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US 4,540,483 AGranted
Hydrotreating process
AssigneeUnion Oil Company of California
InventorsHoward D. Simpson, Ryden L. Richardson, Paul K. Angmorter
Life of this patent
Estimating the term…
Abstract
A hydrotreating catalyst comprising molybdenum, nickel, and phosphorus active components supported on gamma alumina is prepared with gamma alumina support particles which have been contacted with aqueous ammonia and is employed in the hydrotreating process to reduce the sulfer and nitrogen content of hydrocarbons.
Claims22
A process for hydrodenitrogenating and/or hydrodesulfurizing a hydrocarbon feedstock containing organonitrogen and/or organosulfur compounds comprising the steps of:
- (a) contacting said feedstock with hydrogen in the presence of a catalyst composition at elevated temperatures and pressures such that some of said organonitrogen and/or organosulfur compounds are converted to ammonia and/or hydrogen sulfide, thereby yielding a denitrogenated and/or desulfurized hydrocarbon product phase and an ammonia and/or hydrogen sulfide phase, said catalyst composition being comprised of molybdenum, nickel and phosphorous active components on support particles comprising gamma alumina, and said catalyst having been prepared by a method comprising the steps of (1) contacting said gamma alumina support particles with an aqueous solution containing ammonium hydroxide, (2) impregnating the resultant support particles with molybdenum, nickel and phosphorous, (3) calcining the impregnated particles at an elevated temperature in the presence of oxygen, and (4) sulfiding the calcined particles such that essentially all molybdenum and nickel components are converted to metal sulfides;
- and
- (b) separating said hydrocarbon product phase from said ammonia and/or hydrogen sulfide phase.
A process for treating hydrocarbons comprising contacting a hydrocarbon feedstock containing organonitrogen or organosulfur compounds or both organonitrogen and organosulfur compounds with a catalyst under hydrotreating conditions including an elevated temperature, an elevated pressure and the presence of molecular hydrogen, so as to produce a hydrocarbon product of reduced organonitrogen or organosulfur content, said catalyst comprising molybdenum, nickel and phosphorous active components on support particles comprising gamma alumina, said catalyst having been prepared by a method comprising the steps of:
- (a) contacting said support particles with an aqueous ammonia solution;
- (b) subsequently impregnating the resultant support particles with molybdenum, nickel and phosphorous by contacting said support particles with an acidic impregnating solution containing molybdenum, nickel and phosphorous;
- (c) calcining impregnated particles from step (b) at an elevated temperature in the presence of oxygen;
- and
- (d) sulfiding calcined particles obtained from step (c) to convert essentially all of the molybdenum and nickel components to metal sulfides.
2 more elements
A process for treating hydrocarbons comprising contacting a hydrocarbon feedstock containing organonitrogen or organosulfur compounds or both organonitrogen and organosulfur compounds with a catalyst under hydrotreating conditions including an elevated temperature, an elevated pressure and the presence of molecular hydrogen, so as to produce a hydrocarbon product of reduced organonitrogen or organosulfur content, said catalyst comprising molybdenum, nickel and phosphorous active components on support particles comprising gamma alumina, said catalyst having been prepared by a method comprising the steps of:
- (a) contacting said support particles with an aqueous ammonia solution, said support particles having more than 60 percent of their aggregate particle pore volume in pores having diameters between about 60 and about 80 angstroms;
- (b) subsequently impregnating the resultant support particles with molybdenum, nickel and phosphorous by contacting said support particles with molybdenum, nickel and phosphorous;
- (c) calcining impregnated particles from step (b) at an elevated temperature in the presence of oxygen;
- and
- (d) sulfiding calcined particles obtained from step (c) to convert essentially all of the molybdenum and nickel components to metal sulfides.
2 more elements
A process for hydrotreating a hydrocarbon feedstock containing organonitrogen compounds comprising the steps of:
- (a) contacting said feedstock with hydrogen in the presence of a catalyst composition at elevated temperatures and pressures such that some of said organonitrogen compounds are converted to ammonia, thereby yielding a denitrogenated hydrocarbon product phase and an ammonia phase, said catalyst composition being comprised of molybdenum, nickel and phosphorous active components on support particles comprising gamma alumina and having more than 60 percent of this aggregate particle pore volume in pores having diameters between about 60 and about 80 angstroms, and said catalyst having been prepared by a method comprising the steps of (1) contacting selected gamma alumina support particles with a volume of an aqueous ammonia solution containing between about 20 and about 30 weight percent ammonium hydroxide, said volume being sufficient to essentially fill the aggregate pore volume of said particles, and said support particles being selected such that more than 60 percent of the aggregate particle pore volume is in pores having diameters between about 60 and about 80 angstroms;
- (2) drying the resultant support particles;
- (3) contacting dried particles obtained from step (2) with an aqueous solution of citric acid;
- (4) introducing an acidic aqueous solution containing ammonium heptamolybdate, nickel nitrate, and phosphoric acid into the pores of particles obtained from step (3) so as to provide composites containing, when dry, between about 12 and about 30 weight percent molybdenum components, calculated as molybdenum trioxide, between about 2 and about 6 weight percent nickel components, calculated as nickel oxide, and between about 2 and about 6 percent phosphorous components, calculated as elemental phosphorous, such that the ratio of said nickel components, calculated as nickel oxide, to said molybdenum components, calculated as molybdenum trioxide, is between about 0.15:1 and about 0.20:1, and such that the ratio of said phosphorous components, calculated as elemental phosphorous, to said nickel components, calculated as nickel oxide, is between about 0.5:1 and 1:1;
- (5) drying composites obtained from step (4);
- (6) calcining dried composites obtained from step (5) at temperatures between about 975.degree. F. and about 1,025.degree. F. in the presence of oxygen such that said molybdenum and nickel components are essentially converted to metal oxides;
- (7) sulfiding said dried composites obtained from step (6) by contacting said composites with hydrogen sulfide and/or organic sulfur compounds in a hydrogen atmosphere such that said metal oxides are essentially converted to metal sulfides;
- and
- (b) separating said hydrocarbon product phase from said ammonia phase.
