Rare earth-containing Y zeolite compositions

Claim 2

A zeolite produced by a method comprising cation-exchanging a crystalline aluminosilicate zeolite of the Y type with rare earth-containing cations, calcining the resultant rare earth-exchanged zeolite in the presence of water vapor at a partial pressure of at least about 0.2 p.s.i.a., ion-exchanging the calcined product with ammonium ions, and subsequently ion-exchanging with Group VIII metal cations.

Claim 3

A zeolite produced by a method comprising cation-exchanging a crystalline aluminosilicate zeolite of the Y type with rare earth-containing cations, calcining the resultant rare earth-exchanged zeolite in the presence of water vapor at a partial pressure of at least about 0.2 p.s.i.a., ion-exchanging the calcined product with ammonium ions followed by calcining, and subsequently ion-exchanging with Group VIII metal cations.

Claim 4

A zeolite produced by a method comprising cation-exchanging a crystalline aluminosilicate zeolite of the Y type with rare earth-containing cations, calcining the resultant rare earth-exchanged zeolite in the presence of water vapor at a partial pressure of at least about 0.2 p.s.i.a., ion-exchanging the calcined product with ammonium ions followed by calcining, and subsequently ion-exchanging with Group VIII metal cations.

Claim 5

A zeolite produced by a method comprising cation-exchanging a crystalline aluminosilicate zeolite of the Y type with rare earth-containing cations, calcining the resultant zeolite in the presence of water vapor at a partial pressure of at least about 0.2 p.s.i.a., ion-exchanging the calcining product with ammonium ions, and subsequently ion exchanging with cations containing a noble metal.

Claim 6

A zeolite produced by a method comprising cation-exchanging a crystalline aluminosilicate zeolite of the Y type with rare earth-containing cations, calcining the resultant zeolite in the presence of water vapor at a partial pressure of at least about 0.2 p.s.i.a., ion-exchanging the calcining product with ammonium ions, and subsequently ion exchanging with cations containing a noble metal.

Claim 7

A zeolite as defined in claim 3 wherein said zeolite initially is a sodium Y zeolite and said calcining is accomplished in the presence of water vapor at a partial pressure above 1.0 p.s.i.a.

Claim 8

A zeolite as defined in claim 4 wherein after said noble metal cation exchange, the zeolite contains less than about 0.05 percent by weight of sodium, calculated as Na 2 O.

Claim 9

A zeolite as defined in claim 4 or 5 wherein said noble metal is palladium or platinum.

Claim 10

A zeolite as defined in claim 4 or 5 wherein the zeolite, after said noble metal exchange, contains at least about 2 percent by weight of rare earth metals, calculated as RE 2 O 3 .

Claim 11

A zeolite as defined in claim 4 wherein said calcining is carried out at a temperature between about 1100° and 1350° F. and a water vapor partial pressure above about 12 p.s.i.a.

Claim 12

A zeolite as defined in claim 8 wherein, after said ammonium ion exchange, the zeolite is exchanged with noble metal cations, with the resulting zeolite containing at least about 2.0 percent by weight rare earth metals, calculated as RE 2 O 3 , less than about 0.5 percent by weight of sodium, calculated as Na 2 O, and at least about 0.1 percent by weight of total noble metals, calculated as the metals.

Claim 13

A zeolite containing a rare earth metal and a noble metal prepared by a method comprising cation exchanging a sodium Y zeolite with cations containing one or more rare earth metals but retaining at least some residual sodium ions, calcining the resultant rare earth-exchanged zeolite in thc presence of water vapor at a partial pressure of at least about 0.2 p.s.i.a. and at a temperature between about 600° and 1600° F. so as to result in at least some shrinkage of the unit cell size of the zeolite, ion exchanging the resultant zeolite with ammonium ions so as to reduce the residual sodium content thereof to below about 0.5 percent by weight, calculated as Na 2 O, and subsequently ion-exchanging with cations containing a noble metal.

Claim 14

A zeolite containing a rare earth metal and a noble metal prepared by a method comprising cation exchanging a sodium Y zeolite with cations containing one or more rare earth metals but retaining at least some residual sodium ions, calcining the resultant rare earth-exchanged zeolite in thc presence of water vapor at a partial pressure of at least about 0.2 p.s.i.a. and at a temperature between about 600° and 1600° F. so as to result in at least some shrinkage of the unit cell size of the zeolite, ion exchanging the resultant zeolite with ammonium ions so as to reduce the residual sodium content thereof to below about 0.5 percent by weight, calculated as Na 2 O, and subsequently ion-exchanging with cations containing a noble metal.

Claim 15

A zeolite as defined in claim 10 wherein the unit cell size of said zeolite after said calcination is between about 24.20 and 24.64 Å.

Claim 16

A zeolite as defined in claim 10 wherein the unit cell size of said zeolite after said calcination is between about 24.40 and 24.64 Å.

Claim 17

A zeolite as defined in claim 12 wherein at least 25% of the residual sodium ions are removed by ion exchange with said ammonium ions.

Claim 18

A zeolite as defined in claim 10, 12, or 13 wherein said noble metal is platinum or palladium.

Claim 19

A zeolite as defined in claim 12 wherein said zeolite, after said ammonium ion exchange, contains less than about 0.5 percent by weight sodium, calculated as Na 2 O.

Claim 20

A zeolite as defined in claim 12 wherein said zeolite, after said ammonium exchange but prior to said noble metal exchange, is calcined.

Claim 21

A zeolite as defined in claim 15 wherein said calcination is carried out in the presence of water vapor at a partial pressure between about 2 and 15 p.s.i.a.

Claim 22

A zeolite as defined in claim 17 wherein said zeolite after said ammonium ion exchange contains less than 0.05 percent by weight sodium.

Claim 23

A zeolite as defined in claim 12, 16, or 17 wherein said zeolite after said ammonium ion exchange contains at least 5 percent by weight of rare earth metals, calculated as RE 2 O 3 .

Claim 24

A zeolite as defined in claim 17 wherein said zeolite after said rare earth cation exchange contains more than about 1 percent by weight sodium.

Claim 25

A catalyst useful in hydrocarbon conversion reactions involving hydrogenation, said catalyst being prepared by admixing the zeolite of claim 1, 2, 3, 4, 10, 12, or 16 with a refractory oxide component and calcining.

Claim 26

A catalyst useful in hydrocracking prepared by admixing the zeolite of claim 14 with a refractory oxide component and calcining.

Claim 27

A hydrocracking catalyst comprising a zeolite containing a rare earth metal, Group VIII metal, and hydrogen ions, said catalyst being prepared by a method including the steps of cation exchanging a Y-type zeolite with rare earth-containing cations, calcining the resultant rare earth-exchanged zeolite in the presence of water vapor at a partial pressure of at least 0.2 p.s.i.a., ion-exchanging the calcined product with ammonium ions, subsequently admixing with a refractory oxide component, calcining the resulting admixture so as to convert at least some of the ammonium ions to hydrogen ions, impregnating the calcined admixture with a solution containing Group VIII metal cations under conditions such that at least some Group VIII metal cations are exchanged into the zeolite contained in the calcined admixture, and again calcining.

Claim 28

A hydrocracking catalyst comprising a zeolite containing a rare earth metal, Group VIII metal, and hydrogen ions, said catalyst being prepared by a method including the steps of cation exchanging a Y-type zeolite with rare earth-containing cations, calcining the resultant rare earth-exchanged zeolite in the presence of water vapor at a partial pressure of at least 0.2 p.s.i.a., ion-exchanging the calcined product with ammonium ions, subsequently admixing with a refractory oxide component, calcining the resulting admixture so as to convert at least some of the ammonium ions to hydrogen ions, impregnating the calcined admixture with a solution containing Group VIII metal cations under conditions such that at least some Group VIII metal cations are exchanged into the zeolite contained in the calcined admixture, and again calcining.

Claim 29

A hydrocracking catalyst prepared by a method including the steps of: (1) cation exchanging a sodium Y zeolite with rare earth cations such that the resultant zeolite contains at least about 2 percent by weight of rare earth metals, calculated as RE 2 O 3 , but still retains at least some sodium; (2) calcining the resultant rare earth-sodium Y zeolite in the presence of water vapor at a partial pressure of at least about 0.2 p.s.i.a. so as to effect at least some reduction in the unit cell size of said zeolite, with the resultant unit cell size being between 24.40 and 24.64 Å; (3) ammonium ion exchanging the calcined zeolite from step (2) so as to further reduce the sodium content thereof; (4) ion-exchanging the ammonium-exchanged zeolite from step (3) with cations containing a noble metal; and (5) admixing the zeolite from step (4) with a refractory oxide component and calcining the resultant admixture.

