Preparation of catalyst composition comprising a boron containing crystalline material having the structure of zeolites ZSM-5, ZSM-11, ZSM-12, Beta or Nu-1

Claim 3

The method of claim 1, wherein the boron-containing crystalline material synthesis step comprises forming a reaction mixture having a composition, in terms of mole ratios, falling within the following ranges: ______________________________________ OH.sup.- /SiO.sub.2 0.07-1.0 R.sub.4 N.sup.+ /(R.sub.4 N.sup.+ + Na.sup.+) 0.2-0.95 H.sub.2 O/OH.sup.- 10-300 SiO.sub.2 /Al.sub.2 O.sub.3 500-∞ SiO.sub.2 /B.sub.2 O.sub.3 4-300 ______________________________________ wherein R is selected from hydrogen and at least one organic aliphatic moiety selected from the group consisting of those containing from 2 to 10 carbon atoms, and heating said reaction mixture to a temperature of from about 90° to about 200° C. for a period of time of from about 6 hours to about 120 days.

Claim 4

The method of claim 1, wherein said boron-containing crystalline material has a composition as crystallized in terms of mole ratios of oxides on a anydrous basis as follows: (R.sub.2 O, M.sub.2/n O).sub.W :(Al.sub.2 O.sub.3).sub.X :(B.sub.2 O.sub.3).sub.Z :(SiO.sub.2).sub.Y wherein W/(X+Z) is from greater than about 0.5 to less than about 3; Y/(X+Z) is greater than about 20; Z/(X+Z) is from about 0.6 to about 1.0; R is a nitrogen-containing cation provided by a primary amine containing from 2 to 10 carbon atoms or a tetraalkylammonium compound in which alkyl contains from 2 to 5 carbon atoms; M is a metal from Group IA of the Periodic Table of the Elements, ammonium, hydrogen, or mixtures thereof, and n is the valence of M.

Claim 5

The method of claim 1, wherein said pH in said ion-exchange solution contacting step is from about 9 to about 11.

Claim 6

The method of claim 1, wherein said inorganic oxide of said compositing step is alumina.

Claim 7

The method of claim 2, wherein R 4 N + is a cation of a tetraalkylammonium compound in which alkyl contains from 2 to 5 carbon atoms.

Claim 8

The method of claim 6, wherein R 4 N + is a cation of a tetrapropylammonium compound.

Claim 9

In a method for preparing a catalyst composition comprising a boron-containing crystalline material having the structure of zeolite ZSM-5, ZSM-11, ZSM-12, Beta or Nu-1, which comprises the steps of (1) synthesizing a boron-containing crystalline material having the structure of zeolite ZSM-5, ZSM-11, ZSM-12, Beta or Nu-1; (2) drying said crystalline material at a temperature of from about ambient to less than about 170° C.; (3) calcining said dried crystalline material at a temperature of from about 200° to about 600° C. and adsorbing ammonia on said calcined crystalline material; (4) contacting said crystalline material with an ion-exchange solution at a pH of from about 7 to about 11; (5) compositing said ion-exchange solution contacted crystalline material with an inorganic oxide material; (6) drying said composite at a temperature of from about ambient to less than about 170° C.; and (7) calcining said dried composite at a temperature of from about 200° to about 600° C., the improvement which comprises conducting said steps in sequential order, and maintaining said calcining step (3) in an oxygen-free and water-free environment of anhydrous ammonia, anhydrous nitrogen, other anhydrous inert gases, or a mixture thereof, to minimize hydrolysis of boron in the boron-containing material.

Claim 10

In a method for preparing a catalyst composition comprising a boron-containing crystalline material having the structure of zeolite ZSM-5, ZSM-11, ZSM-12, Beta or Nu-1, which comprises the steps of (1) synthesizing a boron-containing crystalline material having the structure of zeolite ZSM-5, ZSM-11, ZSM-12, Beta or Nu-1; (2) drying said crystalline material at a temperature of from about ambient to less than about 170° C.; (3) calcining said dried crystalline material at a temperature of from about 200° to about 600° C. and adsorbing ammonia on said calcined crystalline material; (4) contacting said crystalline material with an ion-exchange solution at a pH of from about 7 to about 11; (5) compositing said ion-exchange solution contacted crystalline material with an inorganic oxide material; (6) drying said composite at a temperature of from about ambient to less than about 170° C.; and (7) calcining said dried composite at a temperature of from about 200° to about 600° C., the improvement which comprises conducting said steps in sequential order, and maintaining said calcining step (3) in an oxygen-free and water-free environment of anhydrous ammonia, anhydrous nitrogen, other anhydrous inert gases, or a mixture thereof, to minimize hydrolysis of boron in the boron-containing material.

Claim 11

The method of claim 8, wherein the boron-containing crystalline material synthesis step (1) comprises forming a reaction mixture having a composition in terms of mole ratios within the following ranges: ______________________________________ OH.sup.- /SiO.sub.2 0.07-1.0 R.sub.4 N.sup.+ /(R.sub.4 N.sup.+ + Na.sup.+) 0.2-0.95 H.sub.2 O/OH.sup.- 10-300 SiO.sub.2 /Al.sub.2 O.sub.3 500-∞ SiO.sub.3 /B.sub.2 O.sub.3 4-300 ______________________________________ wherein R is selected from hydrogen and at least one organic aliphatic moiety selected from the group consisting of those containing from 2 to 10 carbon atoms, and heating said reaction mixture to a temperature of from about 90° to about 200° C. for a period of time of from about 6 hours to about 120 days.

