IP Library Granted Patent US 12,239,966
Granted Patent B2
US 12,239,966 · App. 18/051,910 · Granted Mar 4, 2025

Methods of producing catalyst compositions, and methods of cracking hydrocarbon feed streams using such catalyst compositions

Inventors: Lianhui Ding (Dhahran, SA); Faisal Alotaibi (Dhahran, SA)
Assignee: Saudi Arabian Oil Company
B01J29/7815B01J21/04B01J29/084B01J29/80B01J35/615B01J35/633B01J35/635B01J35/647B01J37/0018B01J37/031B01J37/04B01J37/08C10G47/20B01J2029/062C10G2300/202C10G2300/301C10G2300/308
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Quick Facts
Patent No.
US 12,239,966
App. No.
18/051,910
Granted
Mar 4, 2025
Kind
B2
Abstract

This disclosure generally relates to methods for producing catalyst compositions, which may include forming a precursor solution comprising a silicon-containing material, an aluminum-containing material, and a quaternary amine, hydrothermally treating the precursor solution at a first temperature to form an intermediate mixture, hydrothermally treating the intermediate mixture at a second temperature to form beta zeolite, wherein the first temperature is less than the second temperature by at least 200° C., forming an extrudable mixture comprising the beta zeolite, alumina, a metal precursor, and a binder, extruding the extrudable mixture to form extrudates, and calcining the extrudates to form the catalyst composition.

Claims (46)

1. A method for producing a catalyst composition, the method comprising:

forming a precursor solution comprising a silicon-containing material, an aluminum-containing material, and a quaternary amine;

hydrothermally treating the precursor solution at a first temperature to form an intermediate mixture;

hydrothermally treating the intermediate mixture at a second temperature to form beta zeolite, wherein the first temperature is less than the second temperature by at least 200° C.;

forming an extrudable mixture comprising the beta zeolite, alumina, a metal precursor, and a binder;

extruding the extrudable mixture to form extrudates; and

calcining the extrudates to form the catalyst composition.

2. The method of claim 1 , wherein the beta zeolite is not calcined before extruding the extrudable mixture.

3. The method of claim 1 , wherein the intermediate mixture is not dried before forming the beta zeolite.

4. The method of claim 1 , wherein the silicon-containing material comprises SiO 2 , sodium silicate, tetramethylsiloxane, tetraethylsiloxane, silicon salt, silicon alkoxide, fumed silica, or combinations thereof.

5. The method of claim 1 , wherein the aluminum-containing material comprises aluminum nitrate, aluminum sulfate, aluminum alkoxide, other aluminum salts, or combinations thereof.

6. The method of claim 1 , wherein the quaternary amine comprises tetraethylammonium hydroxide, tetraethylammonium bromide, or combinations thereof.

7. The method of claim 1 , wherein the first temperature is of from 100° C. to 150° C.

8. The method of claim 1 , wherein the second temperature is of from 500° C. to 650° C.

9. The method of claim 1 , further comprising cooling the intermediate mixture before hydrothermally treating the intermediate mixture.

10. The method of claim 1 , further comprising washing the intermediate mixture before hydrothermally treating the zeolite intermediate.

11. The method of claim 1 , wherein the metal precursor comprises molybdenum, nickel, tungsten, or combinations of two or more thereof.

12. The method of claim 1 , wherein the extrudable mixture further comprises a zeolite Y.

13. The method of claim 1 , wherein the beta zeolite has a surface area of greater than or equal to 400 cm 2 /g.

14. The method of claim 1 , wherein one or more of:

the beta zeolite has a mesopore volume of greater than 0.5 mL/g;

the beta zeolite has a micropore volume of greater than 0.1 mL/g;

the beta zeolite has an average pore size of greater than 3 nanometers;

the beta zeolite has a crystallinity of at least 70% as measured using x-ray diffraction;

the catalyst composition has a surface area of greater than or equal to 250 cm 2 /g;

the catalyst composition has a mesopore volume of greater than 0.4 mL/g; or

the catalyst composition has an average pore size of greater than 3 nanometers.

15. A method of cracking a hydrocarbon feed stream comprising contacting the hydrocarbon feed stream with the catalyst composition of claim 1 to crack at least a portion of the hydrocarbon feed stream to form a product effluent.