Claim 30

A hydrocracking catalyst prepared by a method including the steps of: (1) cation exchanging a sodium Y zeolite with rare earth cations such that the resultant zeolite contains at least about 2 percent by weight of rare earth metals, calculated as RE 2 O 3 , but still retains at least some sodium; (2) calcining the resultant rare earth-sodium Y zeolite in the presence of water vapor at a partial pressure of at least about 0.2 p.s.i.a. so as to effect at least some reduction in the unit cell size of said zeolite, with the resultant unit cell size being between 24.40 and 24.64 Å; (3) ammonium ion exchanging the calcined zeolite from step (2) so as to further reduce the sodium content thereof; (4) ion-exchanging the ammonium-exchanged zeolite from step (3) with cations containing a noble metal; and (5) admixing the zeolite from step (4) with a refractory oxide component and calcining the resultant admixture.

Claim 31

A catalyst as defined in claim 24 wherein the zeolite in the calcined product of step (5) contains at least 2 weight percent of rare earth metals, calculated as RE 2 O 3 , and at least 0.1 weight percent of one or more noble metals, calculated as the metals.

Claim 32

A catalyst as defined in claim 25 wherein said zeolite after said rare earth cation exchange in step (1) contains no more than 5 weight percent by weight of sodium but the ammonium-exchanged zeolite from step (3) contains less than 0.5 weight percent sodium.

Claim 33

A catalyst as defined in claim 26 wherein the rare earth-sodium Y zeolite produced in step (1) contains between 1 and 5 percent by weight of sodium, calculated as Na 2 O, and the zeolite in the calcined product of step (5) contains at least 5 weight percent rare earth metals, calculated as RE 2 O 3 .

Claim 34

A catalyst as defined in claim 24 or 27 wherein said calcination in step (2) is accomplished in the presence of an atmosphere consisting essentially of steam.

Claim 35

A catalyst as defined in claim 24, 25, or 27 wherein the noble metal exchanged into said zeolite in step (4) is palladium and said calcining in step (2) is accomplished in the presence of water vapor at a partial pressure above about 12 p.s.i.a.

Claim 38

A method as defined in claim 30 wherein said calcining results in some shrinkage of the unit cell size of the zeolite.

Claim 39

A method as defined in claim 31 wherein said Group VIII metal is a noble metal.

Claim 40

A zeolite as defined in claim 3 wherein said calcining is carried out in the presence of water vapor at a partial pressure between about 2 and 15 p.s.i.a. under conditions such that the unit cell size of the zeolite undergoes some shrinkage.

Claim 41

A zeolite as defined in claim 33 wherein said water vapor partial pressure during said calcining is between 5 and 15 p.s.i.a., and said noble metal is platinum or palladium.

Claim 42

A zeolite as defined in claim 34 wherein said zeolite contains, due to said exchange wth the rare earth cations, at least 5 percent by weight of rare earth metals, calculated as RE 2 O 3 .

Claim 43

A zeolite as defined in claim 35 wherein said zeolite contains less than about 0.5 percent by weight of sodium, calculated as Na 2 O, after said noble metal exchange.

Claim 44

A zeolite as defined in claim 36 wherein said calcining is carried out at a temperature of about 1100° to 1350° F. at essentially atmospheric pressure in the presence of water vapor at a partial pressure above about 12 p.s.i.a.

Claim 45

A zeolite as defined in claim 1, 2, 3, 10, or 34 wherein the rare earth cation exchange introduces a mixture of rare earth cations into said zeolite, said mixture containing cerium, lanthanum, praeseodymium, and neodymium cations.

Claim 46

A catalyst as defined in claim 23, 24, or 27 wherein the rare earth cation exchange introduces a mixture of rare earth cations into said zeolite, said mixture containing cerium, lanthanum, praeseodymium, and neodymium cations.

Claim 47

A zeolite as defined in claim 37 wherein the rare earth cation exchange introduces a mixture of rare earth cations into said zeolite, said mixture containing cerium, lanthanum, praeseodymium, and neodymium cations.

Claim 48

A zeolite as defined in claim 40 wherein said noble metal comprises palladium.

Claim 49

A zeolite as defined in claim 34, 35, 37, 40, or 41 wherein said zeolite contains less than about 0.05 percent by weight of sodium, calculated as Na 2 O, after said noble metal exchange.