Hydrotreating catalyst and a method for preparing the catalyst

Claim 2

A catalyst composition useful for denitrogenation and desulfurization of hydrocarbon feedstocks by reaction with hydrogen, said catalyst composition 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 so as to provide composites containing molybdenum, nickel and phosphorous components; (c) drying composites obtained from step (b) at temperatures less than about 150° F.; and (d) calcining impregnated particles from step (c) at an elevated temperature in the presence of oxygen.

Claim 3

The composition defined in claim 1 comprising the additional step of sulfiding calcined particles obtained from step (d) to convert essentially all of the molybdenum and nickel components to metal sulfides.

Claim 4

The composition defined in claim 1 wherein support particles obtained from step (a) are impregnated with molybdenum, nickel and phosphorous by introducing an aqueous solution containing molybdenum, nickel and phosphorous components into the pores of said hydroxylated support particles 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 weight percent phosphorous components, calculated as elemental phosphorous.

Claim 5

The composition defined in claim 1 wherein said gamma alumina support particles are contacted with a volume of aqueous ammonia solution which is greater than 8 percent of the aggregate pore volume of said particles.

Claim 6

A catalyst composition useful for the denitrogenation and desulfurization of hydrocarbon feedstocks by reaction with hydrogen, said catalyst composition comprised substantially of 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 a volume of aqueous ammonia which is greater than 8 percent of the aggregate pore volume of said particles; (b) drying the resultant particles; (c) contacting dried particles obtained from step (b) with an aqueous solution containing an organic acid having a pK a less than 5; (d) introducing an acidic aqueous solution containing molybdenum, nickel and phosphorous components into the pores of particles obtained from step (c) 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 6 weight percent nickel components, calculated as nickel oxide, and between about 2 and about 6 weight percent phosphorous components, calculated as elemental phosphorous; (e) drying composites obtained from step (d) at temperatures less than about 150° F.; (f) calcining dried composites obtained from step (e) at temperatures between about 800° F. and about 1,100° F. in the presence of oxygen so as to essentially convert said molybdenum and nickel components to metal oxides; and (g) sulfiding composites obtained from step (f) to convert essentially all of said metal oxides to metal sulfides.

Claim 7

A catalyst composition useful for the denitrogenation and desulfurization of hydrocarbon feedstocks by reaction with hydrogen, said catalyst composition comprised substantially of 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 a volume of aqueous ammonia which is greater than 8 percent of the aggregate pore volume of said particles; (b) drying the resultant particles; (c) contacting dried particles obtained from step (b) with an aqueous solution containing an organic acid having a pK a less than 5; (d) introducing an acidic aqueous solution containing molybdenum, nickel and phosphorous components into the pores of particles obtained from step (c) 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 6 weight percent nickel components, calculated as nickel oxide, and between about 2 and about 6 weight percent phosphorous components, calculated as elemental phosphorous; (e) drying composites obtained from step (d) at temperatures less than about 150° F.; (f) calcining dried composites obtained from step (e) at temperatures between about 800° F. and about 1,100° F. in the presence of oxygen so as to essentially convert said molybdenum and nickel components to metal oxides; and (g) sulfiding composites obtained from step (f) to convert essentially all of said metal oxides to metal sulfides.

Claim 8

The composition defined in claim 5 wherein said support particles are contacted with a volume of aqueous ammonia solution sufficient to essentially fill the aggregate pore volume of said particles.

Claim 9

The composition defined in claim 5 wherein said aqueous ammonia solution contains greater than about 0.1 weight percent ammonium hydroxide.

Claim 10

The composition defined in claim 5 wherein said aqueous ammonia solution contains between about 20 and 30 weight percent ammonium hydroxide.

Claim 11

The composition defined in claim 5 wherein dried particles obtained from step (b) are contacted with an aqueous solution containing an organic acid having a PK a less than 5 but greater than 3.

Claim 12

The composition defined in claim 5 wherein dried particles obtained from step (b) are contacted with an aqueous solution containing citric acid.

Claim 13

The composition defined in claim 5 wherein dried particles obtained from step (b) are contacted with water.

Claim 14

The composition defined in claim 5 wherein said aqueous solution containing molybdenum, nickel and phosphorous components is introduced into the pores of particles obtained from step (c) 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 at nickel oxide, is about 0.5:1 and 1:1.

Claim 15

The composition defined in claim 5 wherein said dried composites obtained from step (e) are calcined at temperatures between about 975° F. and about 1,025° F.

Claim 16

A catalyst composition useful for the denitrogenation and desulfurization of hydrocarbon feedstocks by reaction with hydrogen, said catalyst composition consisting essentially of molybdenum, nickel and phosphorous active components on support particles consisting essentially of gamma alumina, said catalyst having been prepared by a method comprising the steps of: (a) 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; (b) drying the resultant support particles; (c) contacting dried particles obtained from step (b) with an aqueous solution of citric acid; (d) introducing an acidic aqueous solution containing ammonium heptamolybdate, nickel nitrate, and phosphoric acid into the pores of particles obtained from step (c) 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 weight 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; (e) drying composites obtained from step (d) at temperatures less than about 150° F.; (f) calcining dried composites obtained from step (e) at temperatures between about 975° F. and about 1,025° F. in the presence of oxygen such that said molybdenum and nickel components are essentially converted to metal oxides; and (g) sulfiding said dried composites obtained from step (f) 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.