16. The method of claim 15 , wherein the hydrocarbon feed stream is crude oil.

17. The method of claim 15 , wherein the hydrocarbon feed stream is hydrotreated before the contacting.

18. The method of claim 15 , wherein the product effluent comprises at least 40 wt. % naphtha.

19. A method for producing a catalyst composition, the method comprising:

forming a precursor solution comprising a silicon-containing material, an aluminum-containing material, and a quaternary amine;

hydrothermally treating the precursor solution at a first temperature to form an intermediate mixture;

hydrothermally treating the intermediate mixture at a second temperature to form beta zeolite, wherein the first temperature is less than the second temperature by at least 200° C.;

forming an extrudable mixture comprising the beta zeolite, alumina, a metal precursor, and a binder;

extruding the extrudable mixture to form extrudates; and

calcining the extrudates to form the catalyst composition;

wherein:

the beta zeolite is not calcined before extruding the extrudable mixture;

the silicon-containing material comprises fumed silica;

the quaternary amine comprises tetraethylammonium hydroxide;

the first temperature is of from 100° C. to 150° C.;

the second temperature is of from 500° C. to 650° C.; and

the metal precursor comprises molybdenum and nickel.

20. The method of claim 19 , wherein the extrudable mixture further comprises a zeolite Y.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 3, 2022
From: DING, LIANHUI; ALOTAIBI, FAISAL
To: SAUDI ARABIAN OIL COMPANY
Reel/Frame 061641/0337 →
Continuity (1)
Related Publication 20240139720A1 · May 2, 2024
References Cited (20)
US 7462276B2 · Wang et al. · 2008 [cited by applicant]
US 11148124B2 · Ding · 2021 [cited by applicant]
US 11213810B1 · Ding et al. · 2022 [cited by applicant]
US 20120258852A1 · Martinez et al. · 2012 [cited by applicant]
US 20200156052A1 · Eid · 2020 [cited by examiner]
US 20210213432A1 · Fan · 2021 [cited by examiner]
US 20220001363A1 · Ding et al. · 2022 [cited by applicant]
EP 1194236B1 · 2003 [cited by applicant]
Camblor et al., “Characterization of nanocrystalline zeolite Beta”, Microporous and Mesoporous Materials, vol. 25, pp. 59-74, 1998. [cited by applicant]
Ding et al., “Effect of agitation on the synthesis of zeolite beta and its synthesis mechanism in absence of alkali cations”, Microporous and Mesoporous Materials, vol. 94, pp. 1-8, 2006. [cited by applicant]
Ding et al., “LCO hydrotreating with Mo—Ni and W—Ni supported on nano- and micro-sized zeolite beta”, Applied Catalysis A: General, vol. 353, pp. 17-23, 2009. [cited by applicant]
Kim et al., “Oligomerization and isomerization of dicyclopentadiene over mesoporous materials produced from zeolite beta”, Catalysis Today, vol. 232, pp. 69-74, 2014. [cited by applicant]
Prokesova et al., “Preparation of nanosized micro/mesoporous composites via simultaneous synthesis of Beta/MCM-48 phases”, Microporous and Mesoporous Materials, vol. 64, pp. 165-174, 2003. [cited by applicant]
Notification of Transmittal of the International Search Report and the Written Opinion of the International Searching Authority, or the Declaration dated Mar. 4, 2024 pertaining to International application No. PCT/US20… [cited by applicant]
Jin, Yingjie et al. “Synthesis of mesoporous MOR materials by varying temperature crystallizations and combining ternary organic templates” Microporous and Mesoporous Materials, vol. 147, No. 1, Jun. 23, 2011, pp. 259-2… [cited by applicant]
Deneyer, Aron et al. “Zeolite Synthesis under Nonconventional Conditions: Reagents, Reactors, and Modi Operandi” Chemistry of Materials, Apr. 30, 2020, vol. 32, No. 12, pp. 4884-4919. [cited by applicant]
Feng, Rui et al. “Two-stage glucose-assisted crystallization of ZSM-5 to improve methanol to propylene (MTP)” Microporous and Mesoporous Materials, vol. 270, May 7, 2018, pp. 57-66. [cited by applicant]
Kerstens, Dorien et al. “State of the Art and Perspectives of Hierarchical Zeolites: Practical Overview of Synthesis Methods and Use in Catalysis” Advanced Materials, vol. 32, No. 44, Sep. 23, 2020, pp. 1-47. [cited by applicant]
Liu, Baoyu et al. “Fabrication of a hierarchically structured beta zeolite by a dual-porogenic surfactant” Journal of Materials Chemistry, vol. 22, No. 35, Jul. 13, 2012, pp. 18631-18638. [cited by applicant]
Serrano, D. P. et al. “Synthesis strategies in the search for hierarchical zeolites” Chemical Society Reviews, vol. 42, No. 9, Jan. 1, 2013, p. 4004-4035. [cited by applicant]