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Heavy oil hydrotreatment method

A technology for hydroprocessing and heavy oil, which is applied in the treatment of hydrocarbon oil, petroleum industry, refining to remove heteroatoms, etc. It can solve the problems of inability to achieve deep desulfurization, reduce the steric hindrance effect, and moderate the number of lamellar layers , The effect of improving the utilization rate of the active phase

Active Publication Date: 2020-04-28
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This method can reduce the content of metals and residual carbon in residual oil hydrogenation products, but cannot achieve the purpose of deep desulfurization

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] This example provides a catalyst gradation combination and the preparation process of the gradation catalyst. Catalyst gradation scheme is adopted, the catalyst is loaded in the reactor, and the bed is filled with sulfurized hydrogenation catalyst I, sulfurized hydrogenation catalyst II and sulfurized hydrogenation catalyst III from top to bottom.

[0037] The preparation method of sulfided hydrogenation catalyst Ⅰ is as follows: the carrier Ⅰ is used to contain MoO 3 , NiO active components were supersaturated impregnated to obtain a catalyst precursor, which was dried at 250°C for 4h, heated to 580°C at 5°C / min, and roasted at constant temperature for 4.5h to obtain the desired catalyst. The catalyst MoO 3 is 12.0%, NiO is 2.1%; the specific surface area is 120m 2 / g, the pore volume is 0.87ml g -1 ; The pore diameter is 17.8nm. Load the catalyst into the vulcanization reactor, introduce sulfurized oil into it, and wet the catalyst bed; then adjust the bed tempera...

Embodiment 2

[0041] With embodiment 1, only the preparation method of sulfurized state hydrogenation catalyst I, II and III is different, specifically:

[0042] The preparation method of sulfided hydrogenation catalyst Ⅰ is as follows: the carrier Ⅰ is used to contain MoO 3 , NiO active components were supersaturated impregnated to obtain a catalyst precursor, which was dried at 300°C for 5h, heated to 550°C at 4°C / min, and roasted at constant temperature for 4.5h to obtain the desired catalyst. The catalyst MoO 3 is 11.0%, NiO is 2.8%; the specific surface area is 130m 2 / g, the pore volume is 0.91ml·g -1 ; A few pore diameter 21.5nm. Load the catalyst into the vulcanization reactor, introduce sulfurized oil into it, and wet the catalyst bed; then adjust the bed temperature to 170°C, and inject the vulcanizing agent; after the hydrogen sulfide penetrates the catalyst bed, the catalyst bed The bed temperature was raised to 260°C at a rate of 3°C / h and kept at a constant temperature for...

Embodiment 3

[0046] With embodiment 2, only the preparation method of sulfurized state hydrogenation catalyst III is different, specifically:

[0047] Same as Example 2

[0048] The preparation method of sulfided state hydrogenation catalyst III is as follows: the carrier III is used to contain MoO 3 , NiO active components and lactose (the amount is 17% of the mass of the catalyst carrier) mixed solution saturated impregnation to obtain a catalyst precursor, the precursor was dried at 120 ° C for 1.5 h to obtain the desired catalyst. The catalyst MoO 3 is 24.9%, NiO is 5.8%; the specific surface area is 198m 2 / g, the pore volume is 0.55ml g -1 ; A few pore diameter 8.1nm. Load the catalyst into the vulcanization reactor, introduce sulfurized oil into it, and wet the catalyst bed; then adjust the bed temperature to 160°C, and inject the vulcanizing agent; after the hydrogen sulfide penetrates the catalyst bed, the catalyst bed The bed temperature was raised to 200°C at a rate of 15°C...

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Abstract

The invention discloses a heavy oil hydrotreatment method, which comprises the following steps that a heavy oil raw material enters a hydrogenation reactor and contacts a hydrogenation catalyst bed layer to carry out a hydrogenation reaction, and the reaction product flows out of the reactor, wherein the hydrogenation catalyst bed layer is filled with at least two stages of vulcanization-state hydrogenation catalysts in a grading manner along the material flow direction, the average length of the metal active phase crystals of each stage of the vulcanization-state hydrogenation catalyst is increased stage by stage along the material flow direction, the average layer number of the lamellar crystals is reduced stage by stage, the content of the active components is increased stage by stage,and the probable pore diameter is reduced stage by stage. According to the method, the specific catalyst gradation is adopted, so that the active center of the catalyst can be effectively utilized, the coupling reaction performance of an active center structure and a reactant molecular structure is improved, the stability of hydrogenation reaction, such as demetalization, desulfurization, denitrification and the like, of the whole system is greatly improved, and deep hydrogenation of heavy oil is facilitated.

Description

technical field [0001] The invention relates to a method for hydrotreating heavy oil. Background technique [0002] In the hydrotreating of heavy oil, catalysts are generally packed in grades, and the sequence is generally protective agent, demetallization, desulfurization and denitrogenation catalysts. The graded packing of the catalyst can not only increase the fouling capacity of the catalyst bed, but also significantly reduce the pressure drop of the catalyst bed. The use of catalyst graded loading technology can increase the metal capacity of the catalyst system at the same time, and because the upstream demetallization catalyst effectively exerts its demetallization function, it protects the hydrogenation activity of the downstream highly active desulfurizer or denitrification agent, so Catalyst graded loading technology can increase the hydrotreating capacity of residue hydrotreating catalysts for heavy raw materials. [0003] The reactions in the hydrotreating proc...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G45/08
CPCC10G45/08C10G2300/1037C10G2300/201
Inventor 吕振辉彭绍忠杨占林隋宝宽薛冬
Owner CHINA PETROLEUM & CHEM CORP
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