A method for hydrogenation of polycyclic aromatic hydrocarbons catalyzed by primary metalloporphyrins of heavy oil

A technology of porphyrin catalyzing polycyclic aromatic hydrocarbons and primary metals, which is applied in the field of thermal upgrading of heavy oil, and achieves the effects of mild and easy-to-control reaction conditions, short reaction time and simple method

Active Publication Date: 2017-12-19
CHINA UNIV OF PETROLEUM (EAST CHINA)
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  • Abstract
  • Description
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  • Application Information

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Problems solved by technology

However, there is no report on the direct study of the catalytic hydrogenation activity of polycyclic aromatic hydrocarbons in the absence of catalysts using primary metal nickel porphyrin and vanadium porphyrin in heavy oil as catalyst precursors.

Method used

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  • A method for hydrogenation of polycyclic aromatic hydrocarbons catalyzed by primary metalloporphyrins of heavy oil
  • A method for hydrogenation of polycyclic aromatic hydrocarbons catalyzed by primary metalloporphyrins of heavy oil
  • A method for hydrogenation of polycyclic aromatic hydrocarbons catalyzed by primary metalloporphyrins of heavy oil

Examples

Experimental program
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Effect test

Embodiment 1

[0024] Adopt acetonitrile extraction, silica gel column chromatographic separation and purification to obtain the petroleum nickel porphyrin in the heavy atmospheric residue (Ni content is 68ppm, V content is 1.7ppm), after anthracene and petroleum nickel porphyrin are dissolved with dichloromethane, carry out homogenization Mixed, heated to reflux (treatment temperature is 60° C., treatment time is 0.5 h), evaporated the solvent and vacuum dried for 1 h to obtain the reaction raw material. Wherein, the addition ratio of anthracene and petroleum nickel porphyrin is determined by the nickel content (taking the nickel content as 200ppm) in the reaction raw material, and the specific mathematical relationship is as follows:

[0025] For petroleum nickel porphyrin components, but

[0026] where w Me For the content of metal nickel in the reaction raw material, the unit is ppm; w Me ' is the content of metal nickel in the petroleum nickel porphyrin component, in ppm; m PP an...

Embodiment 2

[0029] Adopt same petroleum nickel porphyrin in embodiment 1, naphthalene and petroleum nickel porphyrin are according to the standard of nickel content 100ppm, adopt the same mixing method among the embodiment 1 to obtain reaction raw material, get 0.1g raw material and add 0.05g carbon disulfide again at 460 ℃, 20MPa and hydrogen reaction for 30min. The results of naphthalene hydrogenation are listed in Table 1.

Embodiment 3

[0031] Adopt acetonitrile extraction, silica gel column chromatographic separation and purification to obtain the petroleum vanadium porphyrin in the heavy atmospheric residue (Ni content is 68ppm, V content is 1.7ppm) used in embodiment 1, with naphthalene and petroleum vanadium porphyrin by vanadium content 200ppm The standard, using the same mixing method in Example 1 to obtain the reaction raw materials, take 0.1g of raw materials and then add 0.005g of sulfur elemental hydrogen reaction at 400 ℃, 20MPa for 30min. The results of naphthalene hydrogenation are listed in Table 1.

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Abstract

The invention discloses a method for catalyzing the hydrogenation of polycyclic aromatic hydrocarbons by using heavy oil primary nickel porphyrin and vanadium porphyrin. , react for a certain period of time under hydrogen conditions, and wash out the product completely with dichloromethane. By adopting the method of the invention, the metalloporphyrin can be activated to become a species with catalytic hydrogenation activity, and the hydrogenation of polycyclic aromatic hydrocarbons can be promoted under the condition of hydrogen modification. It is of great significance to improve the effect of hydrogen modification of heavy oil. The method is simple, the reaction time is short, the reaction conditions are mild and easy to control, and complex and expensive equipment is not required.

Description

technical field [0001] The invention belongs to the technical field of thermal upgrading of heavy oil, and in particular relates to a method for hydrogenating polycyclic aromatic hydrocarbons catalyzed by primary metalloporphyrins of heavy oil. Background technique [0002] Heavy oil contains a variety of metals, among which nickel and vanadium are the most harmful. Nickel and vanadium can cause poisoning and deactivation of the catalyst in the catalytic process, promote the dehydrogenation and condensation reaction of heavy oil during thermal processing, and accelerate coke formation, etc. Therefore, high content of nickel and vanadium is one of the key restrictive factors for heavy oil upgrading. However, on the other hand, the sulfides of metallic nickel and vanadium in the presence of hydrogen are the active species of common hydrogenation catalysts, especially the dispersed catalysts in the suspension bed hydrogenation process. At the same time, heavy oil has a high co...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10G45/44
CPCC10G45/44
Inventor 刘贺王宗贤范士广林存辉郭爱军陈坤
Owner CHINA UNIV OF PETROLEUM (EAST CHINA)
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