# US 2022/0032273 A1 · Hydrocracking catalysts containing rare earth containing post-modified usy zeolite, method for preparing hydrocracking catalysts, and method for hydrocracking hydrocarbon oil with hydrocracking catalysts

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- Number: US 2022/0032273 A1
- Document ID: US20220032273A1
- Status: Published application
- Kind: A1
- Application number: 16/940,711
- Filed: 2020-07-28
- Published: 2022-02-03
- Earliest claimed: 2020-07-28
- Assignees: Saudi Arabian Oil Company; JGC Catalysts and Chemicals Ltd.; Japan Cooperation Center Petroleum
- Applicants: Saudi Arabian Oil Company; JGC Catalysts and Chemicals, Ltd.; Japan Cooperation Center Petroleum
- Inventors: Omer Refa Koseoglu; Robert Peter Hodgkins; Mitsunori Watabe; Koji Uchida
- Web page: https://patentgrep.com/patent/US20220032273A1

## CPC

- B01J 29/088: {Y-type faujasite}
- B01J 21/04: Alumina
- B01J 29/166: {Y-type faujasite}
- B01J 35/615: {100-500 m2/g}
- B01J 35/617: {500-1000 m2/g}
- B01J 35/633: {less than 0.5 ml/g}
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 35/651: {50-500 nm}
- B01J 37/0018: {Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- C10G 47/18: the catalyst containing platinum group metals or compounds thereof
- C10G 47/20: the catalyst containing other metals or compounds thereof
- C10G 2300/1074: Vacuum distillates
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- C10G 2300/301: Boiling range
- C10G 2300/308: Gravity, density, e.g. API
- C10G 2300/4018: Spatial velocity, e.g. LHSV, WHSV
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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

## Abstract

In accordance with one or more embodiments of the present disclosure, a catalyst composition includes a catalyst support and at least one hydrogenative component disposed on the catalyst support. The catalyst support includes at least one USY zeolite having a framework substituted with titanium and zirconium. The framework-substituted USY zeolite comprises at least one rare earth element. Methods of making and using such a catalyst in a hydrocracking process are also disclosed.

## Claims

### Claim 1

A catalyst composition comprising:
a catalyst support comprising at least one framework-substituted ultra-stable Y-type (USY) zeolite substituted with zirconium atoms and titanium atoms, the at least one framework-substituted USY zeolite comprising at least one doped rare earth element; and
at least one hydrogenative component disposed on the catalyst support.

### Claim 2 (depends on 1)

The catalyst composition of claim 1, wherein the at least one framework-substituted USY zeolite is substituted with 0.1 wt. % to 5 wt. % zirconium atoms and 0.1 wt. % to 5 wt. % titanium calculated on an oxide basis.

### Claim 3 (depends on 1)

The catalyst composition of claim 1, wherein the rare earth element is selected from the group consisting of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and a combination of two more thereof.

### Claim 4 (depends on 1)

The catalyst composition of claim 1, wherein the framework-substituted USY zeolite comprises a crystal lattice constant from 2.43 nm to 2.45 nm.

### Claim 5 (depends on 1)

The catalyst composition of claim 1, wherein the framework-substituted USY zeolite comprises a specific surface area from 600 m2/g to 900 m2/g.

### Claim 6 (depends on 1)

The catalyst composition of claim 1, wherein the catalyst composition comprises a specific surface area from 200 m2/g to 450 m2/g.

### Claim 7 (depends on 1)

The catalyst composition of claim 1, wherein the framework-substituted USY zeolite comprises a molar ratio of SiO2 to Al2O3 from 20 to 100.

### Claim 8 (depends on 1)

The catalyst composition of claim 1, wherein the catalyst composition comprises a plurality of pores having a diameter of 600 Å or less, the pores having a volume from 0.4 ml/g to 0.75 ml/g.

### Claim 9 (depends on 1)

The catalyst composition of claim 1, wherein the at least one hydrogenative component comprises from 0.01 wt. % to 40 wt. % of the catalyst composition.

### Claim 10 (depends on 1)

The catalyst composition of claim 1, wherein the at least one hydrogenative component comprises iron, cobalt, nickel, rhodium, palladium, silver, iridium, platinum, gold, chromium, molybdenum, tungsten, or a combination of two or more thereof.

### Claim 11

A method of making a catalyst composition, the method comprising:
heating an ultra-stable Y-type (USY) zeolite in an oven having a temperature from 500° C. to 700° C.;
mixing a zirconium compound and a titanium compound with the ultra-stable Y-type (USY) zeolite to produce a framework-substituted USY zeolite; and
incorporating a doped rare earth element into the framework-substituted USY zeolite.

### Claim 12 (depends on 11)

The method of claim 11, wherein the mixing comprises forming a suspension containing the USY zeolite, the suspension having a liquid/solid mass ratio from 5 to 15 and adding inorganic acid or organic acid.

### Claim 13 (depends on 11)

The method of claim 11, wherein the at least one hydrogenative component is added such that the at least one hydrogenative component comprises from 0.01 wt. % to 40 wt. % of the catalyst composition.

### Claim 14 (depends on 11)

The method of claim 11, further comprising mixing a binder with the framework substituted USY zeolite having the rare earth element, the binder selected from the group consisting of alumina, silica, titania, silica-alumina, alumina-titania, alumina-zirconia, alumina-boria, phosphorus-alumina, silica-alumina-boria, phosphorus-alumina-boria, phosphorus-alumina-silica, silica-alumina-titania, silica-alumina-zirconia, and a combination of two more thereof.

### Claim 15

A method for hydrocracking hydrocarbon oil, comprising:
contacting at least one hydrocarbon oil stream with at least one hydrocracking catalyst composition and hydrogen in a reactor in order to hydrocrack the hydrocarbon oil stream, the hydrocracking catalyst composition comprising:
a catalyst support comprising at least one framework-substituted ultra-stable Y-type (USY) zeolite substituted with zirconium atoms and titanium atoms, the at least one framework-substituted USY zeolite comprising at least one doped rare earth element; and
at least one hydrogenative component disposed on the catalyst support.

### Claim 16 (depends on 15)

The method of claim 15, wherein the reactor has a temperature from 300° C. to 500° C.

### Claim 17 (depends on 15)

The method of claim 15, wherein the hydrocarbon oil has a boiling point from 375° C. to 833° C.

### Claim 18 (depends on 15)

The method of claim 15, wherein the hydrogen is added to the reactor at a pressure from 3.5 MPa to 35 MPa.

### Claim 19 (depends on 15)

The method of claim 15, wherein the reactor has a hydrogen/oil ratio from 500 Nm3/m3 to 2500 Nm3/m3.

### Claim 20 (depends on 15)

The method of claim 15, wherein the reactor has a liquid hourly space velocity from 0.1 per hour to 10 per hour.