# US 5,350,501 A · Hydrocracking catalyst and process

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- Number: US 5,350,501 A
- Document ID: US5350501A
- Status: Granted
- Kind: A
- Application number: 07/663,242
- Filed: 1991-02-28
- Granted: 1994-09-27
- Earliest claimed: 1990-05-22
- Assignees: Union Oil Company of California
- Inventors: John J. Ward
- Web page: https://patentgrep.com/patent/US5350501A

## CPC

- C10G 47/16: Crystalline alumino-silicate carriers
- B01J 29/80: Mixtures of different zeolites
- B01J 29/084: {Y-type faujasite}
- B01J 29/70: of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J 29/7007: {Zeolite Beta}
- B01J 2229/42: Addition of matrix or binder particles
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

A composition of matter comprising both (1) zeolite Beta and a (2) Y zeolite having either a unit cell size below about 24.45 angstroms or a water vapor sorption capacity at 25.degree. C. at p/p.sub.o of 0.10 of less than 10.00 weight percent. Typical of the Y zeolites used in the composition of the invention is a UHP-Y zeolite such as LZ-10 zeolite. The composition is especially suited for use in combination with one or more hydrogenation components as a catalyst for hydrocracking various types of feedstocks to produce either gasoline or middle distillate products.

## Claims

### Claim 1

A process for hydrocracking a hydrocarbon feedstock which comprises contacting said feedstock under hydrocracking conditions in an atmosphere containing no more than about 200 ppmv ammonia with a catalyst devoid of a nonzeolitic molecular sieve and comprising a hydrogenation component, zeolite Beta, and between about 15 and 50 weight percent of a Y zeolite having a unit cell size between about 24.20 and 24.35 angstroms and a water vapor sorption capacity at 25.degree. C. and a p/p.sub.o value of 0.10 of less than about 10 weight percent.

### Claim 2 (depends on 1)

The process of claim 1 carried out in an atmosphere which contains no more than about 20 ppmv ammonia.

### Claim 3 (depends on 1)

The process of claim 1 wherein said Y zeolite has a unit cell size between about 24.25 and 24.35 angstroms.

### Claim 4 (depends on 1)

The process of claim 1 wherein said catalyst comprises both a Group VIB metal hydrogenation component and a Group VIII metal hydrogenation component.

### Claim 5 (depends on 4)

The process of claim 4 wherein said Group VIB metal hydrogenation component is selected from the group consisting of molybdenum, tungsten, and the oxides and sulfides thereof and said Group VIII metal hydrogenation component is selected from the group consisting of nickel, cobalt, and the oxides and sulfides thereof.

### Claim 6 (depends on 1)

The process of claim 1 wherein said catalyst further comprises an inorganic refractory oxide.

### Claim 7 (depends on 6)

The process of claim 6 wherein said inorganic refractory oxide comprises alumina.

### Claim 8 (depends on 1)

The process of claim 1 wherein said catalyst contains between about 20 and 40 weight percent of said Y zeolite.

### Claim 9 (depends on 1)

The process of claim 1 wherein said catalyst contains a nickel hydrogenation component and a molybdenum hydrogenation component.

### Claim 10 (depends on 9)

The process of claim 9 carried out in an atmosphere which contains no more than about 20 ppmv ammonia.

### Claim 11 (depends on 1)

A hydrocracking process as defined by claim 1 wherein said Y zeolite has a unit cell size between about 24.25 and 24.35 angstroms and a water vapor sorption capacity at 4.6 mm water vapor partial pressure and 25.degree. C. less than 8.0 percent by weight of the zeolite.

### Claim 12 (depends on 1)

A process as defined by claim 1 wherein said Y zeolite is prepared by a process comprising the four steps of (1) partially ammonium exchanging a sodium Y zeolite, (2) calcining the resultant zeolite in the presence of water vapor, (3) ammonium exchanging the zeolite a second time, and (4) calcining the zeolite from step (3) in the presence of water vapor.

### Claim 13 (depends on 12)

The process of claim 12 wherein the zeolite is prepared such that in step (1) the sodium Y zeolite is reduced in sodium content to between about 0.6 and 5 weight percent, calculated as Na.sub.2 O, in step (2) a steam atmosphere is employed and the unit cell size of the zeolite is reduced to a value between about 24.45 to 24.64 angstroms, in step (3) the ammonium exchange reduces the sodium content to below about 0.6 weight percent, calculated as Na.sub.2 O, and in step (4) the calcination is conducted in the presence of steam and the unit cell size of the zeolite after calcination is less than about 24.35 angstroms.

### Claim 14

A hydrocracking process comprising contacting a hydrocarbon feedstock with a catalyst under hydrocracking conditions in the presence of hydrogen and in an atmosphere which contains no more than about 200 ppmv ammonia so as to produce a product of lower average boiling point, said catalyst being devoid of a nonzeolitic molecular sieve and comprising one or more hydrogenation components in combination with a support comprising an inorganic refractory oxide, zeolite Beta in a form catalytically active for cracking hydrocarbons, and a Y zeolite catalytically active for cracking hydrocarbons, said Y zeolite having a unit cell size between about 24.20 and 24.35 angstroms and a water vapor sorption capacity at 25.degree. C. and p/p.sub.o value of 0.10 of less than about 10 weight percent, wherein said catalyst contains between about 15 and 50 weight percent of said Y zeolite.

### Claim 15 (depends on 14)

The hydrocracking process of claim 14 wherein said zeolite has a unit cell size between about 24.25 and 24.35 angstroms.

### Claim 16 (depends on 14)

The hydrocracking process of claim 14 wherein said hydrogenation components comprise components selected from the group consisting of Group VIB and Group VIII metals and compounds thereof.

