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A kind of preparation method of bulk hydrorefining catalyst

A catalyst and system technology, which is applied in the field of preparation of low-quality distillate oil deep hydrotreating catalysts, can solve the problems of high catalyst use cost, low utilization rate of active metals, poor dispersion, etc.

Active Publication Date: 2018-10-02
CNOOC TIANJIN CHEM RES & DESIGN INST +1
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Although the catalyst prepared by the above method has high activity, in the catalyst preparation process, Mo source and W source are all added to the reaction system at the same time, and its disadvantage is: due to the reaction ratio of W source and Ni source to Mo source and Ni source The reaction is easy, that is, the Ni-W active phase is easier to form than the Ni-Mo active phase, so the Ni-W active phase is easy to gather inside the catalyst crystal phase, while the Ni-Mo active phase is covered outside the Ni-W active phase, At the same time, the two-phase grains are prone to self-agglomeration, forming large grains, poor dispersion, affecting the pore structure properties of the catalyst, and low utilization of active metals
Since the surface of the catalyst is mostly Ni-Mo active phase, the desulfurization reaction of difficult-to-remove sulfur-containing compounds such as dibenzothiophenes (DBTs) in diesel is mostly carried out under the action of Ni-Mo phase according to hydrodesulfurization (HYD) The path is carried out, that is, a benzene ring is saturated by hydrogenation, and then the C-S bond is broken to achieve the purpose of desulfurization. Only a small part of the direct desulfurization (DDS) path is directly broken by the C-S bond under the action of the Ni-W phase. This not only improves It makes it difficult for the catalyst to desulfurize DBTs, and greatly increases the hydrogen consumption, which significantly increases the cost of the catalyst

Method used

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  • A kind of preparation method of bulk hydrorefining catalyst
  • A kind of preparation method of bulk hydrorefining catalyst

Examples

Experimental program
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Effect test

Embodiment 1

[0020] Mix 25g of basic nickel carbonate and 300ml of deionized water evenly and add it to a 1L high-pressure ultrasonic reactor, set the ultrasonic frequency to 60KHz, heat the mixture to 80°C, keep the temperature for 1 hour, reduce the ultrasonic frequency to 20KHz, and raise the system temperature to 120 ℃, add 26.5g of ammonium molybdate and 3g of polyvinylpyrrolidone, then add 10ml of ammonia water with a concentration of 25wt% dropwise into the system, keep the temperature for 2 hours, turn off the ultrasound, turn on the stirring at a speed of 300 rpm, and add 39.6g of partial tungsten Ammonium acid, then add citric acid until the pH of the system is 4.2, keep the temperature for 2 hours, turn off the heating, collect the slurry after the system drops to room temperature, spray dry the slurry, and control the inlet temperature and outlet temperature at about 200°C and 100°C respectively , The obtained dry powder was calcined in a muffle furnace at 330°C for 3h to obtain...

Embodiment 2

[0022] Mix 44.3g of nickel acetate and 300ml of deionized water evenly and add it to a 1L high-pressure ultrasonic reactor, set the ultrasonic frequency to 60KHz, heat the mixture to 80°C, keep the temperature for 1 hour, reduce the ultrasonic frequency to 20KHz, and raise the system temperature to 120°C , add 21.6g of molybdenum trioxide and 3g of polyvinylpyrrolidone, then add 10ml of ammonia water with a concentration of 25wt% dropwise into the system, keep the temperature for 2 hours, turn off the ultrasonic, turn on the stirring at a speed of 300 rpm, and add 39.6g of metatungstic acid Ammonium, then add citric acid until the pH of the system is 4.2, keep the temperature for 2 hours, turn off the heating, collect the slurry after the system drops to room temperature, and spray dry the slurry. The inlet temperature and outlet temperature are controlled at about 200°C and 100°C, The obtained dry powder was calcined at 330° C. for 3 hours in a muffle furnace to obtain the act...

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Abstract

The invention relates to a preparation method of a bulk-phase hydrofining catalyst. The method comprises steps as follows: an Ni-containing compound and deionized water are mixed and pre-dispersed in an ultrasonic environment, a Mo-containing compound is added, an Ni-Mo fine grain structure is formed by adjusting the ultrasonic frequency and in combination with a surfactant and ammonia water, a W-containing compound and a complexing agent are added for a hydrothermal reaction, spray drying and roasting are performed, and active component powder is obtained; an active component and aluminum hydroxide dry glue are mixed, kneaded and extruded, and the catalyst is obtained through drying and roasting. According to the catalyst prepared with the method, grains of active phases are fine, grains of different active phases are uniformly dispersed, the utilization rate of active metal is high, the catalyst has an excellent pore structure property, the removal efficiency of complicated sulfur-containing compounds in inferior diesel oil is improved, hydrogen consumption is reduced, and the use cost of the catalyst is reduced.

Description

technical field [0001] The invention belongs to the field of preparation of hydrogenation catalysts in petrochemical industry, and relates to the improvement of a preparation method of bulk phase hydrofinishing catalysts, in particular to the preparation method of low-quality distillate deep hydrofinishing catalysts. Background technique [0002] The rise of the oil industry has promoted economic development and social progress. However, as one of the most important energy sources in today's society, the massive consumption of oil has made the crude oil worse and worse, and the processing difficulty has increased, and the quality of oil products has deteriorated. The worse it is, especially for my country, the inferior quality of crude oil will directly lead to the increase of sulfur, nitrogen and aromatic content of diesel oil, and the decrease of cetane number, which will lead to increasingly serious environmental pollution problems. In order to deal with this problem, in r...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/888C10G45/08
CPCB01J23/002B01J23/8885B01J2523/00C10G45/08C10G2300/202C10G2300/70B01J2523/69B01J2523/847B01J2523/845
Inventor 李贺孙彦民曾贤军于海斌隋云乐张学斌张利杰李佳
Owner CNOOC TIANJIN CHEM RES & DESIGN INST
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