Method for producing dual colloid catalyst composition

Claim 1

A method for preparing catalyst compositions which method comprises: (a) forming a gel or suspension by admixing (i) one or more transition metal cyano-containing anionic-complex solutions wherein at least one solution contains one or more reducible transition metals selected from the Groups IB, IIB, VIB, VIIB, and VII of the Periodic Table of the Elements, wherein the cations accompanying the anionic complexes contain one or more alkali metal ions, with (ii) one or more solutions containing metal cations wherein at least one of the metals is a nonreducible metal selected from the group consisting of Cr, Al, Th, U, the lanthanides, and elements of Group IIA of the Periodic Table of the Elements; (b) heating the resulting gel, or suspension, under reflux conditions, to a temperature of about 90° C. to about 150° C. for an effective amount of time to allow hydrolysis and polymerization to occur; (c) separating the resulting solid; (d) modifying the resulting solid by ion-exchanging cations of one or more alkali and alkaline-earth metals with cations of one or more metals selected from Groups IA, IIA, IB, IIB, IIB, IVB, and VIII of the Periodic Table of the Elements; NH 4 + or quarternary ammonium cations; (e) drying the ion-exchanged resulting solid; and (f) heating it at less than 1° C./minute to between about 315° C. and 500° C. in a hydrogen-containing atmosphere and holding it at that temperature for an effective amount of time, thereby resulting in an active catalyst characterized as comprising: (A) from about 15 to about 85 wt.% of crystallites selected from the group consisting of (i) crystallites of one or more transition metals and (ii) crystallites of reducible transition metal carbides, nitrides, and oxides, and mixtures thereof, said transition metal being selected from those reducible metals from Groups IB, IIB, VIB, VIIB, and VIII of the Periodic Table of the Elements, wherein at least 80% of the crystallites have a diameter, d, between about 25 Å and 500 Å with the proviso that the crystallite size distribution of at least about 80% of these be expressed by the relationship 0.5D<d<2D where D is the median of the diameters of this 80%; and (B) from about 15 to about 85 wt.% of an amorphous nonreducible promoter phase interspersed with the metal crystallites, and containing compounds of at least one element selected from the group consisting of Cr, Al, Si, Th, U, the lanthanides and Group IA, IIA, IIB, IVB, and VB of the Periodic Table of the Elements, wherein the promoter phase is comprised of particles of which at least about 80% have a diameter between about 15 Å and 1500 Å wherein the median diameter (D) of the metal crystallites and the median diameter of the 80% of the promoter particles do not differ by more than a factor of about 20.

Claim 2

A method for preparing catalyst compositions which method comprises: (a) forming a gel or suspension by admixing (i) one or more transition metal cyano-containing anionic-complex solutions wherein at least one solution contains one or more reducible transition metals selected from the Groups IB, IIB, VIB, VIIB, and VII of the Periodic Table of the Elements, wherein the cations accompanying the anionic complexes contain one or more alkali metal ions, with (ii) one or more solutions containing metal cations wherein at least one of the metals is a nonreducible metal selected from the group consisting of Cr, Al, Th, U, the lanthanides, and elements of Group IIA of the Periodic Table of the Elements; (b) heating the resulting gel, or suspension, under reflux conditions, to a temperature of about 90° C. to about 150° C. for an effective amount of time to allow hydrolysis and polymerization to occur; (c) separating the resulting solid; (d) modifying the resulting solid by ion-exchanging cations of one or more alkali and alkaline-earth metals with cations of one or more metals selected from Groups IA, IIA, IB, IIB, IIB, IVB, and VIII of the Periodic Table of the Elements; NH 4 + or quarternary ammonium cations; (e) drying the ion-exchanged resulting solid; and (f) heating it at less than 1° C./minute to between about 315° C. and 500° C. in a hydrogen-containing atmosphere and holding it at that temperature for an effective amount of time, thereby resulting in an active catalyst characterized as comprising: (A) from about 15 to about 85 wt.% of crystallites selected from the group consisting of (i) crystallites of one or more transition metals and (ii) crystallites of reducible transition metal carbides, nitrides, and oxides, and mixtures thereof, said transition metal being selected from those reducible metals from Groups IB, IIB, VIB, VIIB, and VIII of the Periodic Table of the Elements, wherein at least 80% of the crystallites have a diameter, d, between about 25 Å and 500 Å with the proviso that the crystallite size distribution of at least about 80% of these be expressed by the relationship 0.5D<d<2D where D is the median of the diameters of this 80%; and (B) from about 15 to about 85 wt.% of an amorphous nonreducible promoter phase interspersed with the metal crystallites, and containing compounds of at least one element selected from the group consisting of Cr, Al, Si, Th, U, the lanthanides and Group IA, IIA, IIB, IVB, and VB of the Periodic Table of the Elements, wherein the promoter phase is comprised of particles of which at least about 80% have a diameter between about 15 Å and 1500 Å wherein the median diameter (D) of the metal crystallites and the median diameter of the 80% of the promoter particles do not differ by more than a factor of about 20.