Process for hydrotreating hydro carbon feeds
AssigneeShell Oil Company
InventorRichard A. Kemp
Life of this patent
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Abstract
This invention relates to a process for preparing highly active hydrotreating catalysts prepared by incorporating cobalt and an element selected from the group consisting of molybdenum, tungsten and mixtures thereof, into an alumina hydrogel support. The final calcined catalysts have surface areas greater than about 300 m.sup.2 /g, flat plate crush strengths greater than about 14 lbs and more than about 80% of their pore volume in pores having diameters less than about 70 .ANG..
Claims42
A process for hydrotreating hydrocarbon feeds by contacting said feeds at a temperature in the range of from about 300.degree. F. to about 850.degree. F. and a pressure in the range of from about 200 psig to about 2500 psig with a hydrotreating catalyst which has a surface area above about 300 m.sup.2 /g and at least about 80% of the pore volume in pores having diameters less than about 70 .ANG., wherein said catalyst is prepared by a process which comprises:
- (a) precipitating an aqueous solution of one or more aluminum salt(s) by adjusting the pH to a range between about 5.5 and about 10.0 at a temperature in the range between about 20.degree. C. and about 90.degree. C.,
- (b) aging the precipitate at a temperature ranging from about 20.degree. C. to about 90.degree. C. for at least about 15 minutes at a pH ranging from about 8.0 to about 12.0,
- (c) washing the precipitate,
- (d) mixing the precipitate with dry, water-soluble salts of cobalt and a heavy metal selected from the group consisting of molybdenum, tungsten and mixtures thereof, at a pH in the range between about 4.0 and about 8.0 and a temperature in the range between about 25.degree. C. and about 100.degree. C. to yield a final catalyst having from about 1% w to about 5% w cobalt and from about 8% w to about 32% w heavy metal,
- (e) extruding the product of step (d), and
- (f) drying and calcining the product of step (e) at a temperature ranging from about 300.degree. C. to about 900.degree. C.
A process for hydrotreating hydrocarbon feeds by contacting said feeds at a temperature in the range of from about 300.degree. F. to about 850.degree. F. and a pressure in the range of from about 200 psig to about 2500 psig with a hydrotreating catalyst which has a surface area above about 300 m.sup.2 /g and at least about 80% of the pore volume in pores having diameters less than about 70 .ANG., wherein said catalyst is prepared by a process which comprises:
- (a) titrating an aqueous solution of an acid aluminum salt and an aqueous solution of a basic aluminum compound at a pH in the range between about 5.5 and about 10.0 and a temperature in the range between about 20.degree. C. and about 90.degree. C., thereby forming a precipitate,
- (b) aging the precipitate at a temperature ranging from about 20.degree. C. to about 90.degree. C. for at least about 15 minutes at a pH ranging from about 8.0 to about 12.0,
- (c) washing the precipitate,
- (d) mixing the precipitate with dry, water-soluble salts of cobalt and a heavy metal selected from the group consisting of molybdenum, tungsten and mixtures thereof, at a pH in the range between about 4.0 and about 8.0 and a temperature in the range between about 25.degree. C. and about 100.degree. C. to yield a final catalyst having from about 1% w to about 5% w cobalt and from about 8% w to about 32% w heavy metal,
- (e) extruding the product of step (d), and
- (f) drying and calcining the product of step (e) at a temperature ranging from about 300.degree. C. to about 900.degree. C.
