Catalyst for hydrotreating of boron-containing residual oil and preparation method thereof

A technology of residual oil hydrogenation and catalyst, which is applied in the direction of catalyst activation/preparation, physical/chemical process catalysts, chemical instruments and methods, etc. It can solve the problems of poor stability, unfavorable catalyst active metal dispersion, low nickel removal activity, etc., to achieve Improve hydrogenation performance, facilitate hydrogenation reaction and removal, and weaken the effect of interaction

Pending Publication Date: 2020-02-28
浙江石油化工有限公司
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  • Abstract
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  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The carrier prepared by this method is prone to uneven surface acid distribution and pore blockage, which is not conducive to the dispersion of catalyst active metals, and the catalyst has low hydrogenation performance, poor anti-coking performance, and poor stability.
[0006] In summary, based on the differences in the diffusion and reaction characteristics of metal Ni, V and other compounds in the residue oil in the catalyst, the problem of high vanadium removal activity and low nickel removal activity of the macroporous residue hydrodemetallation catalyst needs to be developed. Hydrodenickelization Catalyst More Suitable for Metallic Nickel Removal

Method used

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  • Catalyst for hydrotreating of boron-containing residual oil and preparation method thereof

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preparation example Construction

[0032] A preparation method of a boron-containing residue hydrotreating catalyst, the preparation method comprising the steps of:

[0033] Step 1): Prepare the carrier: Prepare the aluminum salt solution, mix the sol by pH swing method, add the organic pore expander solution containing silicon compound during the mixing process, lead it into the gel forming tank, and form it at 60 ° C ~ 90 ° C Glue, after gelation, aging, drying, molding, and then roasting at 550°C to 1100°C to obtain an alumina carrier; the pH swing range is 4 to 10, and the pH of the final reaction system is 8 to 10;

[0034] Step 2): impregnating the alumina support with an equal volume of Mo or W and Co or Ni impregnation solution, then drying at 90-150°C for 2-8 hours, and then calcining at 600-800°C for 1-5 hours , to obtain a hydrodemetallization catalyst;

[0035] The hydrodemetallization catalyst contains MoO 3 or WO 3 and NiO or CoO, the MoO 3 or WO 3 The total mass of NiO or CoO accounts for 5....

Embodiment 1

[0047] (1) Preparation of carrier: prepare 0.98M aluminum chloride solution, and under stirring conditions, add the above aluminum chloride solution and ammonia water into the gelling tank in parallel using the pH swing method, and the flow rate of aluminum chloride is 2.0 ml / min, the temperature in the glue tank is controlled at 70°C, the pH swing range is 4-10, and the pH of the final reaction system is 8-10. At the same time, 2.0 ml / min of a polystyrene ball pore-enlarging agent solution containing a certain amount of boric acid was added, and the total amount of the pore-enlarging agent added was 13% of the mass of the calcined alumina. After gelling, aging for 0.5h, drying at 50°C for 60h under vacuum condition, extruding and sintering at 800°C for 6h, the B-loaded 2 o 3 (accounting for 1.5w% of final catalyst content) alumina carrier B 2 o 3 / γ~Al 2 o 3 .

[0048] (2) Impregnation of active metals: according to the MoO in the final catalyst 3 The content of NiO is...

Embodiment 2

[0050] (1) Preparation of the carrier: prepare 1.0M aluminum chloride solution, under stirring conditions, add the above aluminum chloride solution and ammonia water into the gelling tank in parallel using the pH swing method, and the flow rate of aluminum chloride is 2.0 ml / min, the temperature in the glue tank is controlled at 70°C, the pH swing range is 4-10, and the pH of the final reaction system is 8-10. At the same time, 2.0 ml / min of a polystyrene ball pore-enlarging agent solution containing a certain amount of boric acid was added, and the total amount of the pore-enlarging agent added was 15% of the mass of the calcined alumina. After gelling, aging for 0.5h, drying at 50°C for 60h under vacuum, extruding and sintering at 800°C for 6h, the alumina carrier B loaded with B2O3 (accounting for 2.0w% of the final catalyst content) was obtained 2 o 3 / γ~Al 2 o 3 .

[0051] (2) Impregnation active metal: according to MoO in the final catalyst content 9.2wt%, the conten...

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Abstract

The invention discloses a catalyst for hydrotreating of boron-containing residual oil and a preparation method thereof. The catalyst has mesopores which are intensively distributed and are uniform insize; the pore diameters of the mesopores range from 10 to 30 nm; in-situ modification of a boron-containing compound is carried out in the forming process of pore channels; the surfaces of the pore channels have relatively strong acidity which is uniformly distributed; the mesoporous channels are beneficial for diffusion of macromolecules such as residual oil; the increase of mesoporous acidity of the catalyst is beneficial for improving the adsorption and reaction performance of metallic nickel compounds and sulfur compounds in the residual oil; due to the existence of boron, the interactionbetween the active metal of the catalyst and the carrier of the catalyst is weakened, the formation of a metal hydrogenation active phase is facilitated, the hydrogenation performance of the active metal of the catalyst is improved, hydrogenation removal of a metal nickel compound is better facilitated, and thus, the nickel removal and desulfurization performance of the catalyst are improved; andthe catalyst can be used as a transition agent of a demetalization catalyst and a desulfurization catalyst to improve the overall efficacy of a graded catalyst for fixed-bed residual oil hydrotreatment.

Description

technical field [0001] The invention relates to a catalyst and a preparation method thereof, more specifically, to a boron-containing residual oil hydrotreating catalyst and a preparation method thereof, belonging to the field of petrochemical industry. Background technique [0002] Vacuum residue oil has the characteristics of high content of metal compounds, sulfides and nitrides, complex macromolecular structures such as colloids and asphaltenes, and is difficult to process, which has become the focus and difficulty of refinery processing. Fixed bed residue hydrotreating technology is an effective means to realize the clean utilization of vacuum residue. However, due to the presence of heteroatoms in the residual oil, the hydrotreating catalyst is easily deactivated by the deposition of metals and carbon deposits. The service life of the residual oil hydrotreating catalyst is generally about one year, or even shorter, and the use cost of the catalyst higher. The develop...

Claims

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Application Information

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IPC IPC(8): B01J23/883B01J35/10C10G45/08
CPCB01J23/002B01J23/883B01J37/0018C10G45/08C10G2300/205C10G2300/107C10G2300/1077B01J2523/00B01J35/635B01J35/647B01J35/615B01J2523/305B01J2523/31B01J2523/68B01J2523/847
Inventor 刘亭亭赵杨唐智龙李红良赵旭涛李超然崔登科郭金彪
Owner 浙江石油化工有限公司
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