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Rapid start-up method of hydrocracking catalyst

A hydrocracking and catalyst technology, which is used in hydrocarbon oil cracking, petroleum industry, etc., can solve the problems of difficult control and control, influence of catalyst activity, waste of floor space, etc., to reduce operating fluctuations and operating risks, and accelerate initial activity. The effect of stabilizing the process and stabilizing the catalyst activity

Active Publication Date: 2019-05-21
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] 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 the difficulty of its control is self-evident; If the agent is 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. In addition, it will also be greatly affected. prolongs the time for the catalyst to enter a steady state
[0009] 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
[0013] 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
[0014] 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
[0015] 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
[0017] 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

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Examples

Experimental program
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Effect test

Embodiment 1

[0035] Start the operation according to the start-up process of the conventional hydrocracking unit, control the reactor inlet temperature at 160°C, introduce low-nitrogen oil into the reaction system, raise the reactor inlet temperature to 180°C, and inject vulcanizing agent into the reaction system. After the hydrogen sulfide concentration in the circulating hydrogen reaches 0.1v%, the reactor inlet temperature is increased to 220°C, and the constant temperature sulfuration is carried out for at least 8 hours. Then raise the temperature to 270°C to introduce raw material oil and change it to a one-pass process to continue vulcanization. The temperature rises to 320°C at a rate of 8°C / hour, and the vulcanization ends after 4 hours of constant temperature. Then first raise the reaction temperature to 355° C., adjust the temperature, control the conversion rate to be constant at 35%, and keep it stable for 2 days. After the resurrection process is over, adjust the process condi...

Embodiment 2

[0037] Start the operation according to the start-up process of the conventional hydrocracking unit, control the reactor inlet temperature at 160°C, introduce low-nitrogen oil into the reaction system, raise the reactor inlet temperature to 180°C, and inject vulcanizing agent into the reaction system. After the concentration of hydrogen sulfide in the circulating hydrogen reaches 0.1v%, the inlet temperature of the reactor is raised to 240°C, and the constant temperature sulfuration is carried out for at least 8 hours. Then raise the temperature to 280°C to introduce raw material oil and change it to a one-pass process to continue vulcanization. The temperature rises to 330°C at a rate of 8°C / hour, and the vulcanization ends after 4 hours of constant temperature. Then first increase the reaction temperature to 365°C, adjust the temperature, control the conversion rate to be constant at 35%, and stabilize for 1 day. After the resurrection process is over, adjust the process con...

Embodiment 3

[0039] Start the operation according to the start-up process of the conventional hydrocracking unit, control the reactor inlet temperature at 160°C, introduce low-nitrogen oil into the reaction system, raise the reactor inlet temperature to 180°C, and inject vulcanizing agent into the reaction system. After the hydrogen sulfide concentration in the circulating hydrogen reaches 0.1v%, the reactor inlet temperature is increased to 220°C, and the constant temperature sulfuration is carried out for at least 8 hours. Then raise the temperature to 270°C to introduce raw material oil and change it to a one-pass process to continue vulcanization. The temperature rises to 320°C at a rate of 8°C / hour, and the vulcanization ends after 8 hours of constant temperature. Then first raise the reaction temperature to 360° C., adjust the temperature, control the conversion rate to be constant at 40%, and keep it stable for 2 days. After the resurrection process is over, adjust the process condi...

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Abstract

The invention discloses a rapid start-up method of a hydrocracking catalyst. The start-up method comprises the following steps: introducing raw material oil in the vulcanization process, after vulcanization is completed, adjusting a reaction temperature, and when the mass yield of light oil less than 360 DEG C is stabilized at 35-40%, adjusting to a hydrocracking reaction condition to carry out ahydrocracking reaction, wherein the hydrocracking catalyst comprises 0-10% of a molecular sieve by weight, and the molecular sieve comprises, but not limited, a Y type or a USY (Ultra-Stable Y Zeolite) type molecular sieve. The method is simple in start-up and raw material switching process, stable in operation and capable of avoiding consumption of a passivant in the start-up process and potential danger in the ammonia injection process.

Description

technical field [0001] The invention relates to a rapid start-up method of a hydrocracking catalyst, in particular to a rapid start-up method of a hydrocracking catalyst without ammonia injection passivation. 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...

Claims

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Application Information

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IPC IPC(8): C10G47/36
Inventor 王仲义曹正凯崔哲彭冲孙士可唐兆吉
Owner CHINA PETROLEUM & CHEM CORP
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