### Claim 17 (depends on 16)

The hydrocracking process of claim 16 wherein said hydrogenation component comprises a noble metal.

### Claim 18 (depends on 16)

The hydrocracking process of claim 16 wherein said catalyst comprises both a Group VIB and a Group VIII base metal hydrogenation component.

### Claim 19 (depends on 18)

The hydrocracking process of claim 18 wherein said catalyst comprises a Group VIB hydrogenation component selected from the group consisting of molybdenum, tungsten, and the oxides and sulfides thereof and a Group VIII non-noble metal hydrogenation component selected from the group consisting of nickel, cobalt, and the oxides and sulfides thereof.

### Claim 20 (depends on 19)

The hydrocracking process of claim 19 wherein the two zeolites are present in said catalyst in a weight ratio between 2:1 and 1:2, Beta zeolite to Y zeolite.

### Claim 21 (depends on 14)

The hydrocracking process of claim 14 wherein the product comprises at least 50 volume percent gasoline product boiling in the 50.degree. to 420.degree. F. range, the feedstock containing no more than about 15 volume percent of such gasoline product.

### Claim 22 (depends on 14)

The hydrocracking process of claim 14 wherein said catalyst comprises one or more nickel hydrogenation components and one or more molybdenum hydrogenation components.

### Claim 23 (depends on 22)

The hydrocracking process of claim 22 wherein said support contains at least 20 weight percent of each zeolite.

### Claim 24 (depends on 22)

The hydrocracking process of claim 22 carried out in an atmosphere which contains no more than about 20 ppmv ammonia.

### Claim 25 (depends on 14)

The hydrocracking process of claim 14 wherein said Beta zeolite is in the hydrogen form, has a silica-to-alumina molar ratio between 20 and 30, a crystal size between about 0.1 and 0.7 um, a surface area between 700 and 750 m.sup.2 /gm, and a sodium content less than 1.0 percent by anhydrous weight, calculated as Na.sub.2 O.

### Claim 26 (depends on 14)

The hydrocracking process of claim 14 wherein said catalyst is essentially devoid of noble metals.

### Claim 27 (depends on 14)

The hydrocracking process of claim 14 wherein said support contains the zeolite Beta and the Y zeolite as the only zeolites therein, and the balance consists essentially of alumina in essentially the gamma alumina form, said alumina comprising at least 10 percent by weight of the support.

### Claim 28 (depends on 14)

The hydrocracking process of claim 14 carried out in an atmosphere which contains no more than about 20 ppmv ammonia.

### Claim 29 (depends on 14)

The hydrocracking process of claim 14 wherein said catalyst is devoid of rare earth metals.

### Claim 30 (depends on 14)

The hydrocracking process of claim 14 wherein said catalyst is devoid of an ultrastable Y zeolite, a rare earth-exchanged Y zeolite, ZSM-4 zeolite, ZSM-18 zeolite and ZSM-20 zeolite.

### Claim 31 (depends on 14)

The hydrocracking process of claim 14 wherein said catalyst is devoid of a molecular sieve having a pore size below 7.0 angstroms.

### Claim 32 (depends on 14)

The hydrocracking process of claim 14 wherein said Y zeolite is LZ-10 zeolite.

### Claim 33 (depends on 14)

The hydrocracking process of claim 14 wherein said inorganic refractory oxide comprises alumina.

### Claim 34 (depends on 14)

The hydrocracking process of claim 14 wherein said catalyst contains between about 20 and 40 weight percent of said Y zeolite.

### Claim 35

A hydrocracking process comprising contacting a gas oil feedstock with a catalyst under hydrocracking conditions in the presence of hydrogen and in an atmosphere which contains no more than about 200 ppmv ammonia so as to produce a product of lower average boiling point, said catalyst being devoid of a nonzeolitic molecular sieve and comprising one or more hydrogenation components in combination with a support comprising an inorganic refractory oxide binder, zeolite Beta in a form catalytically active for cracking hydrocarbons, and LZ-10 zeolite, the LZ-10 zeolite having a unit cell size between about 24.25 and 24.35 angstroms and a water vapor sorption capacity at 4.6 mm water vapor partial pressure and 25.degree. C. of less than about 8.0 percent by weight of the zeolite, wherein said catalyst contains between about 15 and about 50 weight percent of said LZ-10 zeolite.

### Claim 36 (depends on 35)

The hydrocracking process of claim 35 wherein the two zeolites are present in said catalyst in a weight ratio between 2:1 and 1:2, Beta zeolite to LZ-10 zeolite, and the hydrogenation component comprises a molybdenum component present in the catalyst in a proportion between about 8 and 30 weight percent, calculated as MoO.sub.3, and a nickel component in a proportion between about 3 and 10 weight percent, calculated as NiO, and wherein said Beta zeolite is in the hydrogen form, has a silica-to-alumina molar ratio between 20 and 30, a crystal size between about 0.1 and 0.7 um, a surface area between 700 and 750 m.sup.2 /gm, and a sodium content less than 1.0 percent by anhydrous weight, calculated as Na.sub.2 O, and wherein said support comprises at least 50 weight percent of the Beta and LZ-10 zeolites combined, and wherein said support comprises at least 20 weight percent of each of the LZ-10 and Beta zeolites, and wherein the product comprises at least 70 volume percent gasoline boiling in the 50.degree. to 420.degree. F. range.

### Claim 37 (depends on 35)

The hydrocracking process of claim 35 wherein said catalyst contains between about 20 and 40 weight percent of said LZ-10 zeolite.

### Claim 38 (depends on 35)

The hydrocracking process of claim 35 carried out in an atmosphere which contains no more than about 20 ppmv ammonia.