6 more elements
A process for hydrodesulfurizing a hydrocarbon feedstock containing organosulfur compounds comprising the steps of:
- (a) contacting said feedstock with hydrogen in the presence of a catalyst composition at elevated temperatures and pressures such that some of said organosulfur compounds are converted to hydrogen sulfide, thereby yielding a desulfurized hydrocarbon product phase and a hydrogen sulfide phase, said catalyst composition being comprised of molybdenum, nickel and phosphorous active components on support particles comprising gamma alumina and having more than 60 percent of this aggregate particle pore volume in pores having diameters between about 60 and about 80 angstroms, and said catalyst having been prepared by a method comprising the steps of (1) contacting selected gamma alumina support particles with a volume of an aqueous ammonia solution containing between about 20 and about 30 weight percent ammonium hydroxide, said volume being sufficient to essentially fill the aggregate pore volume of said particles, and said support particles being selected such that more than 60 percent of the aggregate particle pore volume is in pores having diameters between about 60 and about 80 angstroms;
- (2) drying the resultant support particles;
- (3) contacting dried particles obtained from step (2) with an aqueous solution of citric acid;
- (4) introducing an acidic aqueous solution containing ammonium heptamolybdate, nickel nitrate, and phosphoric acid into the pores of particles obtained from step (3) so as to provide composites containing, when dry, between about 12 and about 30 weight percent molybdenum components, calculated as molybdenum trioxide, between about 2 and about 6 weight percent nickel components, calculated as nickel oxide, and between about 2 and about 6 percent phosphorous components, calculated as elemental phosphorous, such that the ratio of said nickel components, calculated as nickel oxide, to said molybdenum components, calculated as molybdenum trioxide, is between about 0.15:1 and about 0.20:1, and such that the ratio of said phosphorous components, calculated as elemental phosphorous, to said nickel components, calculated as nickel oxide, is between about 0.5:1 and 1:1;
- (5) drying composites obtained from step (4);
- (6) calcining dried composites obtained from step (5) at temperatures between about 975.degree. F. and about 1,025.degree. F. in the presence of oxygen such that said molybdenum and nickel components are essentially converted to metal oxides;
- (7) sulfiding said dried composites obtained from step (6) by contacting said composites with hydrogen sulfide and/or organic sulfur compounds in a hydrogen atmosphere such that said metal oxides are essentially converted to metal sulfides;
- and
- (b) separating said hydrocarbon product phase from said hydrogen sulfide phase.
6 more elements
A process for hydrotreating and hydrodesulfurizing a hydrocarbon feedstock containing organonitrogen and organosulfur compounds comprising the steps of:
- (a) contacting said feedstock with hydrogen in the presence of a catalyst composition at elevated temperatures and pressures such that some of said organonitrogen and organosulfur compounds are converted to ammonia and hydrogen sulfide, thereby yielding a denitrogenated and desulfurized hydrocarbon product phase and an ammonia and hydrogen sulfide phase, said catalyst composition being comprised of molybdenum, nickel and phosphorous active components on support particles comprising gamma alumina and having more than 60 percent of this aggregate particle pore volume in pores having diameters between about 60 and about 80 angstroms, and said catalyst having been prepared by a method comprising the steps of (1) contacting selected gamma alumina support particles with a volume of an aqueous ammonia solution containing between about 20 and about 30 weight percent ammonium hydroxide, said volume being sufficient to essentially fill the aggregate pore volume of said particles, and said support particles being selected such that more than 60 percent of the aggregate particle pore volume is in pores having diameters between about 60 and about 80 angstroms;
- (2) drying the resultant support particles;
- (3) contacting dried particles obtained from step (2) with an aqueous solution of citric acid;
- (4) introducing an acidic aqueous solution containing ammonium heptamolybdate, nickel nitrate, and phosphoric acid into the pores of particles obtained from step (3) so as to provide composites containing, when dry, between about 12 and about 30 weight percent molybdenum components, calculated as molybdenum trioxide, between about 2 and about 6 weight percent nickel components, calculated as nickel oxide, and between about 2 and about 6 percent phosphorous components, calculated as elemental phosphorous, such that the ratio of said nickel components, calculated as nickel oxide, to said molybdenum components, calculated as molybdenum trioxide, is between about 0.15:1 and about 0.20:1, and such that the ratio of said phosphorous components, calculated as elemental phosphorous, to said nickel components, calculated as nickel oxide, is between about 0.5:1 and 1:1;
- (5) drying composites obtained from step (4);
- (6) calcining dried composites obtained from step (5) at temperatures between about 975.degree. F. and about 1,025.degree. F. in the presence of oxygen such that said molybdenum and nickel components are essentially converted to metal oxides;
- (7) sulfiding said dried composites obtained from step (6) by contacting said composites with hydrogen sulfide and/or organic sulfur compounds in a hydrogen atmosphere such that said metal oxides are essentially converted to metal sulfides;
- and
- (b) separating said hydrocarbon product phase from said ammonia and hydrogen sulfide phase.
6 more elements
Dependencies are inferred from the claim text.