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A method of hydroprocessing

A hydrotreating and molecular sieve technology, applied in the petroleum industry, refining hydrocarbon oil, etc., can solve the problems of reducing the content of aromatic hydrocarbons, cracking selectivity, the yield of the target product needs to be improved, and it is difficult to operate for a long time, and achieve high activity and target products. selective effect

Active Publication Date: 2017-08-08
BEIJING ENERGY ENG TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] U.S. Patent US4206036 uses titanium oxide as a carrier, and after loading active components, it is used as a hydrorefining catalyst (desulfurization, denitrogenation), but this carrier has low mechanical strength, small specific surface area, and is expensive, so it cannot be used industrially
[0007] U.S. Patent US2006 / 0052235AI introduces a hydrodesulfurization catalyst using mesoporous molecular sieves, such as MCM-41 as a carrier, cobalt and molybdenum as active components, and silicone resin as a binder. The hydrorefining catalyst has a higher Hydrodesulfurization / olefin saturation activity, but poor stability of mesoporous molecular sieves, it is difficult to operate in harsh hydrodesulfurization environment for a long time
[0008] CN1178238A discloses a diesel hydrogenation conversion catalyst, which is composed of a carrier composed of alumina, amorphous silica-alumina and molecular sieves and a hydrogenation active metal loaded on the carrier. The catalyst is suitable for increasing the cetane number of low-quality diesel oil , to reduce the content of aromatics and the hydrogenation process of desulfurization and denitrogenation. However, in the process of hydrogenation upgrading of diesel oil, the cracking selectivity and yield of target products still need to be improved, and deep desulfurization is difficult

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Experimental program
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Effect test

Embodiment 1

[0061] Preparation of YB molecular sieve: industrially synthesized Y-type molecular sieve (SiO 2 with Al 2 o 3 The weight ratio is 60, the crystallinity is 100, the average grain size is 0.2μm, the pore volume is 0.35ml / g, and the specific surface area is 500m 2 / g,Na 2 O content is less than 0.05% by weight), β molecular sieve (SiO 2 with Al 2 o 3 The weight ratio is 80, the crystallinity is 110, the average grain size is 0.4μm, the pore volume is 0.45ml / g, and the specific surface area is 700m 2 / g,Na 2 O content is less than 0.05% by weight) by weight, mixed according to the ratio of 9:1, soaked in a 70°C water bath (the liquid-solid weight ratio is 2:1) and stirred for 9 hours, and after suction filtration, the filter cake was placed in a 120°C refrigerator Dry in an oven until there is no free water, and then bake in a muffle furnace at 550°C for 4h;

[0062] Add 4000ml of 1.2M (1.2mol / L) HCl aqueous solution to 400g of the roasted solid, stir and heat up to 80°C,...

Embodiment 2

[0065] Preparation of YB molecular sieve: industrially synthesized Y-type molecular sieve (SiO 2 with Al 2 o 3 The weight ratio is 90, the crystallinity is 120, the average grain size is 0.4μm, the pore volume is 0.55ml / g, and the specific surface area is 800m 2 / g,Na 2 O content is less than 0.05% by weight), β molecular sieve (SiO 2 with Al 2 o 3 The weight ratio is 50, the crystallinity is 100, the average grain size is 0.2μm, the pore volume is 0.35ml / g, and the specific surface area is 400m 2 / g,Na 2 O content is less than 0.05% by weight) by weight, mixed according to the ratio of 0.4:1, stirred in an 80°C water bath for 6 hours (the liquid-solid weight ratio is 4:1), and after suction filtration, put the filter cake in an oven at 120°C Dry in medium until there is no free water, and then bake in a muffle furnace at 550°C;

[0066] Add 4000ml of 0.5M HCl aqueous solution to 400g of the roasted solid, stir and heat up to 80°C, stir at constant temperature for 2 ho...

Embodiment 3

[0069] Preparation of YB molecular sieve: take industrially synthesized Y-type molecular sieve (SiO 2 with Al 2 o 3 The weight ratio is 70, the crystallinity is 110, the average grain size is 0.3μm, the pore volume is 0.45ml / g, and the specific surface area is 600m 2 / g,Na 2 O content is less than 0.05% by weight), β molecular sieve (SiO 2 with Al 2 o 3 The weight ratio is 60, the crystallinity is 105, the average grain size is 0.3μm, the pore volume is 0.4ml / g, and the specific surface area is 600m 2 / g,Na 2 O content is less than 0.05% by weight) by weight, mixed according to the ratio of 5:1, stirred in a 90°C water bath for 7 hours (the liquid-solid weight ratio is 5:1), and after suction filtration, put the filter cake in an oven at 120°C Dry in medium until there is no free water, and then bake in a muffle furnace at 550°C;

[0070] Add 4000ml of 3.2M HCl aqueous solution to 400g of the calcined solid, stir and heat up to 90°C, stir at constant temperature for 3 ...

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Abstract

The invention provides a hydroprocessing method, which comprises: under hydroprocessing conditions, contacting hydrocarbon oil and hydrogen with a catalyst, the catalyst contains a carrier and a Group VIB metal element supported on the carrier and Group VIII metal elements, the carrier contains YB molecular sieve, and the YB molecular sieve is prepared according to the following steps: (1) After mixing the Y-type molecular sieve and the β-type molecular sieve, they are soaked in an aqueous solvent, and the solid is separated from the soaked material for Roasting after drying to obtain a first solid; (2) contacting the first solid with an acidic solution, separating the solid from the contacted material and drying to obtain a second solid; (3) subjecting the second solid to water heat treatment. In the present invention, the catalyst prepared by using the carrier obtained by YB molecular sieve has the characteristics of high activity, good selectivity of the target product, etc., and the desulfurization rate and denitrification rate can both reach 99%.

Description

technical field [0001] The present invention relates to a hydroprocessing method. [0002] technical background [0003] Catalytically cracked light cycle oil (LCO), usually used as a low-quality blended diesel component blended with straight-run diesel, or used directly as fuel oil. From the perspective of the composition of LCO, the total aromatic content is as high as 80%, and the others are alkanes, naphthenes and alkenes, etc. Among them, the naphthalene-based bicyclic aromatic hydrocarbons account for about 70% of the total aromatic hydrocarbon content, and the single-ring aromatic hydrocarbons and tricyclic aromatic hydrocarbons account for about 70% of the total aromatic hydrocarbon content. About 15% of the total aromatics content. The sulfur content of LCO is 0.2-1.5wt%, the nitrogen content is 100-750ppm, the cetane number is only 15-25, and the ignition performance is poor. Therefore, a new process of how LCO is applied has also emerged. [0004] In order to me...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10G45/12
Inventor 曲良龙郭贵贵熊震霖轩丽伟董维正孙作霖
Owner BEIJING ENERGY ENG TECH