A process for hydrotreating hydrocarbon feeds by contacting said feeds at a temperature in the range of from about 300.degree. F. to about 850.degree. F. and a pressure in the range of from about 200 psig to about 2500 psig with a hydrotreating catalyst which has a surface area above abpit 300 m.sup.2 /g and at least about 80% of the pore volume in pores having diameters less than about 70 .ANG., wherein said catalyst is prepared by a process which comprises:
- (a) precipitating an aqueous solution of one or more aluminum salts(s) by adjusting the pH to a range between about 5.5 and about 10.0 at a temperature in the range between about 20.degree. C. and about 90.degree. C.,
- (b) aging the precipitate at a temperature ranging from about 20.degree. C. to about 90.degree. C. for at least about 15 minutes at a pH ranging from about 8.0 to about 12.0,
- (c) washing the precipitate,
- (d) mixing a dry, water-soluble salt of a heavy metal selected from the group consisting of molybdenum, tungsten and mixtures thereof, and a mixture of a dry, water-soluble cobalt salt and a phosphorus-containing compound with the precipitate at a pH in the range between about 4.0 and about 8.0 and a temperature in the range between about 25.degree. C. and about 100.degree. C. to yield a final catalyst having from about 1% w to about 5% w cobalt and from about 8% w to about 18% w molybdenum or about 10% w to about 32% w tungsten,
- (e) extruding the product of step (d), and
- (f) drying and calcining the product of step (e) at a temperature ranging from about 300.degree. C. to about 900.degree. C.
A process for hydrotreating hydrocarbon feeds by contacting said feeds at a temperature in the range of from about 300.degree. F. to about 850.degree. F. and a pressure in the range of from about 200 psig to about 2500 psig with hydrotreating catalyst which has a surface area above about 300 m.sup.2 /g and at least about 80% of the pore volume in pores having diameters less than about 70 .ANG., wherein said catalyst is prepared by a process which comprises:
- (a) titrating an aqueous solution of an acid aluminum salt and an aqueous solution of a basic aluminum compound at a pH in the range between about 5.5 and about 10.0 and a temperature in the range between about 20.degree. C. and about 90.degree. C., thereby forming a precipitate,
- (b) aging the precipitate at a temperature ranging from about 20.degree. C. to about 90.degree. C. for at least about 15 minutes at a pH ranging from about 8.0 to about 12.0,
- (c) washing the precipitate,
- (d) mixing a dry, water-soluble salt of a heavy metal selected from the group consisting of molybdenum, tungsten and mixtures thereof, and a mixture of a dry, water-soluble cobalt salt and a phosphorus-containing compound with the precipitate at a pH in the range between about 4.0 and about 8.0 and a temperature in the range between about 25.degree. C. and about 100.degree. C. to yield a final catalyst having from about 1% w to about 5% w cobalt and from about 8% w to about 18% w molybdenum or about 10% w to about 32% w tungsten,
- (e) extruding the product of step (d), and
- (f) drying and calcining the product of step (e) at a temperature ranging from about 300.degree. C. to about 900.degree. C.
A process for hydrotreating hydrocarbon feeds by contacting said feeds at a temperature in the range of from about 300.degree. F. to about 850.degree. F. and a pressure in the range of from about 200 psig with a hydrotreating catalyst which has a surface area above about 300 m.sup.2 /g and at least about 80% of the pore volume in pores having diameters less than about 70 .ANG., wherein said catalyst is prepared by a process which comprises:
- (a) titrating an aqueous solution of an acid aluminum salt selected from the group consisting of aluminum sulfate, aluminum nitrate and aluminum chloride, and an aqueous solution of a basic aluminum compound selected from the group consisting of sodium aluminate and potassium aluminate, at a pH in the range between about 5.5 and about 8.0 and a temperature in the range between about 20.degree. C. and about 90.degree. C., thereby forming a precipitate,
- (b) aging the precipitate at a temperature ranging from about 20.degree. C. to about 90.degree. C. for at least about 15 minutes at a pH ranging from about 9.0 to about 11.0,
- (c) washing the precipitate,
- (d) mixing the precipitate with dry, water-soluble cobalt salts and molybdate or dimolybdate salts at a pH in the range between about 4.0 and about 5.0 and a temperature in the range between about 25.degree. C. and about 100.degree. C. to yield a final catalyst having from about 2.5% w to about 4.0% w cobalt and from about 10% w to about 10% w molybdenum,
- (e) extruding the product of step (d), and
- (f) drying and calcining the product of step (e) at a temperature ranging from about 300.degree. C. to about 900.degree. C.
