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Coal liquefied oil boiling bed hydrogenation treatment catalyst and preparation method thereof

A technology for coal liquefied oil and hydrotreating, which is applied in refining to remove heteroatoms, etc., can solve the influence of catalyst hydrogenation activity and stability, and does not propose problems such as increasing catalyst strength and catalyst bed pressure drop, etc. Effects of hydrogen activity and stability, thin and dense pore walls, improved mechanical strength and wear resistance

Active Publication Date: 2007-12-12
神华煤制油研究中心有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the hydroprocessing of coal liquefied oil by the fixed bed process has the following problems: because the coal liquefied oil is heavy and contains many mechanical impurities, the catalytic reaction conditions will be relatively harsh; high-nitrogen raw materials will accelerate catalyst deactivation, and the service life of the catalyst is very long. short, the product properties cannot be guaranteed; the pressure drop of the catalyst bed is high; in order to meet the product index, the fixed bed reactor system needs to adopt a more complicated design, which will increase the investment cost
Due to the large pore structure of the catalyst and no method for increasing the strength of the catalyst, the strength and wear resistance of the catalyst still need to be further improved.
Moreover, the catalyst contains alkali metal Na, which will affect the hydrogenation activity and stability of the catalyst.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Preparation of modified alumina G-1

[0039] Take the filter cake after washing the alumina precursor prepared by the carbonization method, measure its dry basis as 30wt%, take 1500 grams of the filter cake, add 2.5 liters of deionized water, make a slurry, heat up to 65 ° C, stir for 1 hour, add 90 gram of 85m% phosphoric acid solution, filtered to obtain a filter cake, added 2.0 liters of deionized water, beating, heated to 70 ° C, and added 86 grams of boric acid, and with a concentration of 10gNH 3 / 100ml of ammonia solution to adjust the pH value of the solution to 6, stir for 1 hour, filter and dry at 110°C for 4 hours, the sample is G-1, and its physical and chemical properties are shown in Table 1.

Embodiment 2

[0041] Preparation of modified alumina G-2.

[0042] Take 800 grams of filter cake after washing the aluminum oxide precursor prepared by the aluminum sulfate method, the dry basis is 30wt%, add 3 liters of deionized water, stir evenly, heat up to 85 ° C, and add 53 grams of 85m% phosphoric acid solution, filter to obtain Cake, add 2.5 liters of deionized water, make a slurry, heat up to 70 ° C, and add 120 grams of boric acid, and use a concentration of 10 g NH 3 Adjust the pH of the solution to 6.5 per 100ml of ammonia solution, stir for 1 hour, continue stirring for 30 minutes, and dry at 110°C for 4 hours. The physical and chemical properties of sample G-2 are shown in Table 1.

[0043] Table 1 Physicochemical properties of samples

[0044] Example number

Embodiment 3

[0046] Preparation of ebullating bed hydrogenation catalyst C-1 for stable hydrogenation of coal liquefied oil of the present invention.

[0047] With 168 grams of G-1, 18 grams of alumina fiber powder (length 30 microns, diameter 6 microns, specific surface 183m 2 / g, pore volume 0.08ml / g), 19 grams of nano-silica (the sub-pure nano-silica produced by Tianjin Chemical Co., Ltd.), 193.5 grams are made of SB powder (pore volume 0.46ml / g, specific surface area 260m 2 / g), and the binder (30wt% on a dry basis, the acid-aluminum mol ratio is 0.3) prepared by the above-mentioned SB powder, put into a roller compactor, grind to an extrudable paste, extrude, and dry at 110°C for 4 hours , calcined at 550°C for 3 hours, impregnated with the Mo-Ni-P aqueous solution prepared above, filtered off the solution, dried at 110°C for 4 hours, and calcined at 500°C for 3 hours to obtain catalyst C-1. The physical and chemical properties of the catalyst are listed in Table 2.

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Abstract

The invention discloses a catalyst for coal liquification oil hydrogenation on boiling bed and the preparation method. Besides normal hydrogenation catalyst, the catalyst aslo contains silicon oxide fiber, the content of which in catalyst is 3- 10wt%. The mechanical strength and wearing resistance of catalyst are strong, which increases catalyst stability and life length. It can remove nitrogen and sulfur from coal liquification oil maximumly, reduces olefin and aromatic hydrocarbons content, increases product stability and provides high performance coal liquification solvent oil.

Description

technical field [0001] The invention relates to an ebullating bed hydrogenation treatment catalyst and a preparation method thereof, in particular to an ebullation bed hydrogenation treatment catalyst for stable hydrogenation of coal liquefied oil and a preparation method thereof. Background technique [0002] Due to the characteristics of the ebullating bed hydrogenation reaction itself, the ebullating bed hydrogenation catalyst is always in a boiling state in the reactor, so the strength and wear resistance of the hydrogenation catalyst are higher than those of the fixed bed hydrogenation catalyst. At present, ebullating bed hydrogenation catalysts generally use fixed-bed hydrogenation catalysts, with refractory inorganic oxides as carriers, and Group VIB and / or Group VIII metals as active components, and each component is in the form of fine powder Sintered form exists. The strength and wear resistance of the catalyst still need to be further improved. [0003] CN 13624...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G45/04
Inventor 朱豫飞袁明
Owner 神华煤制油研究中心有限公司
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