Claim 17

A catalyst composition useful for the denitrogenation and desulfurization of hydrocarbon feedstocks by reaction with hydrogen, said catalyst composition consisting essentially of molybdenum, nickel and phosphorous active components on support particles consisting essentially of gamma alumina, said catalyst having been prepared by a method comprising the steps of: (a) 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; (b) drying the resultant support particles; (c) contacting dried particles obtained from step (b) with an aqueous solution of citric acid; (d) introducing an acidic aqueous solution containing ammonium heptamolybdate, nickel nitrate, and phosphoric acid into the pores of particles obtained from step (c) 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 weight 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; (e) drying composites obtained from step (d) at temperatures less than about 150° F.; (f) calcining dried composites obtained from step (e) at temperatures between about 975° F. and about 1,025° F. in the presence of oxygen such that said molybdenum and nickel components are essentially converted to metal oxides; and (g) sulfiding said dried composites obtained from step (f) 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.

Claim 18

The composition defined in claim 14 wherein support particles obtained from step (a) are aged for more than 15 minutes before being dried in step (b).

Claim 19

The composition defined in claim 14 wherein support particles obtained from step (a) are aged for a period of time sufficient to allow hydroxyl ions within said aqueous ammonia solution to substantially reach chemical equilibrium with the surface of said gamma alumina support particles before said support particles are dried in step (b).

Claim 22

The method defined in claim 18 comprising the additional step of sulfiding calcined particles obtained from step (d) such that essentially all molybdenum and nickel components are converted to metal sulfides.

Claim 23

A catalyst composition useful for the denitrogenation and desulfurization of hydrocarbon feedstocks by reaction with hydrogen, said catalyst composition consisting essentially of molybdenum, nickel and phosphorous active components on support particles consisting essentially of gamma alumina, said catalyst having been prepared by a method comprising the steps of: (a) contacting gamma alumina 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 phosphorus so as to provide a composite containing molybdenum, nickel and phosphorus components; (c) drying composites obtained from step (b) at temperatures less than about 150° F.; and (d) calcining impregnated particles from step (c) at an elevated temperature in the presence of oxygen.

Claim 24

A catalyst composition useful for the denitrogenation and desulfurization of hydrocarbon feedstocks by reaction with hydrogen, said catalyst composition consisting essentially of molybdenum, nickel and phosphorous active components on support particles consisting essentially of gamma alumina, said catalyst having been prepared by a method comprising the steps of: (a) contacting gamma alumina 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 phosphorus so as to provide a composite containing molybdenum, nickel and phosphorus components; (c) drying composites obtained from step (b) at temperatures less than about 150° F.; and (d) calcining impregnated particles from step (c) at an elevated temperature in the presence of oxygen.

Claim 25

The composition defined in claim 19 wherein the aqueous ammonia contacted support particles from step (a) are dried before being impregnated in step (b).

Claim 26

The composition defined in claim 20 wherein support particles obtained from the drying of aqueous ammonia contacted support particles from step (a) are contacted before being impregnated in step (b) with an aqueous solution containing an organic acid having a pKa less than 5 but greater than 3.

Claim 27

The composition defined in claim 21 wherein said aqueous solution containing an organic acid having a pKa less than 5 but greater than 3 is an aqueous solution containing citric acid.

Claim 28

A catalyst composition useful for the denitrogenation and desulfurization of hydrocarbon feedstocks by reaction with hydrogen, said catalyst composition consisting essentially of molybdenum, nickle and phosphorous active components on support particles consisting essentially of gamma alumina, said catalyst having been prepared by a method comprising the steps of: (a) contacting gamma alumina 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 an acidic impregnating solution so as to provide a composite containing molybdenum, nickel and phosphorus components; (c) drying composites obtained from step (b) at temperatures less than about 150° F.; and (d) calcining impregnated particles from step (c) at an elevated temperature in the presence of oxygen.

Claim 29

A catalyst composition useful for the denitrogenation and desulfurization of hydrocarbon feedstocks by reaction with hydrogen, said catalyst composition consisting essentially of molybdenum, nickle and phosphorous active components on support particles consisting essentially of gamma alumina, said catalyst having been prepared by a method comprising the steps of: (a) contacting gamma alumina 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 an acidic impregnating solution so as to provide a composite containing molybdenum, nickel and phosphorus components; (c) drying composites obtained from step (b) at temperatures less than about 150° F.; and (d) calcining impregnated particles from step (c) at an elevated temperature in the presence of oxygen.