Ni/Co Mo P On titania-alumina hydrodesulfurizing catalyst

Claim 2

A hydrodesulfurizing catalyst in the form of an anhydrous pellet comprising a substrate, said substrate consisting essentially of an intimate mixture of alumina and an oxide of a Group IV-B metal, the substrate being further associated with an oxide of a Group VI-B metal, said Group VI-B metal being selected from molybdenum or tungsten, and an oxide of Group VIII metal, the catalyst also containing phosphorous in a complex with molybdenum or tungsten.

Claim 3

The catalyst of claim 1, in which the oxide of the Group VI-B metal is molybdenum and said catalyst also contains phosphorous in a complex with molybdenum in which the atomic ratio of Mo to P is less than 4, and more than 0.01.

Claim 4

The catalyst of claim 1, in which the oxide of Group VI-B metal is molybdenum and the catalyst also contains phosphorous in a phospho-molybdenum complex, in which the atomic ratio of Mo to P is 10 to 1.

Claim 5

The catalyst of claim 1, in which the oxide of the Group VI-B metal is tungsten and the catalyst also contains phosphorous in a phospho-tungsten complex in which the atomic ratio of the tungsten to the phosphorous is 12 to 1.

Claim 6

The catalyst of claim 1, in which the oxide of the Group IV-B metal is anatase and the oxide of the Group VI-B metal is an oxide of molybdenum, said catalyst containing phosphorous in a complex with molybdenum in the atomic ratio of molybdenum to phosphorous of less than 4 and more than 0.01.

Claim 7

The process of forming a hydrodesulfurizing catalyst in the form of a hard pellet which comprises mixing hydrated alumina with hydrated titania or hydrated zirconia in water and forming said mixture into a pellet, drying and calcining said pellet and impregnating said pellet with a solution of a salt of a molybdenum anion or a tungsten anion and salts of Ni, or Co, or mixtures of Co and Ni and drying and calcining said impregnated pellet in air at a temperature in the range of from in excess of about 900° to about 1500° F. for about 1/2 hour to about 24 hours, the amounts of said hydrated oxide and the said salts being from about 1% to about 25% expressed as Ti, or Zr, and Ni, or Co salts, or mixtures of Co and Ni salts in amount equal to about 0.1% to about 25%, expressed as Ni, or Co, or mixtures of Ni and Co and molybdate or tungstate salt from about 1% to about 25% expressed as Mo or W based on the weight of the calcined pellet on an anhydrous basis.

Claim 8

The process of forming a hydrodesulfurizing catalyst in the form of a hard pellet which comprises mixing hydrated alumina with hydrated titania or hydrated zirconia in water and forming said mixture into a pellet, drying and calcining said pellet and impregnating said pellet with a solution of a salt of a molybdenum anion or a tungsten anion and salts of Ni, or Co, or mixtures of Co and Ni and drying and calcining said impregnated pellet in air at a temperature in the range of from in excess of about 900° to about 1500° F. for about 1/2 hour to about 24 hours, the amounts of said hydrated oxide and the said salts being from about 1% to about 25% expressed as Ti, or Zr, and Ni, or Co salts, or mixtures of Co and Ni salts in amount equal to about 0.1% to about 25%, expressed as Ni, or Co, or mixtures of Ni and Co and molybdate or tungstate salt from about 1% to about 25% expressed as Mo or W based on the weight of the calcined pellet on an anhydrous basis.

Claim 9

The process of claim 6, in which anatase is mixed with the alumina and the pellet is impregnated with a molybdate and with a salt of Ni or Co, or mixtures of the salts of Ni and Co.

Claim 10

The process of claim 6, in which the alumina hydrate is pseudoboehmite.

Claim 11

The process of claim 6, in which the alumina hydrate is pseudoboehmite of a peptizeability index of less than about 0.5.

Claim 12

The process of claim 6, in which the alumina hydrate is a mixture of a pseudoboehmite having a peptizeability index of less than 0.5 and one having a peptizeability index substantially in excess of 0.5.

Claim 13

The process of claim 6, in which the hydrate of the Group IV-B metal is titania hydrate and a molybdate is used to impregnate the pellet.

Claim 14

The process of forming a hydrodesulfurizing catalyst which comprises forming an extrudate comprising an intimate and substantially uniform aqueous mixture of alumina hydrate and the hydrated oxide of a Group IV-B metal and salts of molybdenum or tungsten and a salt of Group VIII metal, said mixture containing the hydrated oxide of the Group IV-B metal in the range of from about 1% to about 25% expressed as the Group IV-B metal and a salt in which the Group VI-B metal is an anion, being in the range of about 1% to about 25% expressed as the Group VI-B metal and the Group VIII salt or salts being in the range of about 0.1% to about 25% expressed as Group VIII metal, based on the weight of the catalyst on a volatile free basis, extruding said mixture to form a pellet, drying and calcining said pellet to form a substantially anhydrous pellet containing the oxides of the above metals intimately mixed with alumina.

Claim 15

The process of forming a hydrodesulfurizing catalyst which comprises forming an extrudate comprising an intimate and substantially uniform aqueous mixture of alumina hydrate and the hydrated oxide of a Group IV-B metal and salts of molybdenum or tungsten and a salt of Group VIII metal, said mixture containing the hydrated oxide of the Group IV-B metal in the range of from about 1% to about 25% expressed as the Group IV-B metal and a salt in which the Group VI-B metal is an anion, being in the range of about 1% to about 25% expressed as the Group VI-B metal and the Group VIII salt or salts being in the range of about 0.1% to about 25% expressed as Group VIII metal, based on the weight of the catalyst on a volatile free basis, extruding said mixture to form a pellet, drying and calcining said pellet to form a substantially anhydrous pellet containing the oxides of the above metals intimately mixed with alumina.

