Hydrocracking catalysts containing rare earth containing post-modified USY zeolite, method for preparing hydrocracking catalysts, and methods for hydrocracking hydrocarbon oil with hydrocracking catalysts

Patent metadata

Field	Value
Publication number	US-11420192-B2
Application number	US-202016940711-A
Country	US
Kind code	B2
Filing date	Jul 28, 2020
Priority date	Jul 28, 2020
Publication date	Aug 23, 2022
Grant date	Aug 23, 2022

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.

First claim

What is claimed is:

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.

2. 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.

3. 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.

4. 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.

5. The catalyst composition of claim 1 , wherein the framework-substituted USY zeolite comprises a specific surface area from 600 m 2 /g to 900 m 2 /g.

6. The catalyst composition of claim 1 , wherein the catalyst composition comprises a specific surface area from 200 m 2 /g to 450 m 2 /g.

7. The catalyst composition of claim 1 , wherein the framework-substituted USY zeolite comprises a molar ratio of SiO 2 to Al 2 O 3 from 20 to 100.

8. 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.

9. 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.

10. 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.

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;
incorporating a doped rare earth element into the framework-substituted USY zeolite to provide a rare-earth doped framework-substituted USY zeolite; and
combining the rare-earth doped framework-substituted USY zeolite and at least one hydrogenative component to provide the catalyst composition.

12. 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.

13. 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.

14. 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.

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.

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

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

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

19. The method of claim 15 , wherein the reactor has a hydrogen/oil ratio from 500 Nm 3 /m 3 to 2500 Nm 3 /m 3 .

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

Assignees

• Saudi Arabian Oil Co
• Jgc Catalysts & Chemicals Ltd
• Japan Coop Center Petroleum

Inventors

• Koseoglu Omer Refa
• Hodgkins Robert Peter
• Watabe Mitsunori
• Uchida Koji

Classifications

• C10G47/20

  the catalyst containing other metals or compounds thereof · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J21/04

  Alumina · CPC title

• C10G2300/301

  Boiling range · CPC title

• B01J37/0018

  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) · CPC title