A kind of residual oil hydrogenation catalyst and preparation method thereof

A residue hydrogenation and catalyst technology, used in the petroleum industry, hydrocarbon oil treatment, refining to remove heteroatoms, etc., can solve the problem of low metal removal rate and desulfurization activity, low conversion rate of heavy oil or residual oil, and low catalytic activity problems, to achieve high metal removal rate and desulfurization activity, improve catalytic activity, and low coking rate.

Active Publication Date: 2016-04-27
福建三聚福大化肥催化剂国家工程研究中心有限公司 +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The technical problem to be solved by the present invention is that the residual oil hydrogenation catalyst in the prior art has the problem of easy coking and low catalytic activity when it is used in reactions such as hydrodemetallization, hydrodesulfurization, and hydroconversion of heavy oil or residual oil. , metal removal rate and desulfurization activity are low, resulting in low conversion rate of heavy oil or residual oil, and then a residual oil hydrogenation catalyst that is not easy to coke, high catalytic activity, high metal removal rate and its preparation method is proposed

Method used

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  • A kind of residual oil hydrogenation catalyst and preparation method thereof
  • A kind of residual oil hydrogenation catalyst and preparation method thereof

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Embodiment 1

[0028] The present embodiment provides a kind of residual oil hydrogenation catalyst, it comprises following components:

[0029] Active molybdenum sulfide, 70g;

[0030] Graphitized pore-expanding blue carbon, 30g;

[0031] Wherein, the graphitized pore-expanding blue carbon is prepared by the following method:

[0032] (1) Pulverize the semi-coke, pass through a 300-mesh sieve, dry the water at 120°C, perform graphitization treatment in nitrogen at 1500°C for 8.0 hours, and take it out after the temperature drops to room temperature to obtain graphitized blue-coke;

[0033] (2) Take graphitized blue carbon and pore-enlarging agent KOH according to the mass ratio of 1:2 and mix them uniformly, and perform pore-enlarging treatment in a mixed gas atmosphere composed of nitrogen and oxygen at a volume ratio of 1:9 at a temperature of 500°C After 12 hours, the product after the pore expansion treatment was acid-washed and washed with water, centrifuged, and dried at 100°C for 3...

Embodiment 2

[0038] The present embodiment provides a kind of residual oil hydrogenation catalyst, it comprises following components:

[0039] Active molybdenum sulfide, 60g;

[0040] Activated coal activated carbon, 40g;

[0041] Wherein, the activated coal-based activated carbon is prepared by the following method:

[0042] Coal activated carbon (specific surface area 659m 2 / g, radius is that the hole of 100-200nm accounts for 3% of total number of holes, and the hole with radius less than 100nm accounts for 97% of total number of holes) is immersed in the alkali solution that mass concentration is 25%, described coal activated carbon and described alkali The mass ratio of the solution was 1:5, and activation treatment was carried out at 400° C. for 5 hours to obtain the activated coal-based activated carbon.

[0043] Further, the residue hydrogenation catalyst is prepared by the following method:

[0044] (1) The waste Mo-Ni / γ-Al 2 o3 The catalyst is pulverized, washed with dilute...

Embodiment 3

[0047] The present embodiment provides a kind of residual oil hydrogenation catalyst, it comprises following components:

[0048] Active molybdenum sulfide, 50g;

[0049] Graphitized pore-expanding blue carbon, 50g;

[0050] Wherein, the graphitized pore-expanding blue carbon is prepared by the following method:

[0051] (1) Pulverize the semi-coke, pass through a 200-mesh sieve, dry the water at 100°C, and conduct graphitization treatment in argon at 1900°C for 0.5h, and take it out after the temperature drops to room temperature to obtain graphitized blue-coke ;

[0052] (2) Take graphitized blue carbon and pore-enlarging agent KOH according to the mass ratio of 1:6 and mix them evenly, and expand the pores in a mixed gas atmosphere composed of oxygen and carbon dioxide at a volume ratio of 1:9 at a temperature of 1000°C After treatment for 0.5h, pickling and water washing were carried out on the product after the pore expansion treatment, and then centrifuged and dried a...

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Abstract

The invention provides a residual oil hydrogenation catalyst. The residual oil catalyst is obtained by using activated coal-made activated carbon and / or graphitized pore-expanded semi-coke obtained by pore-expansion as a carrier; and then loading an active metal sulfide as an active component on the carrier to obtain the residual oil hydrogenation catalyst. In the residual oil hydrogenation catalyst, the active component is highly dispersed on the carrier and the carrier structure has proper pore size distribution and obvious L weak acid centers, thereby facilitating suppression of coking. In hydrogenation of heavy oil or residual oil, the catalyst has high accommodation capacity for impurities of metal and sulfur in residual oil raw materials; and the proper large pore size distribution is beneficial to approach, diffusion and conversion of asphaltene macromolecules and the active centers, suppresses coking and further enables the catalyst to have increased metal removal rate and desulfurization activity. Besides, the catalyst provided by the invention presents relatively high methanation-resistant capacity at a high temperature and high hydrogen partial pressure.

Description

technical field [0001] The invention relates to a residue oil hydrogenation catalyst and a preparation method thereof, belonging to the field of residue oil hydrogenation catalysis. Background technique [0002] With the development of heavy and inferior crude oil in the world, and the increasing scarcity of crude oil resources, it is particularly important to effectively process heavy oil and crude oil residues, among which hydrogenation technology is to process heavy and residues to make them lighter. One of the most effective programs. However, due to the heavy and residual oil containing a large amount of impurities such as metals, sulfur, and nitrogen, as well as a large amount of residual carbon that is easy to coke, these impurities will pollute the corresponding catalyst in the subsequent processing, and even lead to the poisoning of the corresponding catalyst. , which will have a great impact on the stability of heavy and residual oil catalytic processes and device...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J27/051C10G45/04C10G49/04
Inventor 江莉龙林科曹彦宁马永德魏可镁
Owner 福建三聚福大化肥催化剂国家工程研究中心有限公司
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