US3899441A — Rejuvenation of damaged zeolite-supported metal c…

Claim 1

Independent Claim 54 words

contacting said catalyst, in an oxidized or sulfided state and at a temperature below about 300*F., either simultaneously or in the order named, with water or water vapor and with ammonia to effect adsorption therein of about 5-40 weight-percent of water and about 5-35 weight-percent of ammonia based on the weight of adsorbed water;

Claim 2

Dependent Claim 54 words

contacting said catalyst, in an oxidized or sulfided state and at a temperature below about 300*F., either simultaneously or in the order named, with water or water vapor and with ammonia to effect adsorption therein of about 5-40 weight-percent of water and about 5-35 weight-percent of ammonia based on the weight of adsorbed water;

Claim 3

Independent Claim 153 words

A method for rejuvenating and redispersal of catalytic metal of a catalyst comprising a Group VIII metal supported on particulate aggregates of a siliceous zeolite, said catalyst having been compounded by a procedure which yields mechanically stable calcined aggregates having a crushing strength above about 20 pounds per 1/8 inch pellet, and whose mechanical strength is not increased or decreased more than about 10% by any of the hereinafter recited hydrocarbon conversion, oxidative regeneration or rejuvenation procedures, said catalyst having been utilized in a hydrocarbon conversion process to substantial deactivation and subsequently regenerated by oxidative combustion, and during said hydrocarbon conversion and/or regeneration having been subjected to thermal or hydrothermal conditions of sufficient severity to bring about a maldistribution of said Group VIII metal with resultant loss in hydrogenation activity wherein a substantial proportion of the maldistributed metal is in the form of agglomerates of less that 50 A in diameter, which comprises:

Claim 4

Independent Claim 153 words

A method for rejuvenating and redispersal of catalytic metal of a catalyst comprising a Group VIII metal supported on particulate aggregates of a siliceous zeolite, said catalyst having been compounded by a procedure which yields mechanically stable calcined aggregates having a crushing strength above about 20 pounds per 1/8 inch pellet, and whose mechanical strength is not increased or decreased more than about 10% by any of the hereinafter recited hydrocarbon conversion, oxidative regeneration or rejuvenation procedures, said catalyst having been utilized in a hydrocarbon conversion process to substantial deactivation and subsequently regenerated by oxidative combustion, and during said hydrocarbon conversion and/or regeneration having been subjected to thermal or hydrothermal conditions of sufficient severity to bring about a maldistribution of said Group VIII metal with resultant loss in hydrogenation activity wherein a substantial proportion of the maldistributed metal is in the form of agglomerates of less that 50 A in diameter, which comprises:

Claim 5

Dependent Claim 54 words

contacting said catalyst, in its oxidized regenerated state and at a temperature below about 300*F., either simultaneously or in the order named, with water or water vapor and with ammonia to effect adsorption therein of about 5-40 weight-percent of water and about 5-35 weight-percent of ammonia based on the weight of adsorbed water; and

Claim 6

Dependent Claim 54 words

contacting said catalyst, in its oxidized regenerated state and at a temperature below about 300*F., either simultaneously or in the order named, with water or water vapor and with ammonia to effect adsorption therein of about 5-40 weight-percent of water and about 5-35 weight-percent of ammonia based on the weight of adsorbed water; and

Claim 7

Dependent Claim 53 words

CONTACTING SAID CATALYST, IN ITS OXIDIZED REGENERATED STATE AND AT A TEMPERATURE BELOW ABOUT 300*F, EITHER SIMULTANEOUSLY OR IN THE ORDER NAMED, WITH WATER OR WATER VAPOR AND WITH AMMONIA TO EFFECT ADSORPTION THEREIN OF ABOUT 5-40 WEIGHT-PERCENT OF WATER AND ABOUT 5-35 WEIGHT-PERCENT OF AMMONIA BASED ON THE WEIGHT OF ADSORBED WATER,