A process for hydrotreating hydrocarbon feeds by contacting said feeds at a temperature in the range of from about 300.degree. F. to about 850.degree. F. and a pressure in the range of from about 200 psig to about 2500 psig with a hydrotreating catalyst which has a surface area above about 300 m.sup.2 /g and at least about 80% of the pore volume in pores having diameters less than about 70 .ANG., wherein said catalyst is prepared by a process which comprises:
- (a) titrating an aqueous solution of an acid aluminum salt selecting from the group consisting of aluminum sulfate, aluminum nitrate and aluminum chloride, and an aqueous solution of a basic aluminum compound selected from the group consisting of sodium aluminate and aluminum sulfate, at a pH in the range between about 5.5 and about 8.0 and a temperature in the range between about 20.degree. C. and about 90.degree. C., thereby forming a precipitate,
- (b) aging the precipitate at a temperature ranging from about 20.degree. C. to about 90.degree. C. for at least about 15 minutes at a pH ranging from about 9.0 to about 11.0,
- (c) washing the precipitate,
- (d) mixing the precipitate with dry, water-soluble cobalt salts and molybdate and dimolybdate salts, and phosphoric acid in an amount of from about 0.2 to about 1.5 moles of phosphorus per mole of molybdenum, at a pH in the range between about 4.0 and about 6.0 and a temperature in the range between about 25.degree. C. and about 100.degree. C. to yield a final catalyst having from about 2.5% w to about 4.0% w cobalt and from about 10% w to about 14% w molybdenum,
- (e) extruding the product of step (d), and
- (f) drying and calcining the product of step (e) at a temperature ranging from about 300.degree. C. to about 900.degree. C.
A process for hydrotreating hydrocarbon feeds by contacting said feeds at a temperature in the range of from about 300.degree. F. to about 850.degree. F. and a pressure in the range of from about 200 psig to about 2500 psig with a hydrotreating catalyst which has a surface area above about 300 m.sup.2 /g and at least about 80% of the pore volume in pores having diameters less than about 70 .ANG., wherein said catalyst is prepared by a process which comprises:
- (a) precipitating an aqueous solution of an acid aluminum salt selected from the group consisting of aluminum sulfate, aluminum nitrate and aluminum chloride, with an aqueous solution of a base at a pH in the range between about 5.5 and about 8.0 and a temperature in the range between about 20.degree. C. and about 90.degree. C.,
- (b) aging the precipitate at a temperature ranging from about 20.degree. C. to about 90.degree. C. for at least about 15 minutes at a pH ranging from about 9.0 to about 11.0.
- (c) washing the precipitate,
- (d) mixing the precipitate with dry, water-soluble cobalt salts and molybdate or dimolybdate salts at a pH in the range between about 4.0 and about 6.0 and a temperature in the range between about 25.degree. C. and about 100.degree. C. to yield a final catalyst having from about 2.5% w to about 4.0% w cobalt and from about 10% w to about 14% w molybdenum,
- (e) extruding the product of step (d), and
- (f) drying and calcining the product of step (e) at a temperature ranging from about 300.degree. C. to about 900.degree. C.,
A process for hydrotreating hydrocarbon feeds by contacting said feeds at a temperature in the range of from about 300.degree. F. to about 850.degree. F. and a pressure in the range of from about 200 psig to about 2500 psig with a hydrotreating catalyst which has a surface area above about 300 m.sup.2 /g and at least about 80% of the pore volume in pores having diameters less than about 70 .ANG., wherein said catalyst is prepared by a process which comprises:
- (a) precipitating an aqueous solution of an acid with an aqueous solution of a basic aluminum compound selected from the group consisting of sodium aluminate and potassium aluminate, at a pH in the range between about 5.5 and about 8.0 and a temperature in the range between about 20.degree. C. and about 90.degree. C.,
- (b) aging the precipitate at a temperature ranging from about 20.degree. C. to about 90.degree. C. for at least about 15 minute at a pH ranging from about 9.0 to about 11.0,
- (c) washing the precipitate,
- (d) mixing the precipitate with dry, water-soluble cobalt salts and molybdate or dimolybdate salts at a pH in the range between about 4.0 and about 6.0 and a temperature in the range between about 25.degree. C. and about 100.degree. C. to yield a final catalyst having from about 2.5% w to about 4.0%2w cobalt and from about 10% w to about 14% w molybdenum,
- (e) extruding the product of step (d), and
- (f) drying and calcining the product of step (e) at a temperature ranging from about 300.degree. C. to about 900.degree. C.
