US 7,658,895 B2 · Process for recovering base metals from spent hydroprocessing catalyst

Abstract

A method for recovering metals from a spent dispersed catalyst originating from a Group VIB metal sulfide catalyst containing at least a Group VB and Group VIII metal for hydrocarbon oil hydroprocessing is disclosed. In one embodiment, the method comprises the steps of: contacting the spent dispersed catalyst with a leaching solution containing ammonia and air to dissolve the group VIB metal and the Group VIII metal into the leaching solution at sufficient temperature and pressure; forming a slurry containing at least a group VIB metal complex and at least a group VIII metal complex, ammonium sulfate and solid residue containing at least a Group VB metal complex and coke; separating and removing the solid residue containing ammonium metavanadate and coke from the pressure leach solution (PLS); precipitating from the PLS at least a portion of the Group VIB metal and at least a portion of the Group VIII metal by controlling the pH at a pre-selected pH to selectively precipitate as metal complexes the Group VIB and Group VIII metals.

Claims22

Dependent claims

A method of recovering metals from a spent dispersed catalyst originating from a Group VIB metal sulfide catalyst and at least a Group VB metal promoted with a Group VIII metal for hydrocarbon oil hydroprocessing, the method comprising the steps of:

contacting the spent dispersed catalyst with a leaching solution containing ammonia and air to dissolve the Group VIB metal and the Group VIII metal into the leaching solution at a sufficient temperature and pressure to form a pressure leach slurry containing at least a Group VIB soluble metal complex and at least a Group VIII soluble metal complex and solid residue containing at least a Group VB metal complex and coke;
separating and removing the solid residue containing the Group VB metal complex and coke from the pressure leach slurry, forming a pressure leach solution;
mixing the pressure leach solution with an additive selected from the group consisting of a mineral acid, a sulfide-containing compound, and a sulfur compound under mixing conditions at a temperature in the range of 50 to 90° C. for a sufficient amount of time to precipitate at least a portion of the Group VIB metal and at least a portion of the Group VIII metal, wherein the precipitation being carried out at a first pre-selected pH to precipitate as metal complexes at least a portion of the Group VIB metal and at least a portion of the Group VIII metal.

A method of recovering metals from a spent dispersed catalyst, the method comprising the steps of:

contacting the spent dispersed catalyst with a leaching solution containing ammonia and air to dissolve the Group VIB metal and the Group VIII metal into the leaching solution at a sufficient temperature and pressure to form a pressure leach slurry containing at least a Group VIB soluble metal complex and at least a Group VIII soluble metal complex, ammonium sulfate and solid residue containing at least a Group VB metal complex and coke;
separating and removing the solid residue containing the Group VB metal complex and coke from the pressure leach slurry, forming a pressure leach solution;
mixing the pressure leach solution with an additive selected from the group consisting of a mineral acid, a sulfide-containing compound, and a sulfur compound under mixing conditions at a temperature in the range of 50 to 90° C. for a sufficient amount of time to precipitate at least a portion of the Group VIB metal and at least a portion of the Group VIII metal, wherein the precipitation being carried out at a first pre-selected pH to precipitate as metal complexes at least a portion of the Group VIB metal and at least a portion of the Group VIII metal;
wherein the spent dispersed catalyst originates from a hydroprocessing catalyst having a general formula (X)a(M)b[(CH3CH2)cN(CH3)3]dOz and containing at least a group VB metal, wherein X is a Group VIII non-noble metal, M is a group VIB metal selected from Mo and W and combinations thereof, c is an integer from 10 to 40, the molar ratio of a:b is from 0.5/1 to 3/1.

1 more element

A method of recovering metals including vanadium from a spent dispersed catalyst;

the method comprising the steps of:
contacting the spent dispersed catalyst with a leaching solution containing ammonia and air to dissolve the Group VIB metal and the Group VIII metal into the leaching solution at a sufficient temperature and pressure to form a pressure leach slurry containing at least a group VIB soluble metal complex and at least a group VIII soluble metal complex, ammonium sulfate and solid residue containing at least a Group VB metal complex and coke;
separating and removing the solid residue containing ammonium metavanadate and coke from the pressure leach slurry, forming a pressure leach solution;
mixing the pressure leach solution with an additive selected from the group consisting of a mineral acid, a sulfide-containing compound, and a sulfur compound under mixing conditions at a temperature in the range of 50 to 90° C. for a sufficient amount of time to precipitate at least a portion of the Group VIB metal and at least a portion of the Group VIII metal, wherein the precipitation being carried out at a first pre-selected pH to precipitate as metal complexes at least a portion of the Group VIB metal and at least a portion of the Group VIII metal;
recovering the metal complexes by filtration, forming a first supernatant containing 0.1 to 3% of the Group VIB metal in the spent dispersed catalyst for metal recovery, 1 to 20% of the Group VB metal in the spent dispersed catalyst for metal recovery, and 1 to 35% of the Group VIII metal in the spent dispersed catalyst for metal recovery;
precipitating from the first supernatant at least a portion of the Group VIB metal and at least a portion of the Group VIII metal, wherein the precipitation being carried out at a second pre-selected pH to precipitate as metal complexes at least 95% of the Group VIB metal and at least 95% of the Group VIII metal initially present in the first supernatant prior to the precipitation at the second pre-selected pH;
and
recovering the Group VIB and group VIII metal sulfides by filtration, forming a second supernatant containing less than 100 ppm of the group VIB metal, less than 20 ppm of the Group VIII metal, and less than 100 ppm of the group VB metal;
wherein the spent dispersed catalyst originates from a hydroprocessing catalyst having a general formula (Mt)a(Xu)b(Sv)d(Cw)e(Hx)f(Oy)g(Nz)h containing at least a Group VB metal, wherein M is at least one group VIB metal, X is at least one of a non-noble Group VIII metal, a Group VIIIB metal, a Group VIB metal, a Group IVB metal, and a Group IIB metal, 0=<b/a=<5, (a+0.5b)<=d<=(5a+2b), 0<=e<=11(a+b), 0<=f<=7(a+b), 0<=g<=5(a+b), 0<=h<=0.5(a+b);
t, u, v, w, x, y, z, each representing total charge for each of:
M, X, S, C, H, O and N, respectively;
ta+ub+vd+we+xf+yg+zh=0.

9 more elements

Dependencies are inferred from the claim text.

Process for recovering base metals from spent hydroprocessing catalyst

Life of this patent

Process for recovering base metals from spent hydroprocessing catalyst

Life of this patent

Abstract

Claims22