Claim 8

Dependent Claim 53 words

CONTACTING SAID CATALYST, IN ITS OXIDIZED REGENERATED STATE AND AT A TEMPERATURE BELOW ABOUT 300*F, EITHER SIMULTANEOUSLY OR IN THE ORDER NAMED, WITH WATER OR WATER VAPOR AND WITH AMMONIA TO EFFECT ADSORPTION THEREIN OF ABOUT 5-40 WEIGHT-PERCENT OF WATER AND ABOUT 5-35 WEIGHT-PERCENT OF AMMONIA BASED ON THE WEIGHT OF ADSORBED WATER,

Claim 9

Dependent Claim 53 words

contacting said catalyst, in its oxidized regenerated state and at a temperature below about 300*F., either simultaneously or in the order named, with water or water vapor and with ammonia to effect adsorption therein of about 5-40 weight-percent of water and about 5-35 weight-percent of ammonia based on the weight of adsorbed water;

Claim 10

Dependent Claim 53 words

contacting said catalyst, in its oxidized regenerated state and at a temperature below about 300*F., either simultaneously or in the order named, with water or water vapor and with ammonia to effect adsorption therein of about 5-40 weight-percent of water and about 5-35 weight-percent of ammonia based on the weight of adsorbed water;

Claim 11

Dependent Claim 41 words

stripping the resulting hydrated, ammoniated catalyst in a stream of non-reducing gas at temperatures between about 250* and 500*F. to effect substantial deammoniation and partial drying with removal of at least about one-half of the water added in step (1); and

Claim 12

Dependent Claim 41 words

stripping the resulting hydrated, ammoniated catalyst in a stream of non-reducing gas at temperatures between about 250* and 500*F. to effect substantial deammoniation and partial drying with removal of at least about one-half of the water added in step (1); and

Claim 13

Dependent Claim 41 words

drying and calcining the resulting hydrated, ammoniated catalyst in a stream of substantially dry, oxygen-containing gas at elevated temperatures terminating in the range of about 750* - 1200*F., and recovering a substantially completely dehydrated and deammoniated catalyst having improved hydrogenation activity.

Claim 14

Dependent Claim 41 words

drying and calcining the resulting hydrated, ammoniated catalyst in a stream of substantially dry, oxygen-containing gas at elevated temperatures terminating in the range of about 750* - 1200*F., and recovering a substantially completely dehydrated and deammoniated catalyst having improved hydrogenation activity.

Claim 15

Dependent Claim 41 words

A method as defined in claim 1 wherein said Group VIII metal is a noble metal, and said siliceous zeolite is a molecular sieve of the Y crystal type wherein the zeolitic cations are primarily hydrogen ions and/or polyvalent metal ions.

Claim 16

Dependent Claim 42 words

STRIPPING THE RESULTING HYDRATED, AMMONIATED CATALYSTS IN A STREAM OF NON-REDUCING GAS AT A TEMPERATURES BETWEEN ABOUT 250* AND 500*F TO EFFECT SUBSTANTIALLY DEAMMONIATION AND PARTIZAAL DRYING WITH REMOVAL OF AT LEAST ABOUT ONE-HALF OF THE WATER ADDED IN STEP (1), AND

Claim 17

Dependent Claim 42 words

STRIPPING THE RESULTING HYDRATED, AMMONIATED CATALYSTS IN A STREAM OF NON-REDUCING GAS AT A TEMPERATURES BETWEEN ABOUT 250* AND 500*F TO EFFECT SUBSTANTIALLY DEAMMONIATION AND PARTIZAAL DRYING WITH REMOVAL OF AT LEAST ABOUT ONE-HALF OF THE WATER ADDED IN STEP (1), AND

Claim 18

Dependent Claim 24 words

stripping the resulting hydrated, ammoniated catalyst in a stream of non-reducing gas at temperatures below about 500*F. to effect partial deammoniation and drying; and

Claim 19

Dependent Claim 24 words

stripping the resulting hydrated, ammoniated catalyst in a stream of non-reducing gas at temperatures below about 500*F. to effect partial deammoniation and drying; and

Claim 20

Dependent Claim 36 words

calcining the partially dried and deammoniated catalyst in a stream of substantially dry oxygen-containing gas at temperatures controlled between about 500* and 1200*F., and recovering a substantially completely dehydrated and deammoniated catalyst having improved hydrogenation activity.

Claim 21

Dependent Claim 36 words

calcining the partially dried and deammoniated catalyst in a stream of substantially dry oxygen-containing gas at temperatures controlled between about 500* and 1200*F., and recovering a substantially completely dehydrated and deammoniated catalyst having improved hydrogenation activity.

Claim 22

Dependent Claim 84 words

CALCINING THE PARTIALLY DRIED Z AND DEAMMONIATED CATALYST IN A STREAM OF OXYGEN-CONTAINING GAS AT PROGRESSIVELY INCREASING TEMPERATURES BETWEEN ABOUT 500* AND 1200*F, CONTROLLED TO MAINTAIN THE DEWPOINT OF THE EFFLUENT GAS STREAM BELOW ABOUT 40*F, AT LEAST THE TERMINAL PORTION OF SAID CALCINING BEING CARRIED OUT AT TEMPERATURES BETWEEN ABOUT 750* AND 1200*F, FOR A SUFFICIENT LENGTH OF TIME TO PRODUCE AN EFFLUENT GAS STREAM HAVING A DEWPOINT BELOW ABOUT 0*F, AND A SUBSTANTIALLY COMPLETELY DEHYDRATED AND DEAMMONIATED CATALYST HAVING IMPROVED HYDROGENATION ACTIVITY,

Claim 23

Dependent Claim 84 words

CALCINING THE PARTIALLY DRIED Z AND DEAMMONIATED CATALYST IN A STREAM OF OXYGEN-CONTAINING GAS AT PROGRESSIVELY INCREASING TEMPERATURES BETWEEN ABOUT 500* AND 1200*F, CONTROLLED TO MAINTAIN THE DEWPOINT OF THE EFFLUENT GAS STREAM BELOW ABOUT 40*F, AT LEAST THE TERMINAL PORTION OF SAID CALCINING BEING CARRIED OUT AT TEMPERATURES BETWEEN ABOUT 750* AND 1200*F, FOR A SUFFICIENT LENGTH OF TIME TO PRODUCE AN EFFLUENT GAS STREAM HAVING A DEWPOINT BELOW ABOUT 0*F, AND A SUBSTANTIALLY COMPLETELY DEHYDRATED AND DEAMMONIATED CATALYST HAVING IMPROVED HYDROGENATION ACTIVITY,

Claim 24

Dependent Claim 30 words

A method as defined in claim 2 wherein said noble metal is palladium and wherein the zeolitic cations in said Y molecular sieve comprise a substantial proportion of hydrogen ions.

Claim 25

Dependent Claim 83 words

calcining the partially dried and deammoniated catalyst in a stream of oxygen-containing gas at progressively increasing temperatures between about 500* and 1200*F., controlled to maintain the dewpoint of the effluent gas stream below about 40*F., at least the terminal portion of said calcining being carried out at temperatures between about 750* and 1200*F. for a sufficient length of time to produce an effluent gas stream having a dewpoint below about 0*F., and a substantially completEly dehydrated and deammoniated catalyst having improved hydrogenation activity.

Claim 26

Dependent Claim 83 words

calcining the partially dried and deammoniated catalyst in a stream of oxygen-containing gas at progressively increasing temperatures between about 500* and 1200*F., controlled to maintain the dewpoint of the effluent gas stream below about 40*F., at least the terminal portion of said calcining being carried out at temperatures between about 750* and 1200*F. for a sufficient length of time to produce an effluent gas stream having a dewpoint below about 0*F., and a substantially completEly dehydrated and deammoniated catalyst having improved hydrogenation activity.

Claim 27

Dependent Claim 29 words

A process as defined in claim 1 wherein the water vapor partial pressure in step (2) is maintained at below about 2 psi at all temperatures above about 500*F.

Claim 28

Independent Claim 127 words

A method for rejuvenating and redispersal of catalytic metal of a catalyst comprising a Group VIII metal supported on particulate aggregates of a siliceous zeolite, said catalyst having been compounded by a procedure which yields mechanically stable calcined aggregates having a crushing strength above about 20 pounds per 1/8 inch pellet, and whose mechanical strength is not increased or decreased more than about 10% by the hereinafter recited thermal or hydrothermal conditions or rejuvenation procedure, said catalyst having been subjected to thermal or hydrothermal conditions of sufficient severity to bring about a maldistribution of said Group VIII metal with resultant loss in hydrogenation activity wherein a substantial proportion of the maldistributEd metal is in the form of agglomerates of less than 50 A in diameter, which comprises:

Claim 29

Independent Claim 127 words

A method for rejuvenating and redispersal of catalytic metal of a catalyst comprising a Group VIII metal supported on particulate aggregates of a siliceous zeolite, said catalyst having been compounded by a procedure which yields mechanically stable calcined aggregates having a crushing strength above about 20 pounds per 1/8 inch pellet, and whose mechanical strength is not increased or decreased more than about 10% by the hereinafter recited thermal or hydrothermal conditions or rejuvenation procedure, said catalyst having been subjected to thermal or hydrothermal conditions of sufficient severity to bring about a maldistribution of said Group VIII metal with resultant loss in hydrogenation activity wherein a substantial proportion of the maldistributEd metal is in the form of agglomerates of less than 50 A in diameter, which comprises:

Claim 30

Dependent Claim 19 words

A method as defined in claim 5 wherein said hydration and ammoniation in step (1) are carried out simultaneously.

Claim 31

Dependent Claim 26 words

A method as defined in claim 5 wherein said hydration and ammoniation in step (1) are carried out in the sequence of hydration followed by ammoniation.

Claim 32

Dependent Claim 16 words

A method as defined in claim 5 wherein said Group VIII metal is a noble metal.

Claim 33

Dependent Claim 15 words

A method as defined in claim 5 wherein said zeolite is a crystalline molecular sieve.

Claim 34

Dependent Claim 26 words

A method as defined in claim 5 wherein said catalyst has a crushing strength above 20 pounds per 1/8 inch pellet when subjected to step (1).

Claim 35

Independent Claim 160 words

A METHOD FOR REJUVENATING AND REDISPERSAL OF CATALYTIC METAL OF A CATALYST COMPRISING A GROUP VIII METAL SUPPORTED ON PARTICULATE AGGREGATES OF A SILICEOUS ZEOLITE AND A RELATIVELY NON-ZEOLITIC INORGANIC OXIDE BINDER, SAID CATALYST HAVING BEEN COMPOUNXDED BY A PROCEDURE WHICH YIELDS MECHANICALLY STABLE CALCINED AGGREGATES HAVING A CRUSHING STRENGTH ABOVE ABOUT 20 POUNDS PER 1/8 INCH PELLET, AND WHOSE MECHANICAL STRENGTH IS NOT INCREASED OR DECREASED MORE THAN ABOUT 10% BY ANY OF THE HEREINAFTER RECITED HYDROCARBON CONVERSION, OXIDATIVE REGENERATION OR REJUVENATION PROCEDURES, SAID CATALYST HAVING BEEN UTILIZED IN A HYDROCARBON CONVERSION PROCESS TO SUBSTANTIAL DEACTIVATION AND SUBSEQUENTLY REGENERATED BY OXIDATIVE COMBUSTION, AND DURING SAID HYDROCARBON CONVERSION AND/OR REGENERATION HAVING BEEN SUBJECTED TO THERMAL OR HYDROTHERMAL CONDITIONS OF SUFFICIENT SEVERITY TO BRING ABOUT A MALDISTRIBUTION OF SAID GROUP VIII METAL WITH RESULTANT LOSS IN HYDROGENATION ACTIVITY WHEREIN A SUBSTANTIAL PROPORTION OF THE MALDISTRIBUTED METAL IS IN THE FROM OF AGGLOMERATES OF LESS THAN 50 A IN DIAMETER, WHICH COMPRISES:

Claim 36

Independent Claim 160 words

A METHOD FOR REJUVENATING AND REDISPERSAL OF CATALYTIC METAL OF A CATALYST COMPRISING A GROUP VIII METAL SUPPORTED ON PARTICULATE AGGREGATES OF A SILICEOUS ZEOLITE AND A RELATIVELY NON-ZEOLITIC INORGANIC OXIDE BINDER, SAID CATALYST HAVING BEEN COMPOUNXDED BY A PROCEDURE WHICH YIELDS MECHANICALLY STABLE CALCINED AGGREGATES HAVING A CRUSHING STRENGTH ABOVE ABOUT 20 POUNDS PER 1/8 INCH PELLET, AND WHOSE MECHANICAL STRENGTH IS NOT INCREASED OR DECREASED MORE THAN ABOUT 10% BY ANY OF THE HEREINAFTER RECITED HYDROCARBON CONVERSION, OXIDATIVE REGENERATION OR REJUVENATION PROCEDURES, SAID CATALYST HAVING BEEN UTILIZED IN A HYDROCARBON CONVERSION PROCESS TO SUBSTANTIAL DEACTIVATION AND SUBSEQUENTLY REGENERATED BY OXIDATIVE COMBUSTION, AND DURING SAID HYDROCARBON CONVERSION AND/OR REGENERATION HAVING BEEN SUBJECTED TO THERMAL OR HYDROTHERMAL CONDITIONS OF SUFFICIENT SEVERITY TO BRING ABOUT A MALDISTRIBUTION OF SAID GROUP VIII METAL WITH RESULTANT LOSS IN HYDROGENATION ACTIVITY WHEREIN A SUBSTANTIAL PROPORTION OF THE MALDISTRIBUTED METAL IS IN THE FROM OF AGGLOMERATES OF LESS THAN 50 A IN DIAMETER, WHICH COMPRISES:

Claim 37

Dependent Claim 19 words

A method as defined in claim 11 wherein said hydration and ammoniation in step (1) are carried out simultaneously.

Claim 38

Dependent Claim 26 words

A method as defined in claim 11 wherein said hydration and ammoniation in step (1) are carried out in the sequence of hydration followed by ammoniation.

Claim 39

Dependent Claim 40 words

A METHOD AS DEFINED IN CLAIM 11 WHEREIN SAID GROUP VIII METAL IS A NOBLE METAL, AND SAID ZEOLITE IS A MOLECULAR SIEVE OF THE Y CRYSTAL TYPE WHEREIN THE ZEOLITE CATIONS ARE PRIMARILY HYDROGEN IONS AND/OR POLYVALENT METAL IONS.

Claim 40

Dependent Claim 30 words

A METHOD AS DEFINED IN CLAIM 14 WHEREIN SAID NOBLE METAL IS PALLADIUM AND WHEREIN THE ZEOLITE CATIONS IN SAID Y MOLECULAR SIEVE COMPRISE A SUBSTANTIAL PROPORTION OF HYDROGEN IONS.

Claim 41

Dependent Claim 26 words

A method as defined in claim 11 wherein said catalyst has a crushing strength above 20 pounds per 1/8 inch pellet when subjected to step (1).

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1978-08-11	1979-02-10	1979-08-12	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1982-08-11	1983-02-10	1983-08-12	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1986-08-11	1987-02-10	1987-08-12	$7700.00	Window Closed / Lapsed

Rejuvenation of damaged zeolite-supported metal catalysts

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