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High-denitrification-activity heavy distillate hydrotreating catalyst and preparation method thereof

A technology for hydrotreating and heavy distillate oil, applied in molecular sieve catalysts, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the problems of small mesoporous ratio, poor mixing uniformity, poor pore connectivity, etc. High desulfurization rate and denitrification rate, the effect of improving the denitrification rate

Inactive Publication Date: 2017-07-07
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This composite method is characterized by simplicity and ease of use, and is a commonly used industrial preparation method; but there are also disadvantages such as poor mixing uniformity, poor pore connectivity, and small mesopore ratio.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Embodiment 1 Y / MCM-41 composite molecular sieve / ASA and catalyst

[0038] The surface of molecular sieve HY after the acid treatment in Comparative Example 1 was partially etched with 0.1 mol / L NaOH to obtain Y molecular sieve NY with regular surface structure. During the crystallization process of the MCM-41 molecular sieve synthesis process, 3g NY molecular sieve was added into the crystallization kettle equipped with the above mesoporous molecular sieve precursor, and the micro-mesoporous composite molecular sieve NY / MCM-41 was obtained after crystallization, wherein Y The mass of the molecular sieve accounts for 25% of the total mass of the micro-mesoporous composite molecular sieve, and the mass of the MCM-41 molecular sieve accounts for 75% of the total mass of the composite molecular sieve.

[0039] The acid-treated HY molecular sieve in Comparative Example 1 was replaced with a micro-mesoporous composite molecular sieve NY / MCM-41 molecular sieve, which was evenl...

Embodiment 2

[0041] Embodiment 2 Y / MCM-41 composite molecular sieve / ASA and catalyst

[0042] When preparing silicon-aluminum composite oxide in comparative example 1, the quality of water glass is increased to 140g, and in the prepared silicon-aluminum oxide, SiO 2 The content is 80wt%, and then uniformly mixed with the NY / MCM-41 molecular sieve prepared in Example 1 to prepare a composite carrier. The preparation steps and conditions of the catalyst are the same as in Comparative Example 1.

[0043] The evaluation conditions of the catalyst were the same as in Comparative Example 1. The hydrogenation desulfurization rate of the coker gas oil of the catalyst is 91%, and the denitrogenation rate is 88%.

Embodiment 3

[0044] Embodiment 3 Y / SBA-15 composite molecular sieve / ASA and catalyst

[0045] The surface of molecular sieve HY after the acid treatment in Comparative Example 1 was partially etched with 0.1 mol / L NaOH to obtain Y molecular sieve NY with a regular surface structure. During the crystallization process of the SBA-15 molecular sieve synthesis process, 5g NY molecular sieve was added to the crystallization kettle equipped with the above mesoporous molecular sieve precursor, and the micro-mesoporous composite molecular sieve NY / SBA-15 was obtained after crystallization, wherein The mass of the Y molecular sieve accounts for 20% of the total mass of the composite molecular sieve, and the mass of the SBA-15 molecular sieve accounts for 80% of the total mass of the composite molecular sieve.

[0046] The HY molecular sieve in Comparative Example 1 was replaced with the micro-mesoporous composite molecular sieve NY / SBA-15 molecular sieve, which was uniformly mixed with the silicon-...

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PUM

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Abstract

The invention relates to a high-denitrification-activity heavy distillate hydrotreating catalyst and a preparation method thereof. The catalyst uses a micro mesoporous molecular sieve or a mesoporous oxide as a carrier, and the carrier is prepared in the steps that in-situ growth of beta molecular sieves, MCM-41, SBA-15 and other mesoporous molecular sieves is conducted on the surface of a microporous Y molecular sieve, and the composite molecular sieves serving as main acidic components are combined with a titanium-aluminum mesoporous oxide or a silicon-aluminum mesoporous oxide or the like in situ in a weaving mode to form a weaved structure having communication pore channels; the molecular sieves in the carrier are appropriately subjected to acid pretreatment so as to improve the L acid ratio of the carrier and the catalyst, the high-hydrogenation-activity catalyst good in metal component dispersity and reducibility is thus obtained, and the catalyst is good for hydrogenation and denitrification of heavy distillate.

Description

technical field [0001] The invention relates to a heavy distillate oil hydrogenation treatment catalyst and a preparation method thereof, in particular to a heavy distillate oil hydrogenation treatment catalyst with high denitrification activity and a preparation method thereof. [0002] A new catalyst preparation method based on microporous molecular sieves / mesoporous oxides as a carrier is proposed. Specifically, mesoporous molecular sieves such as β molecular sieves, MCM-41, and SBA-15 are grown in situ on the surface of Y molecular sieve particles, and the composite molecular sieves As the main acidic component, it is interwoven with titanium-aluminum mesoporous oxides or silicon-aluminum mesoporous oxides in situ to form a woven structure with connected pores. This type of carrier has a gradient pore distribution and The acid distribution meets the requirements of the diffusion of heavy distillate macromolecules and different types of hydrogenation reactions; the addition...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/80B01J35/10C10G45/12
CPCC10G45/12B01J29/80B01J2229/20C10G2300/202B01J35/60
Inventor 王刚周亚松魏强马守涛葛冬梅张志华吴显军陆雪峰倪术荣靳丽丽李凤铉谢方明夏恩冬赵晶莹李瑞峰徐铁钢孟祥彬王锐张铁珍王晓峰于强师洪胜张英华赵卫东李圣平张云桐孙庆
Owner PETROCHINA CO LTD