Unsupported hydrodemetallization catalyst and preparation method thereof

A hydrodemetallization and catalyst technology, applied in the direction of metal/metal oxide/metal hydroxide catalysts, chemical instruments and methods, physical/chemical process catalysts, etc., can solve complex temperature control, poor product stability, and hole expansion Poor effect and other problems, to achieve the effect of reducing diffusion limitation, improving mass transfer and reducing loss

Active Publication Date: 2013-05-22
XIAMEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, using organic pore-enlarging agents as templates to improve the pore structure requires a large amount of organic pore-enlarging agents. When the amount of organic pore-enlarging agents is low, the pore-enlarging effect is poor, and there is a phenomenon of overheating during the high-temperature calcination of the carrier. Temperature control Complex, poor product stability
However, for unsupported hydrodemetallization catalyst systems, there are few reports in the literature
If a similar method is used to introduce organic pore-enlarging agents into the preparation of unsupported hydrodemetallization catalysts, due to the need to add a large amount of organic pore-enlarging agents and the influence of high-temperature roasting overheating, this method will greatly limit the use of unsupported catalysts. application in

Method used

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  • Unsupported hydrodemetallization catalyst and preparation method thereof
  • Unsupported hydrodemetallization catalyst and preparation method thereof
  • Unsupported hydrodemetallization catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 10

[0031] Embodiment 10.5NiW-175-450 catalyst

[0032] Weigh 3.1g of nickel nitrate hexahydrate and 6.0g of ammonium metatungstate respectively, add 30mL of deionized water, and stir until they are completely dissolved. After 30 min, the two solutions were mixed evenly, and after stirring for 1 h, they were transferred to a 100 ml hydrothermal synthesis kettle, and subjected to hydrothermal action at a temperature of 175° C. for 48 h. Then directly cool to room temperature with cold water, wash 3 times with deionized water, and dry at 100° C. for 12 h to obtain a catalyst precursor. Then it is placed in a muffle furnace and calcined at 450°C for 4h. The prepared catalyst sample is recorded as 0.5NiW-175-450, the average pore diameter of the catalyst is 13-20nm, the pore volume is 0.2-0.3ml / g, and the specific surface area It is 50-70m2 / g.

[0033] The performance of the catalyst was evaluated by the hydrodemetallation reaction of nickel porphyrin. Get 5,10,15,20-tetramethyl-21...

Embodiment 20

[0037] Embodiment 20.7NiW-175-450 catalyst

[0038] The preparation method of the catalyst is the same as in Example 1, but the addition of nickel nitrate hexahydrate is 4.4g, and the other compositions are unchanged, and the 0.7NiW-175-450 catalyst is prepared, and the performance evaluation and product analysis of the catalyst to the hydrodemetallization catalytic reaction Condition is the same as embodiment 1, and the results are shown in Table 1.

Embodiment 30

[0039] Embodiment 30.9NiW-175-450 catalyst

[0040] The preparation method of the catalyst is the same as in Example 1, but the addition of nickel nitrate hexahydrate is 5.6g, and the other compositions are constant, and the 0.9NiW-175-450 catalyst is prepared, and the performance evaluation and product analysis of the catalyst to the hydrodemetallization catalytic reaction Condition is the same as embodiment 1, and the results are shown in Table 1.

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Abstract

The invention provides an unsupported hydrodemetallization catalyst with large aperture and specific surface area, and a preparation method of the catalyst, and relates to a catalyst. The prepared catalyst is comparatively high in hydrodemetallization activity and stability under mild conditions. The catalyst comprises double metals of nickel and tungsten, and the mol ratio of the nickel to the tungsten is in a range of 0.1 to 2.0. The preparation method comprises the following steps of: mixing a nickel solution and an ammonium metatungstate solution, adding the mixture into a hydro-thermal synthesis kettle to prepare a precursor of the catalyst, and baking the precursor in air atmosphere to obtain the catalyst. The average pore size of the catalyst is 13nm-20nm, the pore volume of the catalyst is 0.2-0.2 ml / g, and the specific surface area of the catalyst is 50-70 m<2> / g. The catalyst has a mesoporous structure, is high in hydrodemetallization activity and stability under comparatively mild conditions, and is applicable to hydrodemetallization reaction of residual oil which is comparatively high in content of metals such as nickel and vanadium.

Description

technical field [0001] The invention relates to a catalyst, in particular to a non-supported hydrogenation demetallization catalyst and a preparation method thereof. Background technique [0002] With the increasing shortage of petroleum resources and the heavy quality of crude oil, the deep processing of residual oil is not only conducive to improving the utilization rate of crude oil and alleviating the tense trend of energy supply, but also reducing environmental pollution and achieving clean utilization of energy. , heavy oil, especially residual oil hydroprocessing technology is getting more and more attention. It is used as a hydrodemetallization catalyst for heavy oil, especially vacuum residue with high metal content such as nickel and vanadium. Due to the deposition of metal impurities such as nickel and vanadium contained in the residue, its activity is likely to decrease rapidly . Catalysts with larger pore diameter and pore volume have strong metal and carbon c...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/888B01J35/10C10G45/08
Inventor 伊晓东吴钟芳方维平宋文静郑进保赖伟坤李娟娟
Owner XIAMEN UNIV
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