Unsupported and supported non-promoted ruthenium sulfide catalyst with high catalytic activity for hydrocarbon hydrotreatments and its method

摘要

The present invention relates to a synthesis method for unsupported and supported ruthenium base (RuS2) catalysts from a ruthenium complex precursor, which is decomposed and activated by a simple activation process; these steps provide a catalyst with very high catalytic activity, in addition the incorporation of ruthenium complex precursor to a support by methods of incipient and wet impregnating is described; the obtained catalytic activities in this invention are in the order of 100 times the molybdenum sulfide catalyst without support and without promoter, 14 times the industrial supported catalyst, and 5 times the activity of the currently most active commercial unsupported catalyst.

主权项

1. A synthesis method for obtaining ruthenium sulfide (RuS2) catalyst without an additional metal or not promoted comprising the steps of:
a) dissolving hydrated ruthenium chloride in a solution of R1COR2, R2-OH, C4H8O (THF), C4H8O2, CH2Cl2 (DCM), C2H3N (MeCN), C3H7ON (DMF), C2H6SO (DMSO) or a combination thereof: wherein: R1 is equal to OH or a lineal chain or branched radical C1 to C8; R2 is equal to H, a lineal chain or branched radical C1 to C8, with relation 0.01 to 40 ml of solvent per gram of salt dissolved in methanol, ethanol or acetone; b) dissolving ammonium chloride in solution of R1COR2, R2-OH, C4H8O (THF), C4H8O2, CH2Cl2 (DCM), C2H3N (MeCN), C3H7ON (DMF), C2H6SO (DMSO) or a combination of these; wherein: R1 is equal to OH or a lineal chain or branched radical C1 to C8; R2 is equal to H, a lineal chain or branched radical C1 to C8, with relation 0.01 to 40 ml of solvent per gram of salt dissolved in water, methanol, ethanol, acetone or combination thereof; c) adding the NH4CI solution of b) in a molar relation of 1:1 to 10:1 to the ruthenium chloride solution of a), keeping in mechanical agitation between 100 to 700 rpm during the addition and up to 30 minutes after the addition has finished; d) adding NH4OH or HCI in proportion of 0.01 to 2 ml per gram of ruthenium chloride; e) adding to the solution of step c) or d) a R3COR4 or R3COOR5 compound,
whereinR3 is a linear chain or branched radical C1 to C8,R4 is equal to H or a linear chain or branched radical C1 to C8 and includes 1 or 2 oxygen atoms or 1 nitrogen atom,R5 is equal to a hydrogen radical or a linear chain or branched radical C1 to C10; f) leaving to the solution of e) in mechanical agitation for 30 minutes between 100-700 rpm and resting from 0.1 to 3 hr to allow crystallization; a family of ruthenium complex compounds very soluble in water and sparingly soluble in acetone is produced and precipitated, the family of ruthenium complex compounds have decomposition temperatures above 200° C. and total decomposition to metallic ruthenium in inert atmosphere to temperatures lower than 415° C.; filtering and washing with acetone the precipitate; g) incorporating the family of ruthenium complex compounds to a support by using a method selected from an incipient impregnating method or a wet impregnating method, wherein a support bed includes: TiO2, zeolitic, MCM-41, SBA-15, alumina, silica, mixed oxides, or a combination thereof; doped or not doped, wherein the support is impregnated with a solution of the precursory complex in weight relation 1-90% of dissolved metallic charge in the minimum amount of solvent, wherein during the impregnation the solution of the ruthenium complex compounds is drip over the catalyst until filling all porosity; and h) decomposing and activating the ruthenium precursor complex at temperatures between 350° C. to 550° C. with a heating rate from 2 to 50° C. per minute under pressure of 1 atm, in a reducing atmosphere of a gas mixture formed by H2S/G where G may be H2, N2, Ar or He; in H2S concentrations from 2 to 99%.