A process for hydrotreating hydrocarbon feeds by contacting said feeds at a temperature in the range of from about 300.degree. F. to about 850.degree. F. and a pressure in the range of from about 200 psig to about 2500 psig with a hydrotreating catalyst which has a surface area above about 300 m.sup.2 /g and at least about 80% of the pore volume in pores having diameters less than about 70 .ANG., wherein said catalyst is prepared by a process which comprises:
- (a) precipitating an aqueous solution of an acid aluminum salt selected from the group consisting of aluminum sulfate, aluminum nitrate and aluminum chloride, with an aqueous solution of a base at a pH in the range between about 5.5 and about 8.0 and a temperature in the range between about 20.degree. C. and about 90.degree. C.,
- (b) aging the precipitate at a temperature ranging from about 20.degree. C. to about 90.degree. C. for at least about 15 minutes at a pH ranging from about 9.0 to about 11.0,
- (c) washing the precipitate,
- (d) mixing the precipitate with dry, water-soluble cobalt salts and molybdate or dimolybdate salts, and phosphoric acid in an amount of from about 0.2 to about 1.5 moles of phosphorus per mole of molybdenum, at a pH in the range between about 4.0 and about 6.0 and a temperature in the range between about 25.degree. C. and about 100.degree. C. to yield a final catalyst having from about 2.5% w to about 4.0% w cobalt and from about 10% w to about 14% w molybdenum,
- (e) extruding the product to step (d), and
- (f) drying and calcining the product of step (e) at a temperature ranging from about 300.degree. C. to about 900.degree. C.
A process for hydrotreating hydrocarbon feeds by contacting said feeds at a temperature in the range of from about 300.degree. F. to about 850.degree. F. and a pressure in the range of from about 200 psig to about 2500 psig with a hydrotreating catalyst which has a surface area above about 300 m.sup.2 /g and at least about 80% of the pore volume in pores having diameters less than about 70 .ANG., wherein said catalyst is prepared by a process which comprises:
- (a) precipitating an aqueous solution of an acid with an aqueous solution of a basic aluminum compound selected from the group consisting of sodium aluminate and potassium aluminate, at a pH in the range between about 5.5 and about 8.0 and a temperature in the range between about 20.degree. C. and about 90.degree. C.,
- (b) aging the precipitate at a temperature ranging from about 20.degree. C. to about 90.degree. C. for at least about 15 minutes at a pH ranging from about 9.0 to about 11.0,
- (c) washing the precipitate,
- (d) mixing the precipitate with dry, water-soluble cobalt salts and molybdate or dimolybdate salts, and phosphoric acid in an amount of from about 0.2 to about 1.5 moles of phosphorus per mole of molybdenum, at a pH in the range between about 4.0 and about 6.0 and a temperature in the range between about 25.degree. C. and about 100.degree. C. to yield a final catalyst having from about 2.5% w to about 4.0% w cobalt and from about 100% w to about 14% w molybdenum,
- (e) extruding the product of step (d), and
- (f) drying and calcining the product of step (e) at a temperature ranging from about 300.degree. C. to about 900.degree. C.
Dependencies are inferred from the claim text.