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A wet start-up method for hydrocracking

A hydrocracking and start-up oil technology, which is applied in the fields of hydrocarbon oil cracking and petroleum industry, can solve the problems of catalyst activity influence, inert gas passivation effect, and long start-up process, so as to accelerate the initial activity stabilization process and improve Catalyst activity, sufficient effect of sulfuration process

Active Publication Date: 2021-02-05
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] Passivators such as anhydrous liquid ammonia injected outside the device can make the start-up process smooth and safe, but it needs to be transported by a pressure pump, which not only increases the one-time investment of the device, but also wastes the floor area. Equipment that is intermittently opened often breaks down and affects the progress of the start-up. At the same time, the danger of anhydrous liquid ammonia has been described above, and its controllability is self-evident; if the cracking catalyst is not passivated outside the device If the catalyst is not injected, the stability and safety of the start-up process will inevitably be reduced, and the vulcanization process will also be shortened or terminated, which will have a great impact on the activity of the catalyst, which may affect the long-term stable operation of the catalyst.
[0008] Both CN101492613A and CN101492607A disclose the start-up method of the hydrocracking process, which has certain safety and convenience, but still belongs to the method of forced injection of ammonia outside the device to inject a certain passivating agent into the reaction system to inhibit the activity of the cracking agent. There are bound to be disadvantages of injecting ammonia in the above-mentioned prior art, which will bring certain hidden dangers and harm
However, there are still other liquid components that are additionally introduced, and the control control is difficult to achieve, and the start-up process takes a long time
[0012] CN102284299A and CN1602999A relate to a method of hydrogenation catalyst presulfurization outside the hydrogenation reactor-activation in the hydrogenation reactor, which completes the deactivation process of the sulfidation agent of the catalyst under specific working conditions outside the reactor, but the introduced The gas contains catalyst "poisons" and is relatively simple, which cannot completely complete the passivation process of the catalyst. In addition, it is difficult to ensure the adsorption and excess of the passivation gas during the transportation and vulcanization process. insufficient
[0013] CN102921441A has introduced a kind of preparation method of tungsten phosphide catalyst, it passes nitrogen flow to passivate the catalyst in the preparation process, although the effect of passivation can be played to a certain extent, but the passivation effect of inert gas is very poor , cannot be applied to the hydrocracking process
[0014] CN104593051A and CN104593050A disclose a method for starting a vulcanized hydrogenation catalyst. The oil film generated by the added chemical substance is used to passivate the exothermic process of the vulcanized catalyst, although it can completely solve the heat control problem of the concentrated release of sulfur during the vulcanization process , but it cannot be applied in the field of hydrocracking, the oil film formed by it will react or decompose during hydrocracking, and cannot play the role of passivation
Although the process of preparing the presulfurized catalyst outside the device is convenient and feasible, and the energy consumption is reduced, the passivation process still has a certain inhibitory effect on the heat release of the presulfurized catalyst outside the device, so it cannot be applied in the field of hydrocracking
[0016] CN104342200A discloses a method for selective hydrogenation of reformed oil, the core of which is to use some "poisons" to passivate the active metals in the catalyst. Although the effect is remarkable, it is not suitable for the hydrocracking process. For molecular sieves passivation process
[0017] The literature "Research on the Presulfidation and Passivation Process of Hydrogenation Catalysts" introduces the reaction mechanism of the passivation process of presulfided hydrogenation catalysts in detail. In the hydrogenation process with cracking reaction, it is different from the passivation mechanism of our conventional hydrocracking catalyst, so it cannot be applied to the hydrocracking process

Method used

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  • A wet start-up method for hydrocracking
  • A wet start-up method for hydrocracking

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Firstly, low nitrogen start-up oil, hydrogen and vulcanizing agent are introduced into the hydrocracking unit, and then the hydrocracking catalyst is subjected to constant temperature vulcanization under the condition of 220°C. 4% of the theoretical dosage, after the hydrogen sulfide content in the circulating hydrogen reaches 4000ppm, reduce the adding rate of the sulfurizing agent to 1% of the theoretical dosage of the sulfurizing agent per hour and increase the bed temperature of the hydrocracking catalyst to 320°C, the time used is 15h, When the bed temperature of the hydrocracking catalyst reaches 320°C, increase the addition rate of the vulcanizing agent to 3% of the theoretical amount of vulcanizing agent per hour, continue the constant temperature vulcanization for 3 hours, then raise the temperature to 365°C and feed the raw material oil for reaction, wherein the The hydrocracking catalyst contains 3% nitrogen element, 5.5% nickel oxide, 18% molybdenum oxide and...

