Hydrodenitrification catalyst carrier as well as preparation method and application thereof

A catalyst carrier, hydrodenitrogenation technology, applied in catalyst carrier, chemical instrument and method, metal/metal oxide/metal hydroxide catalyst, etc. Weak acidity and other problems, achieve highly ordered mesoporous pore structure, improve hydrogenation catalytic activity, and overcome the effect of strong interaction force

Pending Publication Date: 2022-03-29
PETROCHINA CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] CN1448468 discloses a method for preparing silicon-aluminum composite oxide by sol-gel method. Although the silicon-aluminum composite oxide prepared by the method has a large specific surface area and pore volume, the pore diameter of the silicon-aluminum composite oxide is The distribution is not concentrated, and the proportion of mesoporous channels is relatively small, which limits the diffusion and mass transfer of heavy oil macromolecules; The acidity of the protons on the surface of the composite oxide support is weak, which cannot meet the acidity requirements of the catalyst for the support material
[0005] CN102451670A discloses a method for preparing titanium-aluminum composite oxides. The co-current precipitation method is adopted. Titanium sulfate and sodium metaaluminate are used as precursors, and titanium dioxide is introduced to keep the pH value of the solution. The prepared titanium-aluminum composite oxides have It has the advantages of high specific surface area, large pore volume, good thermal stability, etc., and can be used as a carrier component of catalytic cracking, hydrocracking, and hydrotreating catalysts, showing excellent performance; but the preparation method steps are cumbersome, and the preparation The requirements for the preparation conditions (PH value, temperature) are very strict during the process, which limits the industrial application
[0008] In summary, the current preparation of titanium-aluminum composite oxides includes: sol-gel method, co-precipitation method, pH multiple swing method, etc. The prepared composite oxide has the advantages of high specific surface area and large pore volume. , but the preparation steps are complicated and the conditions are harsh; on the other hand, the pore size distribution of titanium-aluminum composite oxide materials is not concentrated and irregular, which is not conducive to the diffusion of heavy distillate macromolecular compounds. It is urgent to find a new titanium alloy in this field. Preparation method of aluminum composite oxide, providing support material for heavy distillate oil ultra-deep denitrification catalyst to meet practical needs

Method used

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  • Hydrodenitrification catalyst carrier as well as preparation method and application thereof
  • Hydrodenitrification catalyst carrier as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0047] Weigh 4.085g of aluminum isopropoxide, add 20mL of absolute ethanol, 3.2mL of nitric acid, and 1.4mL of deionized water in sequence, and mix and stir for 4 hours at room temperature to obtain solution 1; at the same time, weigh 2g of P123 template and dissolve in 20mL of water and ethanol, stirred at room temperature for 2 hours to obtain solution 2; add solution 1 dropwise to solution 2, and continue to stir at room temperature for 4 hours to obtain solution C; the obtained solution C was placed in an oven at 70°C, and the solvent was automatically Evaporate until the sample is dry, and then bake at 550°C (the same heating rate is 2°C / min) for 4h. Tablets were pressed on a tablet machine (15Mpa, 15min), and sieved into 20-40 mesh particles in a Taylor sieve to obtain carrier A.

Embodiment 2

[0049] Weigh 3.819g of aluminum isopropoxide, add 20mL of absolute ethanol, 3.2mL of nitric acid, and 1.4mL of deionized water in sequence, and mix and stir for 4 hours at room temperature to obtain solution 1; at the same time, weigh 2g of P123 template and dissolve in 20mL of Water and ethanol, stirred at room temperature for 2 hours to obtain solution 2; add solution 1 dropwise to solution 2, after mixing evenly, weigh 0.445g of isopropyl titanate, and add dropwise to solution C, room temperature Stirring was continued for 4 hours at low temperature to obtain solution D; the obtained solution D was placed in an oven at 70°C, the solvent evaporated automatically until the sample was dry, and then roasted at 550°C (the same heating rate was 2°C / min) for 4 hours. The above prepared TiO 2 The titanium-aluminum composite oxide with a content of 5wt% is then compressed on a tablet machine (15Mpa, 15min), and sieved into 20-40 mesh particles in a Taylor sieve to obtain the carrier...

Embodiment 3

[0051] Weigh 3.574g of aluminum isopropoxide, add 20mL of absolute ethanol, 3.2mL of nitric acid, and 1.4mL of deionized water in sequence, and mix and stir for 4 hours at room temperature to obtain solution 1; at the same time, weigh 2g of P123 template and dissolve in 20mL of Water and ethanol were stirred at room temperature for 2 hours to obtain solution 2; solution 1 was added dropwise to solution 2, and after mixing evenly, 0.849 g of isopropyl titanate was weighed and added dropwise to solution C, at room temperature Stirring was continued for 4 hours at low temperature to obtain solution D; the obtained solution D was placed in an oven at 70°C, the solvent evaporated automatically until the sample was dry, and then roasted at 550°C (the same heating rate was 2°C / min) for 4 hours. The above prepared TiO 2 The titanium-aluminum composite oxide with a content of 10wt% was compressed on a tablet machine (15Mpa, 15min), and sieved into 20-40 mesh particles in a Taylor sieve...

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Abstract

The invention discloses a hydrodenitrification catalyst carrier as well as a preparation method and application thereof, the catalyst carrier is prepared by adopting a solvent evaporation self-assembly method, and the solvent evaporation self-assembly method comprises the following steps: sequentially dropwise adding aluminum isopropoxide and an isobutyl titanate solution into an ethanol solution containing a template agent, and then drying and roasting. The catalyst carrier prepared by the preparation method disclosed by the invention is suitable for a hydrotreating process of petroleum distillates, and is particularly suitable for a deep hydrodenitrogenation process of heavy distillates, and the interaction force between the carrier and active metals is modulated by adopting a solvent evaporation self-assembly method with simple preparation steps, so that the hydrodenitrogenation of the heavy distillates is realized. The defects of strong interaction force between traditional aluminum oxide and active metal and low metal active center utilization rate are overcome, and the hydrogenation catalytic activity of the catalyst is remarkably improved.

Description

technical field [0001] The invention relates to a catalyst carrier and its preparation method and application, in particular to a heavy distillate oil ultra-deep hydrodenitrogenation catalyst carrier and its preparation method and application. Background technique [0002] With the increasing trend of heavy and inferior crude oil worldwide, the proportion of inferior heavy oil in refinery processing raw materials has increased year by year, and the output of heavy distillate oil (such as coker gas oil, vacuum gas oil and deasphalted oil, etc.) also increased. The main use of heavy distillates is as a raw material for subsequent secondary processing. However, since nitrogen compounds are very easy to poison cracking catalysts, it must be hydrotreated to improve its utilization. Nitride usually has the characteristics of strong aromaticity and stable C-N bond, which requires that the hydrotreating catalyst must have both strong hydrogenation performance and cleaning performan...

Claims

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Application Information

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IPC IPC(8): B01J21/06B01J21/04B01J23/883B01J32/00C10G45/08
CPCB01J21/063B01J21/04B01J23/883C10G45/08C10G2300/202
Inventor 魏强夏恩冬李瑞峰王刚周亚松葛冬梅倪术荣吴显军吕倩张铁珍张文成郭金涛梁宇王紫东靳丽丽
Owner PETROCHINA CO LTD
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