US 4,525,267 A · Process for hydrocracking hydrocarbons with hydrotreatment-regeneration of spent catalyst

Abstract

A process for hydrocracking hydrocarbons for residuum conversion in the presence of a fluidized catalyst, which is characterized by extracting at least part of the fluidized catalyst from the reaction system as a spent catalyst, subjecting at least part of the spent catalyst to hydrotreatment for solubilizing toluene-insoluble carbonaceous materials deposited on the catalyst thereby regenerating the spent catalyst, and recycling the regenerated catalyst to the hydrocracking step. According to this process, the spent catalyst is recycled to the hydrocracking step in a highly activated state after the regenerative hydrotreatment, so that it becomes possible to suppress the coke production within the reactor to a considerable degree, to maintain the coke level of the catalyst below a predetermined value and to preclude the contamination of the reactor walls with coke. The process of the invention which regenerates the spent catalyst by a hydrotreatment, in contrast to the conventional catalyst regeneration by oxidative roasting, eliminates all the difficult problems as encountered in the oxidative roasting methods.

Claims24

Dependent claims

A residuum conversion process comprising the steps of:

hydrocracking, in a first zone, a heavy hydrocarbon oil at a temperature of 350.degree.-500.degree. C. and a partial pressure of hydrogen of 10-350 Kg/cm.sup.2 in the presence of a first catalyst which is maintained in a fluidized state, which contains at least one hydrogenation-active metal component selected from the group consisting of the metals of Groups Ib, IIb, IIIa, IVa, Va, VIa and VIII, manganese and tin and which has a volume mean particle size of not greater than 50.mu. wherein toluene insoluble carbonaceous materials are disposited on the first catalyst;
discharging at least part of the first catalyst on which toluene-insoluble carbonaceous materials are deposited from said first zone as spent catalyst;
hydrotreating, in a second zone, at least part of the spent catalyst at a temperature of 350.degree.-450.degree. C. and a partial pressure of hydrogen of 30-350 Kg/cm.sup.2 in the presence of a liquid hydrocarbon and in the further presence of a second catalyst having an average pore diameter of 20-150 .ANG., a specific surface area of 50 m.sup.2 /g or more and a larger bulk volume than said first catalyst and containing at least 5 wt % of one or more metals selected from the group consisting of vanadium, molybdenum, tungsten, nickel, cobalt and copper supported on an acidic carrier, thereby to regenerate the spent catalyst by solubilizing the toluene-insoluble carbonaceous materials deposited thereon;
and
recycling the regenerated catalyst to said first zone as at least part of said first catalyst.

2 more elements

A process for hydrocracking heavy petroleum oils, wherein a heavy petroleum oil containing at least 80% of heavy components with a boiling point of 350.degree. C. or higher, at least 200 ppm of soluble metals and no more than 0.1% of insoluble solid components, is hydrocracked in the presence of a fluidized catalyst for converting said heavy oil into a light oil containing at least 30% of a fraction of a boiling point of 350.degree. C. or lower and no more than 20 ppm of soluble metals and being substantially free of n-heptane insoluble asphaltenes, said process being characterized by the steps of:

(a) hydrocracking the above-mentioned feed oil under a partial pressure of hydrogen of 30-250 kg/cm.sup.2 and at a temperature of 400.degree.-480.degree. C., using, as the fluidized catalyst, a first finely particulate catalyst having a volume means particle size of 0.1-50.mu. in a concentration of 0.1-5 wt %, said first catalyst containing at least one hydrogenation-active component selected from the group consisting of metals of Groups Ib, IIb, IIIa, Va, IVa, VIa and VIII, maganese and tin;
(b) separating at least 10% of spent catalyst contained in the product oil of said hydrocracking by solid-liquid separation;
(c) separating the product oil containing the remainder of the spent catalyst into a light oil substantially free of the spent catalyst and a heavy oil containing the spent catalyst;
(d) dispersing at least part of the spent catalyst separated in step (b) in the light oil separated in step (c) having a boiling point of at least 200.degree. C. or a hydrotreated oil thereof, subjecting the dispersed spent catalyst to a hydrotreatment under a hydrogen pressure of 30-250 kg/cm.sup.2 and at a temperature of 350.degree.-450.degree. C. to solubilize at least part of insoluble carbonaceous materials in said spent catalyst thereby to regenerate said spent catalyst, said hydrogeneration being performed in the pressure of a second catalyst having an average pore diameter of 20-150 .ANG., a specific surface area of 50 m.sup.2 /g or more and a larger bulk volume than said first catalyst and containing at least 5 wt % of one or more metals selected from the group consisting of vanadium, molybdenum, tungsten, nickel, cobalt, copper and composited with an acidic carrier;
and
(e) recycling said light oil containing the regenerated catalyst to step (a), if necessary along with at least part of the heavy oil obtained in step (c).

3 more elements

A process for hydrocrcking heavy hydrocarbon oils containing insoluble solids whereby tar sand bitumen or oil tar with an insoluble solid content of at least 0.2%, or a residue separated therefrom is hydrocracked in the presence of a fluidized catalyst, said process comprising the steps of:

(a) hydrocracking the feed oil using, as the fluidized catalyst, a first catalyst under a hydrogen pressure of 30-250 kg/cm.sup.2 and a temperature fo 400.degree.-480.degree. C., said first catalyst containing at least one hydrogenation-active metal component selected from the group consisting of the metals of Groups Ib, IIb, IIIa, IVa, Va, VIa and VIII, manganese and tin and which has a volume mean particle size of not greater than 50.mu.;
(b) subjecting the product oil of the hydrocracking to a high gradient magnetic separation to effect separation of magnetizable solids composed of insoluble solid components with high iron and vanadium contents from the product oil;
(c) separating from said product oil a light oil fraction substantially free of insoluble solids;
(d) dispersing at least part of said solids separated in step (b) in the light oil obtained in step (c) and having a boiling point of at least 200.degree. C. or a hydrotreated oil thereof, the resulting dispersion being subjected to a hydrotreatment in the presence of a second catalyst under a hydrogen pressure of 30-250 kg/cm.sup.2 and at a temperature of 350.degree.-450.degree. C. for solubilizing the carbonaceous materials deposited on said solids, said second catalyst having an average pore diameter of 20-150 .ANG., a specific surface area of 50 m.sup.2 /g or more and a larger bulk volume than said first catalyst and containing at least 5 wt % of one or more metals selected from the group consisting of vanadium, molybdenum, tungsten, nickel, cobalt and copper and composited with an acidic carrier;
(e) recycling the thus hydrotreated solids so as to serve as the catalyst in step (a).