Embodiment 2

[0039] Firstly, low nitrogen start-up oil, hydrogen and vulcanizing agent are introduced into the hydrocracking unit, and then the hydrocracking catalyst is vulcanized at a constant temperature at 230°C. 5% of the theoretical dosage, after the hydrogen sulfide content in the circulating hydrogen reaches 5000ppm, reduce the adding rate of the sulfurizing agent to 1.5% of the theoretical dosage of the sulfurizing agent per hour and increase the bed temperature of the hydrocracking catalyst to 325°C, and the time used is 13h. When the bed temperature of the hydrocracking catalyst reaches 325°C, increase the addition rate of the vulcanizing agent to 4% of the theoretical amount of vulcanizing agent per hour, continue the constant temperature vulcanization for 2 hours, then raise the temperature to 365°C and feed the raw material oil for reaction, wherein the The hydrocracking catalyst contains 3% nitrogen element, 5.5% nickel oxide, 18% molybdenum oxide and 30% Y-type molecular sie...

Embodiment 3

[0041] Firstly, low-nitrogen start-up oil, hydrogen and vulcanizing agent are introduced into the hydrocracking unit, and then the hydrocracking catalyst is subjected to constant temperature vulcanization under the condition of 240°C. 3% of the theoretical amount, after the hydrogen sulfide content in the circulating hydrogen reaches 3000ppm, reduce the addition rate of the sulfide agent to 0.8% of the theoretical amount of the sulfide agent per hour and increase the bed temperature of the hydrocracking catalyst to 330°C, and the time used is 10h. When the bed temperature of the hydrocracking catalyst reaches 330°C, increase the addition rate of the vulcanizing agent to 3% of the theoretical amount of vulcanizing agent per hour, continue the constant temperature vulcanization for 4 hours, then raise the temperature to 360°C and feed the raw material oil for reaction, wherein the The hydrocracking catalyst contains 2.5% nitrogen element, 5.5% nickel oxide, 18% molybdenum oxide a...

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Abstract

The invention discloses a hydrocracking commencement method which comprises the following steps: firstly, introducing low-nitrogen commencement oil, nitrogen and a vulcanizing agent into a hydrocracking device, carrying out constant-temperature vulcanization on a hydrocracking catalyst at 220-260 DEG C, reducing the addition velocity of the vulcanizing agent and increasing the temperature of a hydrocracking catalyst bed layer when the content of hydrogen sulfide in circulation hydrogen is up to 3000-5000ppm, increasing the addition velocity of the vulcanizing agent when the temperature of thehydrocracking catalyst bed layer is up to 310-330 DEG C, carrying out constant-temperature vulcanization continuously, increasing the temperature to 360-370 DEG C, and introducing raw material oil tocarry out reactions, wherein the hydrocracking catalyst comprises 0.4-6%, preferably 0.5-4%, of nitrogen elements in percentage by weight, and the nitrogen elements are derived from low-molecule nitride and alkalescent or non-alkaline annular nitride. By adopting the method, the time for commencement, raw material switching and production state stabilization is short, consumption of a passivant inthe commencement process is avoided, potential danger in the ammonia injection process is avoided, and not only is energy consumption reduced, but also environmental pollution and human body damage caused by the passivant can be reduced.

Description

technical field [0001] The invention relates to a hydrocracking start-up method, in particular to a hydrocracking start-up process method without external injection of a passivating agent. Background technique [0002] The hydrocracking process is under the action of hydrogen, high temperature, high pressure and catalysts to hydrodesulfurize, hydrodenitrogenate, polycyclic aromatic hydrocarbons, hydrosaturation and ring-opening cracking of heavy distillate oils (VGO, CGO, DAO). The process of conversion into target products such as light oil and middle distillates. The hydrocracking catalysts currently produced in domestic industry are basically oxidative. New catalysts or regenerated catalysts produced in industry contain active metal components (Mo, Ni, Co, W) in the oxidation state (MoO 3 , NiO, CoO, WO 3 ) exists in the form of The practice of basic research and industrial application shows that most of the active metal components of hydrogenation catalysts have high...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10G47/12
Inventor 王仲义崔哲彭冲孙士可吴子明刘昶
Owner CHINA PETROLEUM & CHEM CORP
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