A kind of stable start-up method of hydrocracking catalyst

A hydrocracking and catalyst technology, which is used in the start-up of hydrotreating operations, hydrocarbon oil cracking, and the petroleum industry. As well as operational risk, the effect of accelerating the initial activity stabilization process, and stabilizing the catalyst activity

Active Publication Date: 2021-08-06
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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  • A kind of stable start-up method of hydrocracking catalyst
  • A kind of stable start-up method of hydrocracking catalyst
  • A kind of stable start-up method of hydrocracking catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] 按照常规加氢裂化装置的开工过程进行开工,将反应器入口温度控制在160℃,向反应系统引进低氮油,提升反应器入口温度至180℃,向反应系统注硫化剂。在循环氢中硫化氢浓度达到0.1v%后,提升反应器入口温度至220℃,恒温硫化至少8h。而后引入原料油并改为一次通过流程继续硫化,以20℃ / 时的升温速度升至320℃,恒温4小时后硫化结束。而后首先提高反应温度至325℃,进行温度调整,控制转化率恒定为35%,稳定2天;继续调整反应温度,控制转化率恒定为50%,稳定2天;继续调整反应温度,控制转化率恒定为55%,稳定2天;继续调整反应温度,控制转化率恒定为70%,稳定2天。复活过程结束,调整工艺条件进入正常生产。进行硫化过程操作条件为操作压力15MPa,氢油体积比1000∶1,体积空速为0.8h -1 .

Embodiment 2

[0037] 按照常规加氢裂化装置的开工过程进行开工,将反应器入口温度控制在160℃,向反应系统引进低氮油,提升反应器入口温度至180℃,向反应系统注硫化剂。在循环氢中硫化氢浓度达到0.1v%后,提升反应器入口温度至240℃,恒温硫化至少8h。而后引入原料油并改为一次通过流程继续硫化,以20℃ / 时的升温速度升至330℃,恒温4小时后硫化结束。而后首先提高反应温度至335℃,进行温度调整,控制转化率恒定为35%,稳定2天;继续调整反应温度,控制转化率恒定为50%,稳定1天;继续调整反应温度,控制转化率恒定为55%,稳定2天;继续调整反应温度,控制转化率恒定为70%,稳定1天。复活过程结束,调整工艺条件进入正常生产。进行硫化过程操作条件为操作压力15MPa,氢油体积比1000∶1,体积空速为0.8h -1 .

Embodiment 3

[0039] 按照常规加氢裂化装置的开工过程进行开工,将反应器入口温度控制在160℃,向反应系统引进低氮油,提升反应器入口温度至180℃,向反应系统注硫化剂。在循环氢中硫化氢浓度达到0.1v%后,提升反应器入口温度至220℃,恒温硫化至少8h。而后引入原料油并改为一次通过流程继续硫化,以20℃ / 时的升温速度升至320℃,恒温8小时后硫化结束。而后首先提高反应温度至330℃,进行温度调整,控制转化率恒定为40%,稳定2天;继续调整反应温度,控制转化率恒定为45%,稳定2天;继续调整反应温度,控制转化率恒定为60%,稳定2天;继续调整反应温度,控制转化率恒定为65%,稳定2天。复活过程结束,调整工艺条件进入正常生产。进行硫化过程操作条件为操作压力15MPa,氢油体积比1000∶1,体积空速为0.8h -1 .

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Abstract

The invention discloses a stable start-up method for a hydrocracking catalyst. In the start-up method, raw material oil is introduced during the vulcanization process, and the reaction temperature is adjusted after the vulcanization is completed so that the mass yield of light oil at <360°C is constant at 65-70%. Adjust to the hydrocracking reaction conditions to carry out the hydrocracking reaction, the hydrocracking catalyst contains 50%-70% molecular sieve by weight, and the molecular sieve includes but not limited to Y-type or USY molecular sieve. The method has the advantages of simple start-up and raw material switching process, stable operation, and avoids the consumption of passivating agent and the potential danger in the ammonia injection process during start-up.

Description

technical field [0001] The invention relates to a stable start-up method of a hydrocracking catalyst, in particular to a stable 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 hydrogenati...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10G49/24C10G47/16C10G45/12
Inventor 王仲义崔哲彭冲唐兆吉孙士可曹正凯
Owner CHINA PETROLEUM & CHEM CORP
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