Claim 16

The process of claim 12, in which the alumina hydrate is pseudoboehmite.

Claim 17

The process of claim 12, in which the Group IV-B hydrated oxide is titania hydrate and the Group VI-B salt is a molybdate and the Group VIII salt is a salt of Ni, or Co, or mixtures of Ni and Co.

Claim 18

The process of claim 14, in which the alumina hydrate is pseudoboehmite.

Claim 19

The process of claim 14, in which the molybdate is associated in a complex with a phosphate in an atomic ratio of Mo to P of more than 0.01 and less than 4.

Claim 20

The process of claim 16, in which the aluminum hydrate is pseudoboehmite.

Claim 21

The process of claim 16, which includes the step of forming a mixture of water and alumina hydrate, and a hydrolyzeable compound of titanium and with ammonium hydroxide to convert said titanium compound into titania hydrate.

Claim 22

The process of claim 16, which includes the step of forming a mixture of water, alumina hydrate, and a hydrolyzeable compound of titanium and with ammonium hydroxide and forming titania hydrate in said mixture and in which said Group VI-B metal is molybdenum and said Group VIII metal is Ni, or Co, or mixtures of Ni and Co.

Claim 23

The process of forming a hydrodesulfurizing catalyst in the form of a hard pellet which comprises mixing hydrated alumina with hydrated titania or hydrated zirconia in water and forming said mixture into a pellet, drying and calcining said pellet and impregnating said pellet with a solution of a salt of a molybdenum anion, phosphoric acid, and salts of Ni, or Co, or mixtures of Co and Ni, the ratio of the Ni or Co to the Mo being about 1 atomic weight of Ni or Co to about 0.3 to about 2.5 atomic weights of Mo and in which the atomic ratio of the Mo to the P is less than 4 and more than 0.01, said solution being at a pH of less than about 4, and drying and calcining said impregnated pellet in air at a temperature of about 100° F. or higher or from about 1/2 hour to about 24 hours, the amounts of said oxides of titanium, or zirconium oxide and the said salts being from about 1% to about 25% expressed as Ti, or Zr, and Ni, or Co salts, or mixtures of Co and Ni salts in amount equal to about 0.1% to about 25%, expressed as Ni, or Co, or mixtures of Ni and Co and molybdate or tungstate salt from about 5% to 25% expressed as Mo or W based on the weight of the impregnated calcined pellet on an anhydrous basis.

Claim 24

The process of forming a hydrodesulfurizing catalyst in the form of a hard pellet which comprises mixing hydrated alumina with hydrated titania or hydrated zirconia in water and forming said mixture into a pellet, drying and calcining said pellet and impregnating said pellet with a solution of a salt of a molybdenum anion, phosphoric acid, and salts of Ni, or Co, or mixtures of Co and Ni, the ratio of the Ni or Co to the Mo being about 1 atomic weight of Ni or Co to about 0.3 to about 2.5 atomic weights of Mo and in which the atomic ratio of the Mo to the P is less than 4 and more than 0.01, said solution being at a pH of less than about 4, and drying and calcining said impregnated pellet in air at a temperature of about 100° F. or higher or from about 1/2 hour to about 24 hours, the amounts of said oxides of titanium, or zirconium oxide and the said salts being from about 1% to about 25% expressed as Ti, or Zr, and Ni, or Co salts, or mixtures of Co and Ni salts in amount equal to about 0.1% to about 25%, expressed as Ni, or Co, or mixtures of Ni and Co and molybdate or tungstate salt from about 5% to 25% expressed as Mo or W based on the weight of the impregnated calcined pellet on an anhydrous basis.

Claim 25

The process of forming a hydrodesulfurizing catalyst which comprises forming an extrudate comprising an intimate and substantially uniform mixture of alumina hydrate and the hydrated oxide of a Group IV-B metal and the salts of molybdenum or tungsten and a salt of Group VIII metal, said mixture containing an amount of water in the range of about 50% to about 70% of the weight of the mixture, said mixture containing the hydrated oxide of the Group IV-B metal in the range of from about 1% to about 25% expressed as the Group IV-B metal and an ammonium molybdate anion, of about 1% to about 25% expressed as molybdenum metal and a cobalt salt or nickel salt or a mixture of said salts being in the range of about 0.1% to about 25% expressed as the Co or Ni metal, based on the weight of the composite catalyst on a volatile free basis, and phosphoric acid, the atomic ratio of the Mo to the phosphorous equivalent of the phosphoric acid being in the range of about 4 to less than 0.01, extruding said mixture to form a pellet, drying and calcining said pellet to form substantially anhydrous pellet containing the oxides of the above metals intimately mixed with alumina.

Claim 26

The process of forming a hydrodesulfurizing catalyst which comprises forming an extrudate comprising an intimate and substantially uniform mixture of alumina hydrate and the hydrated oxide of a Group IV-B metal and the salts of molybdenum or tungsten and a salt of Group VIII metal, said mixture containing an amount of water in the range of about 50% to about 70% of the weight of the mixture, said mixture containing the hydrated oxide of the Group IV-B metal in the range of from about 1% to about 25% expressed as the Group IV-B metal and an ammonium molybdate anion, of about 1% to about 25% expressed as molybdenum metal and a cobalt salt or nickel salt or a mixture of said salts being in the range of about 0.1% to about 25% expressed as the Co or Ni metal, based on the weight of the composite catalyst on a volatile free basis, and phosphoric acid, the atomic ratio of the Mo to the phosphorous equivalent of the phosphoric acid being in the range of about 4 to less than 0.01, extruding said mixture to form a pellet, drying and calcining said pellet to form substantially anhydrous pellet containing the oxides of the above metals intimately mixed with alumina.