A kind of residual oil hydrothermal cracking catalyst and its preparation and application

Abstract

The invention relates to a thermal cracking catalyst for residual oil in presence of hydrogen, and preparation and application thereof; the thermal cracking catalyst disclosed by the invention is composed of an iron-containing compound and carbon powder and is of a compound catalyst; the primary particle of the iron-containing compound is a microsphere with the diameter of 10-50 nm; the average particle size of secondary particles is less than 100 mu m; and the average particle size of the carbon powder is less than 100 mu m. When the compound catalyst is used for thermal cracking catalyst for residual oil in presence of hydrogen, in terms of Fe, the addition amount of the catalyst is 0.2-2.0% by weight of the residual oil raw material; and the use amount of the carbon powder is 0.5-10.0% by weight of the residual oil raw material. The catalyst provided by the invention is particularly suitable for carrying out thermal cracking on asphaltene super-heavy oil and poor-quality residual oil having high metal content in presence of hydrogen; and the catalyst disclosed by the invention has the advantages of being high in cracking activity, little to coke, simple in preparation method, free from noble metal and low in cost.

Description

technical field [0001] The invention relates to a composite catalyst for hydrothermal cracking of residual oil, a preparation method of the catalyst, and a method for thermal cracking of residual oil by using the catalyst. Background technique [0002] The increasingly heavy and inferior oil resources in the world and the contradiction between the rapid economic growth and the increasing demand for petroleum products have made refineries pay more and more attention to the technology of lightening heavy oil. The cracking process has strong competitiveness and good development prospects because it can deal with low-quality raw materials with high carbon residue and high metal content. Catalyst is one of the core technologies of residual oil hydrothermal cracking process. It is very important for reducing reaction severity, improving reaction efficiency, increasing oil yield, reducing coke yield, thereby reducing residual oil processing cost and improving its economic competiti...

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Problems solved by technology

[0004] Carbonaceous powder catalyst is a kind of residual oil slurry bed hydrothermal cracking catalyst that is widely used. For example, in the prior art of residual oil slurry bed hydrothermal cracking, ferrous sulfate, ore powder or coal powder are used as additives. These The additive has a certain coke-carrying performance, but due to the low iron content in the additive, there are disadvantages such as a large amount of addition, poor dispersion in raw materials, and serious wear and tear on equipment

[0005] CN1020112C proposes the hydrothermal cracking of heavy oil in the presence of superfine ferric sulfate, which requires ferric sulfate or iron ore to be mixed with oil, and ground to a particle size of less than 45 microns in a stirring ball mill, preferably at least 50% of the particles The particle size of the catalyst is less than 5 microns. Although the use of this catalyst is beneficial to reduce coke formation and improve asphalt conversion, it is easy to operate in the laboratory to grind the solid to several microns, but the industrial implementation has higher requirements for the grinding machine and a large loss , it is difficult to achieve

Solid-phase method is difficult to form nano-scale grains, hydrothermal / solvothermal synthesis method needs to be in a closed container, under the conditions of relatively high temperature and high pressure (generally 200 ° C, the pressure is generated by heating the solution), and requires a large amount of solvent, production high cost

[0007] CN1255407A and USP5866501 disclose a kind of dispersive fine-grained, anion-modified and phosphorus-promoted iron oxide slurry catalyst, this catalyst has large specific surface area and the particle size less than 50 angstroms, the applicant recommends with wet cake gel However, the wet cake contains at least 60% of water. The introduction of this part of water will not only increase the load on the reactor, but also cause difficulties in the separation of subsequent products. After drying, it is added as a dry powder. Due to the aggregation between particles, Catalyst activity decreases, heavy fractions are more

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