Process for the hydroconversion of a low quality hydrocarbonaceous feedstock
The invention concerns a process for upgrading lower quality carbonaceous feedstock using a slurry catalyst composition. The use of particular organometallic compounds as precursors for the dispersed active catalyst allows for reduced coke formation.
1. A process for the hydroconversion of a lower quality hydrocarbonaceous feedstock, wherein the process comprises:
converting a precursor composition into an active slurry catalytic phase, and
hydroconverting the lower quality hydrocarbonaceous feedstock using the active slurry catalytic phase; and
wherein the precursor composition comprises at least one organometallic coordination compound of formula C 1 C 2 ML n (I), where
M is a transition metal selected from group IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB or IIB of the periodic table of elements, and wherein M is not Fe,
—C 1 and —C 2 are monocyclic or polycyclic aryl hydrocarbon ligands that are pi-bonded to M, —C 1 and —C 2 being the same or different, each of —C 1 or —C 2 comprising from 0 to 5 substituents R, each substituent R being the same or different, R being selected from:
a C3-C8 substituted or unsubstituted, monocyclic or polycyclic ring structure that is partially unsaturated, unsaturated or aromatic, fused or not fused to the ligand —C1 or —C2,
a C3-C8 substituted or unsubstituted, partially unsaturated or unsaturated, linear or branched, alicyclic hydrocarbyl radical,
a C1-C8, substituted or unsubstituted, linear or branched, saturated hydrocarbyl radical,
—C 1 and —C 2 being independent or connected via at least one substituent R,
-L is a ligand that is sigma-bonded to M, n is an integer equal to 0 to 3, each -L is, independently, a univalent ligand.
2. The process according to claim 1 , wherein each of C 1 or C 2 is a C5-C8 monocyclic polyene ligand comprising from 0 to 5 substituents R, each substituent R being the same of different, R being defined as in claim 1 .
3. The process according to claim 1 , wherein each of C 1 and C 2 is a cyclopentadienyl ligand comprising from 0 to 5 substituents R, each substituent R being the same or different, R being defined as in claim 1 .
4. The process according to claim 1 , wherein the organometallic coordination compound is a metallocene compound presenting the general formula (II) below
wherein the R substituted or unsubstituted cyclopentadienyl ligands are pi-bonded to M, and L ligands are sigma-bonded to M, and where M, L, R and n are defined as in formula (I).
5. The process according to claim 1 , wherein -L is selected from Hydride (-L=—H), Halide (-L=—F, —Cl, —Br, —I), cyanide (-L=—CN), Alkoxide (-L=—OR), Thiolate (-L=—SR), Amide (-L=—NR2), Phosphide (-L=—PR2), Alkyl (-L=—CH2R or other), Alkenyl (-L=—CHCHR), Alkynyl (-L=—CCR), Acyl (-L=—COR), Isocyanide (-L=—CNR), Nitrosyl (-L=—NO), Diazenide (-L=—NNR), Imide (-L=═NR), L=-ER3 or -EX3 (with E=Si, Ge, Sn), -L=—PR3, —PX3, —AsR3, —SbR3, amines, L=ER2 (with E=O, S, Se, Te), where X is an halogen atom, R is a C1-C8, preferably a C1-C6, linear or branched, alkyl, alkenyl Group or a C3-C8 alicyclic or aromatic group.
6. The process according to claim 1 , wherein M is selected from Group IIA, IIB, IIIB, IVB, VB, VIB, VIIB or VIII of the periodic table of the elements, and wherein M is not Fe.
7. The process according to claim 1 , wherein M is V or Mo.
8. The process according to claim 1 , wherein said precursor composition furthermore comprises at least one surfactant and/or a least one promoter.
9. The process according to claim 1 , wherein said precursor composition furthermore comprises a solvent.
10. The process according to claim 9 , wherein the solvent is a hydrocarbonaceous compound.
11. The process according to claim 1 , comprising a step of sulfiding said precursor composition using a sulfiding agent.
12. The process according to claim 11 , wherein said sulfiding step is performed before introduction of said precursor in the feedstock or after introduction of said precursor in the feedstock.
13. The process according to claim 1 , wherein the lower quality hydrocarbonaceous feedstock an atomic H/C ratio of at least 0.25.
14. The process according to claim 1 , wherein the lower quality hydrocarbonaceous feedstock is selected from atmospheric and vacuum residues, pitch coming from deasphalting, deasphalted oil, visbroken effluents, shale oils, biomass ex-pyrolysis, biomass ex-hydrothermal treatment, coal, petcoke from delayed coker, tires, polymers, road bitumen.