CN-121986070-A - Process for preparing beta zeolite material

Abstract

According to one or more embodiments, a beta zeolite material may be prepared by a process that may include adding a parent beta zeolite in an alkaline solution to form an alkaline beta zeolite suspension, adding water to the alkaline beta zeolite suspension to form a diluted alkaline beta zeolite suspension, hydrothermally treating the diluted alkaline beta zeolite suspension to form a hydrothermally treated mixture, and separating a solid beta zeolite material consisting essentially of polymorph a and polymorph B from the hydrothermally treated mixture. The molar ratio of polymorph a to polymorph B in the solid beta zeolite material is greater than the molar ratio of polymorph a to polymorph B in the parent beta zeolite.

Inventors

• Rajesh Kumar Passapur
• Robert Peter Hodgkins
• Omer Refa Kozeoglu
• HUANG GUOWEI
• Magnus Lv Ping
• Anisa Benjeriu Sijerari

Assignees

• 沙特阿拉伯石油公司
• 阿卜杜拉国王科技大学

Dates

Publication Date

20260505

Application Date

20241010

Priority Date

20231012

Claims (15)

1. 1. A method of preparing a solid beta zeolite material, the method comprising: adding a parent beta zeolite to an alkaline solution to form an alkaline beta zeolite suspension; adding water to the basic beta zeolite suspension to form a diluted basic beta zeolite suspension; subjecting the diluted basic beta zeolite suspension to a hydrothermal treatment to form a hydrothermally treated mixture, and Separating a solid beta zeolite material consisting essentially of polymorph a and polymorph B from the hydrothermally treated mixture, wherein the solid beta zeolite material has a molar ratio of polymorph a to polymorph B that is greater than the molar ratio of polymorph a to polymorph B of the parent beta zeolite.
2. 2. The method of claim 1, wherein the method does not use an organic structure directing agent.
3. 3. The method of claim 2, wherein the organic structure directing agent is one or more of tetraethylammonium cation, N, N-dimethyl-2, 6-cis-dimethylpiperidinium cation, dimethyldiisopropylammonium cation, N, N, N-trimethylcyclohexylammonium cation, N-ethyl-N, N-dimethylcyclohexylammonium cation, N-isopropyl-N-methyl-pyrrolidinium cation, N-isopentyl-N-methyl-pyrrolidinium cation, and N-isobutyl-N-methyl-pyrrolidinium cation.
4. 4. The process of any one of claims 1 to 3 wherein the molar ratio of polymorph A to modified polymorph B in the solid beta zeolite material is 30% or more greater than the molar ratio of polymorph A to polymorph B in the parent beta zeolite, and optionally wherein the solid beta zeolite material is chiral.
5. 5. The method according to any one of claims 1 to 4, wherein the parent beta zeolite comprises BEA framework comprising polymorph a and polymorph B.
6. 6. The method of claim 5, wherein, The mole ratio of the polymorphic form A to the polymorphic form B in the parent beta zeolite is less than or equal to 1, or The mole ratio of polymorph a to polymorph B in the parent beta zeolite is greater than 1.
7. 7. The method according to any one of claims 1 to 6, wherein the alkaline solution comprises urea, and optionally wherein the mass ratio of urea to water in the alkaline solution is from 1:10 to 1:100.
8. 8. The process of claim 7, wherein the mass ratio of urea to zeolite beta in the basic zeolite beta suspension is from 0.8:1 to 1.2:1.
9. 9. The process of any one of claims 1 to 8, wherein adding water to the basic beta zeolite suspension comprises adding a first portion of water to the basic beta zeolite suspension, stirring the suspension at a temperature of 20 ℃ to 40 ℃ for 1 minute to 12 hours, and adding a second portion of water to the suspension to form the diluted basic beta zeolite suspension.
10. 10. The process of any one of claims 1 to 9, further comprising stirring the diluted basic beta zeolite suspension at a temperature of 20 ℃ to 40 ℃ for 1 minute to 12 hours prior to performing the hydrothermal treatment.
11. 11. The process of any one of claims 1 to 10, wherein the mass ratio of beta zeolite to water in the diluted basic beta zeolite suspension is from 1:15 to 1:60.
12. 12. The process of any one of claims 1 to 11, wherein hydrothermally treating the diluted basic beta zeolite suspension comprises exposing the diluted basic beta zeolite suspension to a temperature of 100 ℃ to 200 ℃ for 1 hour to 120 hours.
13. 13. The method of any one of claims 1 to 12, wherein the solid beta zeolite material is separated from the hydrothermally treated mixture by filtration.
14. 14. The method of any one of claims 1 to 13, further comprising washing and drying the solid beta zeolite material.
15. 15. The method of any one of claims 1 to 14, wherein at least one of: The solid beta zeolite material is capable of contacting with a reactant to catalyze a chemical reaction; The solid beta zeolite material can be used to separate the chiral components of a mixture; an increase in the unit cell parameters of polymorph B in the solid beta zeolite material; The polymorph B in the solid beta zeolite material comprises defect-induced mesopores, and The solid beta zeolite material comprises multi-modal pores.

