature of the solution in reaction tank 1 was raised to 40°C, and ammonia water with a concentration of 25wt% was added to solution A until a dark blue solution was formed. 7.8, to obtain the precipitate slurry I containing nickel and aluminum. Add 1000mL of clean water into the r...

Embodiment 2

[0041]According to the method of embodiment 1, press the component content ratio of catalyst composition B in table 1, add nickel nitrate, aluminum nitrate, zirconium oxychloride solution in dissolving tank 1, add nickel and aluminum in the solution to oxidize 15wt% polyvinyl alcohol with a molecular weight of 18,000 based on the weight of nickel and aluminum oxide was uniformly stirred to form solution A. Add aluminum nitrate, ammonium metatungstate and ammonium molybdate into the dissolution tank 2 to prepare working solution B. The temperature of the solution in reaction tank 1 was raised to 50°C, and ammonia water with a concentration of 20wt% was added to solution A until a dark blue solution was formed. 8.2, Obtain the precipitate slurry I containing nickel and aluminum. Add 1000mL of clean water into the reaction tank 2, add ammonia water with a concentration of 8 wt% and solution B into the reaction tank 2 in parallel, keep the gelling temperature at 55°C, and control...

Embodiment 3

[0043] According to the method of embodiment 1, press the component content proportioning ratio of catalyst composition C in table 1, add nickel chloride, aluminum chloride, phosphoric acid solution in dissolving tank 1, add nickel and aluminum in the solution with nickel oxide Mix polyvinyl alcohol with a molecular weight of 14000 and 40wt% by weight of alumina, stir evenly and configure solution A, add aluminum chloride, ammonium metatungstate and ammonium molybdate to the dissolution tank 2 to prepare working solution B. The temperature of the solution in reaction tank 1 was raised to 55°C, and ammonia water with a concentration of 18wt% was added to solution A until a dark blue solution was formed. 8.0, the precipitate slurry I containing nickel and aluminum was obtained. Add 1000mL of clean water into the reaction tank, add ammonia water with a concentration of 12 wt % and solution B into the reaction tank concurrently, keep the gelling temperature at 50°C, and control th...

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Abstract

The invention discloses a preparation method of a hydrofining catalyst composition. The catalyst composition is a bulk phase hydrofining catalyst composition, and comprises hydrogenation active metal components W, Ni and MO, and alumina. The preparation method of the catalyst composition comprises the following steps: preparing a nickel and aluminum mixed precipitate through an ammonia distillation and precipitation technology in the presence of an organic compound, preparing a tungsten, molybdenum and aluminum mixed precipitate through a parallel flow precipitation technology, mixing the nickel and aluminum mixed precipitate with the tungsten, molybdenum and aluminum mixed precipitate, ageing the obtained mixture, carrying out hydrothermal treatment and adding urea, and molding the finally obtained mixture to prepare the catalyst composition. The catalyst composition prepared through the method is especially suitable for being applied to ultra deep hydrodesulfurization and nitrogen removal reactions of diesel oil fractions, and has high hydrodesulfurization and hydrodenitrogenation reaction performances.

Description

technical field [0001] The invention relates to a method for preparing a hydrorefining catalyst composition, in particular to a method for preparing a high-activity bulk phase hydrotreating catalyst composition. Background technique [0002] At present, in the world, crude oil is becoming increasingly heavy and inferior, coupled with the continuous development of the world economy and increasingly stringent environmental protection regulations, it is necessary to produce a large amount of light clean fuel. The development and use of ultra-low sulfur or even sulfur-free gasoline and diesel is the trend of clean fuel development in the world today. The use of traditional hydrodesulfurization catalysts can also achieve deep desulfurization or even ultra-deep desulfurization of diesel oil by increasing the severity of the reaction, such as increasing the reaction temperature, hydrogen partial pressure or reducing the reaction space velocity, but the increase in the reaction temp...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/888C10G45/08
Inventor 王海涛徐学军刘东香冯小萍
Owner CHINA PETROLEUM & CHEM CORP
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