METHOD OF HYDROCONVERSION OF HEAVY HYDROCARBON RAW MATERIAL (VERSIONS) Russian patent published in 2017 - IPC C10G49/04 C10G47/20 C10G47/26 B01J23/28 

FIELD: technological processes.

SUBSTANCE: invention relates to methods of hydroconversion of heavy hydrocarbon raw material (HHRM) in presence of dispersed, ultra dispersed or nano-sized catalysts. Said method can be used in hydroconversion of heavy bituminous oils, natural bitumen, high-boiling oil refining residues and is intended for production of liquid hydrocarbon products with lower boiling temperature than the starting material. Method of hydroconversion of heavy hydrocarbon raw material involves preparation of an aqueous solution of a catalyst precursor – polymolybdic acid H_n[H_2+2kMo_1+mO_4+3m+k], where m>7, k>2, n=1–5, having the pH from 0.5 to 3 (preferably 1–2.5), emulsification of this solution into the raw material or its part, mixing the prepared raw material containing the emulsified catalyst precursor with a hydrogen-containing gas, heating the obtained gas-liquid mixture to sulfidizing the catalyst precursor, hydroconversion in the ascending stream of the raw material at the pressure of 5–9 MPa in presence of a catalyst formed from the precursor with the particle size less than 100 nm, separation of the obtained products in a separators system and recirculation of the hydrogen-containing gas into the stage of mixing. In one version before emulsification the raw material is introduced with a catalyst precursor extractant selected from primary, secondary and tertiary amines with the number of carbon atoms in alkyl substitutes of not less than 8, organic compounds, which include pyridine, quinoline or pyrrole groups, and industrial nitrogen-containing extractants. Molar ratio of the introduced extractant and precursor (in terms of MoO₃ mole) is from 2:1 to 20:1, the ratio of volumes of the organic and the water phases at the emulsification is from 20:1 to 200:1, preferably, from 25:1 to 100:1. In another version the hydrocarbon raw material contains nitrogenous bases, which are the extractant in relation to the catalyst precursor at the atomic ratio of the basic nitrogen content in the raw material Ν_basic to the content of molybdenum as part of the precursor from 20:1 to 100:1 (preferably 40:1–80:1) and the content of N_basic in the hydrocarbon raw material of not less than 0.3 %. Viscosity of the raw material containing the extractant at the emulsification temperature of 50–90 °C is from 0.5 to 2.5 Pa⋅sec. Before mixing the hydrogen-containing gas is heated up to 420–450 °C. Hydroconversion is carried out at 420–450 °C, at the ratio of hydrogen to the raw material = (500–1,500):1 nl/l, the raw material holding in the reaction zone for 0.33–2 parts. Preferably part of unconverted residue of the hydroconversion is recycled into the stage of mixing, and the other part is used for regeneration of the catalyst precursor, which is recycled into the stage of emulsification.

EFFECT: increasing the catalyst activity, conversion, output of distillate products, reducing coke formation.

17 cl, 2 dwg, 3 tbl, 7 ex