A kind of heavy oil hydrocracking catalyst and preparation method thereof

A cracking catalyst and heavy oil hydrogenation technology, applied in physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, chemical instruments and methods, etc., can solve the problems of poor oil solubility, low metal content, and non-environmental protection and other problems, to achieve the effect of improving hydrogenation reaction activity, simple preparation process, and inhibiting reaction coke

Active Publication Date: 2021-01-08
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
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  • Claims
  • Application Information

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Problems solved by technology

[0003] CN101384607A discloses that a molybdenum source, water, amine and carbon disulfide react under pressure to obtain a kind of amplification of highly sulfurized molybdenum dihydroxy dithiocarbamate, but the synthetic product does not have oil solubility
The compound obtained by the reaction has good anti-wear and anti-friction properties, and also has anti-oxidation ability, but the sulfur contained in the compound cannot meet the increasingly stringent energy-saving and environmental protection requirements
Moreover, due to the high price of molybdenum-containing compounds, the cost of preparing organic molybdenum with them is generally high. The main reason is that the molybdenum content in organic molybdenum is generally low
[0004] The existing organic molybdenum is mainly used in the field of lubricating oil, but most of the developed organic molybdenum has poor oil solubility, low metal content, corrosion problems and environmental protection problems caused by the presence of sulfur, phosphorus and other compounds.
CN101165141A discloses a method for preparing molybdenum naphthenate as a catalyst for coal-to-liquids, but the content of molybdenum naphthenate prepared by this method is relatively low
Organic molybdenum is used as a catalyst precursor in the hydrogenation reaction process, and the amount of organic molybdenum containing sulfur and phosphorus elements is not environmentally friendly during the synthesis process, and it is not suitable for large-scale production and use.

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  • A kind of heavy oil hydrocracking catalyst and preparation method thereof
  • A kind of heavy oil hydrocracking catalyst and preparation method thereof

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preparation example Construction

[0024] The preparation method of above-mentioned hydrocracking catalyst comprises the following steps:

[0025] (1) Dissolve and disperse the hexavalent molybdenum source compound with the solvent, add an inorganic acid catalyst, the mass ratio of the inorganic acid catalyst to the hexavalent molybdenum source is (0.05~0.2):1, then add C1~C5 organic acid at a temperature of 40~150 Reaction under ℃, described solvent is benzene, toluene or water;

[0026] (2) adding C6-C16 organic acid or C6-C16 ester to the product of step (1), and reacting at a temperature of 160-320°C;

[0027] (3) separating the product obtained in step (2), removing the solvent phase, washing the oil phase with water, and distilling under reduced pressure to obtain a hydrocracking catalyst.

[0028] In the preparation method of the heavy oil hydrocracking catalyst provided by the present invention, preferably, in step (1), the solvent and the hexavalent molybdenum source compound are dissolved and dispers...

Embodiment 1

[0038] (NH 4 ) 6 Mo 7 o 24 Dissolve and disperse in a flask with water at a mass ratio equal to 1:20, add 1.5ml of concentrated hydrochloric acid dropwise, purging with an inert gas, add formic acid at a temperature of 70°C for 4 hours, the amount of formic acid is the same as (NH 4 ) 6 Mo 7 o 24 The molar ratio is 3:1; according to (NH 4 ) 6 Mo 7 o 24 Add hexanoic acid at a molar ratio of 1:6 and add hexanoic acid for 20 minutes. After the addition of hexanoic acid, react at a temperature of 170°C for 10 hours; separate the product, remove the solvent phase, wash the oil phase with water, and collect it by distillation under reduced pressure. The product organic molybdenum salt. The infrared spectrogram of gained organic molybdenum salt sees figure 1 ,Depend on figure 1 Visible: Mo atom and carboxyl RCOO - Bonded, 1500cm -1 COO nearby - The asymmetric and symmetric stretching vibrations can confirm that the synthesized compound is an organic molybdenum salt. T...

Embodiment 2

[0040] Molybdenum trioxide and toluene were dissolved and dispersed in the flask according to the mass ratio equal to 1:10, 0.8ml of concentrated sulfuric acid was added dropwise, purged with inert gas, and acetic acid was added to react at a temperature of 105°C for 4 hours, the amount of acetic acid was the same as the amount of molybdenum trioxide The ratio is 2; add heptanoic acid according to the mass ratio of molybdenum trioxide and heptanoic acid is 1:8, the addition time is 5min, after the addition of heptanoic acid is completed, react at a temperature of 220°C for 4 hours; separate the product and remove the solvent phase, the oil phase was washed with water, and the product was collected by distillation under reduced pressure. The infrared spectrum of the resulting product is shown in figure 2 ,Depend on figure 2 Visible: Mo atom and carboxyl RCOO - Bonded, 1500cm -1 COO nearby - The asymmetric and symmetric stretching vibrations can confirm that the synthesize...

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Abstract

The invention relates to a hydrocracking catalyst for heavy oil and a preparation method of the hydrocracking catalyst. The hydrocracking catalyst for the heavy oil is organic molybdenum salt containing molybdenum ions and C1-C16 organic anions bound with the molybdenum ions, wherein the organic anions contain oxygen atoms, and the valence state of molybdenum in the molybdenum ions is +4, +5 and +6 in a molar ratio of (0.1-25.0):(10.0-40.0):(45.0-85.0). The provided hydrocracking catalyst for the heavy oil has good solubility in hydrocarbon oil, hydrogenation reaction activity is improved, reaction coke generation is inhibited, and conversion of residual oil is effectively promoted. The preparation process of the hydrocracking catalyst for the heavy oil is simple, a filtration step is notneeded, and the synthesis cost is lower.

Description

technical field [0001] The invention relates to a heavy oil hydrocracking catalyst and a preparation method thereof, more specifically, an organic molybdenum salt used for heavy oil hydrocracking reaction and a preparation method thereof. Background technique [0002] Global oil resources are becoming increasingly heavy and inferior. In order to meet the needs of national economic growth and people's living needs, deep processing of heavy oil and improvement of resource utilization have become increasingly concerned issues. Heavy oil processing technology is divided into two categories: decarburization and hydrogenation. In order to further increase the yield of light oil, hydrogenation technology plays an increasingly important role in the field of heavy oil processing. The hydrogenation process includes fixed bed, moving bed, ebullating bed, and slurry bed processes. Among them, the fixed bed hydrogenation technology is the most mature, but its adaptability to raw material...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/04C10G47/02
CPCB01J31/04C10G47/02
Inventor 王红王子军王翠红申海平佘玉成
Owner CHINA PETROLEUM & CHEM CORP
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