Claim 12

The method of claim 8, wherein said boron-containing crystalline material has a composition as crystallized in synthesis step (1) in terms of mole ratios of oxides on an anhydrous basis as follows: (R.sub.2 O, M.sub.2/n O).sub.W :(Al.sub.2 O.sub.3).sub.X :(B.sub.2 O.sub.3).sub.Z :(SiO.sub.2).sub.Y wherein W/(X+Z) is from greater than about 0.5 to less than about 3; Y/(X+Z) is greater than about 20; Z/(X+Z) is from about 0.6 to about 1.0; R is a nitrogen-containing cation provided by a primary amine containing from 2 to 10 carbon atoms or a tetraalkylammonium compound in which alkyl contains from 2 to 5 carbon atoms; M is a metal from Group IA of the Periodic Table of the Elements, ammonium, hydrogen, or mixtures thereof, and n is the valence of M.

Claim 13

The method of claim 8, wherein said oxygen- and water-free environment in said calcining step (3) comprises anhydrous ammonia.

Claim 14

The method of claim 8, wherein said pH in said ion-exchange solution contacting step (4) is from about 9 to about 11.

Claim 15

The method of claim 8, wherein said inorganic oxide of said compositing step (5) is alumina.

Claim 18

In a method for preparing a catalyst composition for processing high nitrogen containing oils comprising a boron-containing crystalline material having the structure of zeolite ZSM-12, which comprises the steps of (1) synthesizing a boron-containing crystalline material having the structure of zeolite ZSM-12; (2) drying said crystalline material at a temperature of from about ambient to less than about 170° C.; (3) calcining said dried drystalline material at a temperature of from 200° to about 600° C. and adsorbing ammonia on said calcined crystalline material; (4) contacting said crystalline material with an ion-exchange solution at a pH of from above about 7 to about 11; (5) compositing said ion-exchange solution contacted crystalline material with an inorganic oxide material; (6) drying said composite at a temperature of from about ambient to less than about 170° C.; and (7) calcining said dried composite at a temperature of from about 200° to about 600° C., the improvement which comprises conducting said steps in sequential order, and maintaining said calcining step (3) in an oxygen- and water-free environment of anhydrous ammonia, anhydrous nitrogen, other anhydrous inert gases, or a mixture thereof, to minimize hydrolysis of boron in the boron-containing crystalline material.

Claim 19

In a method for preparing a catalyst composition for processing high nitrogen containing oils comprising a boron-containing crystalline material having the structure of zeolite ZSM-12, which comprises the steps of (1) synthesizing a boron-containing crystalline material having the structure of zeolite ZSM-12; (2) drying said crystalline material at a temperature of from about ambient to less than about 170° C.; (3) calcining said dried drystalline material at a temperature of from 200° to about 600° C. and adsorbing ammonia on said calcined crystalline material; (4) contacting said crystalline material with an ion-exchange solution at a pH of from above about 7 to about 11; (5) compositing said ion-exchange solution contacted crystalline material with an inorganic oxide material; (6) drying said composite at a temperature of from about ambient to less than about 170° C.; and (7) calcining said dried composite at a temperature of from about 200° to about 600° C., the improvement which comprises conducting said steps in sequential order, and maintaining said calcining step (3) in an oxygen- and water-free environment of anhydrous ammonia, anhydrous nitrogen, other anhydrous inert gases, or a mixture thereof, to minimize hydrolysis of boron in the boron-containing crystalline material.

Claim 26

The method of claim 18, wherein said crystalline material is composited with an inorganic oxide material.

Claim 27

The method of claim 19, wherein said inorganic oxide material is silica, silica-zirconia, silica-magnesia or silica-titania.

Claim 28

The method of claim 18, wherein the boron-containing crystalline material synthesis step comprises forming a reaction mixture having a composition, in terms of mole ratios, falling within the following ranges: ______________________________________ OH.sup.- /SiO.sub.2 0.07-1.0 R.sub.4 N.sup.+ /(R.sub.4 N.sup.+ + Na.sup.+) 0.2-0.95 H.sub.2 O/OH.sup.- 10-300 SiO.sub.2 /Al.sub.2 O.sub.3 500-∞ SiO.sub.2 /B.sub.2 O.sub.3 4-300 ______________________________________ wherein R is selected from hydrogen and at least one organic aliphatic moiety selected from the group consisting of those containing from 2 to 10 carbon atoms, and heating said reaction mixture to a temperature of from about 90° to about 200° C. for a period of time of from about 6 hours to about 120 days.

Claim 29

The method of claim 18, wherein said boron-containing crystalline material has a composition as crystallized in terms of mole ratios of oxides on a anhydrous basis as follows: (R.sub.2 O, M.sub.2/n O).sub.W :(Al.sub.2 O.sub.3).sub.X :(B.sub.2 O.sub.3).sub.Z :(SiO.sub.2).sub.Y wherein W/(X+Z) is from greater than about 0.5 to less than about 3; Y/(X+Z) is greater than about 20; Z/(X+Z) is from about 0.6 to about 1.0; R is a nitrogen-containing cation provided by a primary amine containing from 2 to 10 carbon atoms or a tetraalkylammonium compound in which alkyl contains from 2 to 5 carbon atoms; M is a metal from Group IA of the Periodic Table of the Elements, ammonium, hydrogen, or mixtures thereof, and n is the valence of M.

Claim 30

The method of claim 18, wherein said pH in said ion-exchange solution contacting step is from about 9 to about 11.

Claim 31

The method of claim 21, wherein R 4 N + is a cation of a tetraalkylammonium compound in which alkyl contains from 2 to 5 carbon atoms.

Claim 32

The method of claim 24, wherein R 4 N + is a cation of a tetrapropylammonium compound.