Description

Process for preparing beta zeolite material Cross Reference to Related Applications The application claims the benefit of U.S. application Ser. No. 18/485,844, filed on 10/12 of 2023, the entire contents of which are incorporated herein by reference. Technical Field Embodiments described herein relate generally to porous materials, and more particularly to zeolites. Background Materials including pores, such as zeolites, are useful in many petrochemical applications. For example, such materials may be used as catalysts in many reactions that convert hydrocarbons or other reactants from a feed chemical to a product chemical. Zeolites can be characterized by a framework type of microporous structure. Over the past few decades, various types of zeolites have been identified, with the zeolite types generally described by framework types, and specific zeolite materials being identifiable by various names such as ZSM-5 or beta more specifically. Zeolite-containing catalysts and adsorbents find wide use in many different industries. Exemplary industries include the petrochemical industry in oil refining, gas separation, and carbon dioxide separation and capture processes. For example, in the petroleum industry, zeolite-containing catalysts may be included in processes such as Fluid Catalytic Cracking (FCC) and hydrocracking to catalyze reactions such as hydrogenation, dehydrogenation, isomerization, alkylation, and cracking. Zeolite-containing adsorbents are useful for separating paraffins or aromatic isomers, as well as for removing water and other impurities from hydrocarbon streams in drying processes. Disclosure of Invention Embodiments of the present disclosure relate to zeolitic materials and methods of preparing beta zeolitic materials having a molar ratio of polymorph a to polymorph B that is greater than the molar ratio of polymorph a to polymorph B in the starting beta zeolitic material (sometimes referred to herein as "polymorph a-enriched" beta zeolitic material). Conventional beta zeolite materials typically include a co-organism of chiral polymorph a and achiral polymorph B. Due to the chirality of polymorph a, a higher mole percentage of polymorph a to polymorph B zeolite beta material may have desirable chemical properties. For example, when used as a catalyst, a higher mole percent of the beta zeolite material of polymorph a to polymorph B may have desirable shape selectivity and enantioselectivity. Conventional methods for preparing beta zeolite materials enriched in polymorphic form a can be relatively difficult to implement 3 or/and expensive, e.g., complicated procedures and reagents can be used in the synthesis of beta zeolite materials enriched in polymorphic form a. For example, conventional methods for preparing beta zeolite materials enriched in polymorphic form a may require the use of chiral reagents (e.g., organic structure directing agents), or may use highly corrosive compounds such as HF. Thus, there is a need for new processes for preparing beta zeolite materials enriched in polymorphic form a. According to various embodiments disclosed herein, the methods of the present disclosure for preparing a polymorph a-enriched zeolite beta material meet this need. For example, some methods of the present disclosure may not require the use of complex reagents and procedures. Conversely, according to one or more embodiments, the methods of the present disclosure can prepare a polymorph a-enriched beta zeolite material by adding the parent beta zeolite to an alkaline solution prior to dilution of the suspension. The diluted suspension may then be subjected to a hydrothermal treatment to form a solid beta zeolite material, wherein the molar ratio of polymorph a to polymorph B in the solid beta zeolite material is greater than the molar ratio of polymorph a to polymorph B in the parent beta zeolite. Some such methods may avoid the use of organic structure directing agents and/or highly corrosive compounds. According to one or more embodiments, the beta zeolite material may be prepared by a process that may include adding a parent beta zeolite to an alkaline suspension to form an alkaline beta zeolite suspension, adding water to the alkaline beta zeolite suspension to form a diluted alkaline beta zeolite suspension, hydrothermally treating the diluted alkaline beta zeolite suspension to form a hydrothermally treated mixture, and separating a solid beta zeolite material consisting essentially of polymorph a and polymorph B from the hydrothermally treated mixture. The solid beta zeolite material can have a molar ratio of polymorph a to polymorph B that is greater than the molar ratio of polymorph a to polymorph B in the parent beta zeolite. It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter.