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CN-117651692-B - Use of 1-methyl-6, 7-dihydro-5H-cyclopenta [ B ] pyridin-1-ium cations as structure directing agents for the preparation of zeolites and zeolites obtained therewith

CN117651692BCN 117651692 BCN117651692 BCN 117651692BCN-117651692-B

Abstract

The present disclosure relates to the use of 1-methyl-6, 7-dihydro-5H-cyclopenta [ b ] pyridin-1-ium cations as Structure Directing Agents (SDA) for the preparation of zeolites. The disclosure also relates to compositions of matter, known as EMM-64 and EMM-65, obtainable by using the SDA, and methods of making and using the same. The disclosure also relates to a process for preparing an aluminosilicate molecular sieve of an RTH framework type using the SDA, an aluminosilicate molecular sieve of an RTH framework type obtainable by the process, and uses thereof.

Inventors

  • BURTON ALLEN W.
  • S.L. Sherid
  • VROMAN HILDA B.

Assignees

  • 埃克森美孚技术与工程公司

Dates

Publication Date
20260505
Application Date
20220608
Priority Date
20210618

Claims (12)

  1. 1. A crystalline material, designated EMM-64, having in calcined form an X-ray diffraction pattern comprising at least 9 peaks selected from table 1: TABLE 1 。
  2. 2. The material of claim 1 having an X-ray diffraction pattern comprising all peaks selected from table 1.
  3. 3. The material of claim 1 having the formula II: (m) X 2 O 3 :YO 2 (formula II), Wherein 0≤m≤0.025, X is Al, and Y is Si.
  4. 4. A crystalline material called EMM-64 having in its as-produced form an X-ray diffraction pattern comprising at least 7 peaks selected from table 3: TABLE 3 Table 3 。
  5. 5. The material of claim 4 having an X-ray diffraction pattern comprising all peaks selected from table 3.
  6. 6. The material of claim 4 having the formula of formula III: (n) Q (m) X 2 O 3 :YO 2 (formula III), Wherein n is more than or equal to 0 and less than or equal to 0.2, m is more than or equal to 0 and less than or equal to 0.025, Q is 1-methyl-6, 7-dihydro-5H-cyclopenta [ b ] pyridin-1-ium cation of formula I, (Formula I); x is Al and Y is Si.
  7. 7. The crystalline material of any one of claims 1 to 6 having a framework defined by the connectivity of tetrahedral T atoms in the unit cell, the tetrahedral T atoms being connected by bridging atoms, as shown in table 2 below: TABLE 2 a The positions of topologically equivalent atoms have the same "T-type" sign, b The size and number of smallest rings at each angle of the T-atom are defined as m.o' Keeffe and s.t. Hyde, zeolite, 19,370,1997.
  8. 8. A method of preparing an EMM-64 crystalline material according to any one of claims 1 to 7, comprising: (a) Preparing a synthesis mixture comprising water, a source of an oxide of tetravalent element Y, optionally a source of an oxide of trivalent element X, a structure directing agent Q, a source of fluoride ion F, optionally a source of hydroxide ion OH, and optionally a source of alkali and/or alkaline earth metal element M, Wherein the structure directing agent Q comprises a 1-methyl-6, 7-dihydro-5H-cyclopenta [ b ] pyridin-1-ium cation of formula I: (formula I), Wherein the synthesis mixture comprises fluoride F in a F/Y molar ratio of at least 0.1, and Wherein X is Al and Y is Si; (b) Heating the synthesis mixture under crystallization conditions including a temperature of 100 ℃ to 200 ℃ for a time sufficient to form crystals of the crystalline material; (c) Recovering at least a portion of the crystalline material from step (b), and (D) Optionally, treating the crystalline material recovered in step (c) to remove at least a portion of the structure directing agent Q.
  9. 9. The method of claim 8, wherein the synthesis mixture has the following composition expressed by molar ratios: 。
  10. 10. The method of claim 8, wherein the synthesis mixture has the following composition expressed by molar ratios: 。
  11. 11. the method of claim 8, wherein the synthesis mixture has the following composition expressed by molar ratios: 。
  12. 12. A method of converting an organic compound to a conversion product comprising contacting the organic compound with the crystalline material of any one of claims 1 to 7.

Description

Use of 1-methyl-6, 7-dihydro-5H-cyclopenta [ B ] pyridin-1-ium cations as structure directing agents for the preparation of zeolites and zeolites obtained therewith Cross Reference to Related Applications The present application claims priority and benefit from U.S. provisional application No.63/212205 filed on 6/18 of 2021, the entire contents of which are incorporated herein by reference. Technical Field The present disclosure relates to the use of 1-methyl-6, 7-dihydro-5H-cyclopenta [ b ] pyridin-1-ium cations as Structure Directing Agents (SDA) for the preparation of zeolites. The disclosure also relates to compositions of matter, known as EMM-64 and EMM-65, obtainable using the SDA, and methods of making and using the same. The disclosure also relates to a method of making an aluminosilicate molecular sieve of an RTH framework type using the SDA, an RTH material obtainable from the method, and uses thereof. Background Both natural and synthetic molecular sieve materials can be used as adsorbents and have catalytic properties for hydrocarbon conversion reactions. Certain molecular sieves, such as zeolites, alPOs and mesoporous materials, are ordered, porous crystalline materials having a well-defined crystalline structure as determined by X-ray diffraction (XRD). Certain molecular sieves are ordered and produce a specific identifiable XRD pattern. Within certain molecular sieve materials there may be a large number of cavities that may be interconnected by a number of channels or pores. Within a particular zeolite material, these cavities and pores are of uniform size. Since the size of these pores allows adsorption of molecules of a specific size while blocking molecules of a larger size, these materials are known as "molecular sieves" and are used in various industrial processes such as cracking, hydrocracking, disproportionation, alkylation, oligomerization and isomerization. Molecular sieves useful in catalysis and adsorption include any natural or synthetic crystalline molecular sieve. Examples of these molecular sieves include large pore zeolites, intermediate pore size zeolites, and small pore zeolites. These zeolites and their isoforms are classified by Structure Commission of the International Zeolite Association according to the rules of IUPAC Commission on zeolite naming. From this classification, framework-type zeolites and other crystalline microporous molecular sieves for which structures have been established are assigned a three letter code and are described in "Atlas of Zeolite Framework Types", eds.ch.baerlocher, l.b.mccuser and d.h.olson, elsevier, 6 th edition, 2007, which are incorporated herein by reference. These zeolites and their isoforms are also described in http:// america. IZA-structure. Org/IZA-SC/ftc_table. Php. Large pore zeolites generally have a molecular weight of at least aboutIncluding LTL, VFI, MAZ, FAU, OFF, BEA and MOR framework types. Examples of large pore zeolites include zeolite (mazzite), offretite (offretite), zeolite L, VPI-5, zeolite Y, zeolite X, ω, and β. Intermediate pore size zeolites generally have aboutTo less than aboutIncluding, for example, MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW and TON framework types of zeolites. Examples of intermediate pore size zeolites include ZSM-5, ZSM-11, ZSM-22, MCM-22, silicalite 1 and Silicalite 2. The small pore zeolite has a pore size of aboutTo less than aboutIncluding, for example, CHA, RTH, ERI, KFI, LEV, SOD and LTA framework type zeolites. Examples of small pore zeolites include ZK-4, ZSM-2, SAP0-34, SAP0-35, ZK-14, SAP0-42, ZK-21, ZK-22, ZK-5, ZK-20, zeolite A, chabazite, zeolite T, and ALPO-17. The ideal inorganic framework structure of a zeolite is a silicate framework in which all tetrahedral atoms are connected by oxygen atoms to four nearly nearest tetrahedral atoms. The term "silicate" as used herein refers to a material that contains at least silicon and oxygen atoms (i.e., -O-Si-) alternately bonded to each other, and optionally includes other atoms within the inorganic framework structure, including atoms such as boron, aluminum, or other metals (e.g., transition metals such as titanium, vanadium, or zinc). Atoms in the framework silicate other than silicon and oxygen occupy a portion of the lattice sites, with the remaining sites being occupied by silicon atoms in the "all-silica" framework silicate. Thus, the term "framework silicate" as used herein refers to an atomic lattice comprising any of silicate, borosilicate, gallosilicate, iron silicate, aluminosilicate, titanosilicate, zinc silicate, vanadiosilicate, and the like. The structure of the framework silicate within a given zeolite determines the size of the pores or channels present therein. The size of the pores or channels may determine the type of process for which a given zeolite is suitable. Currently, more than 200 unique zeolite framework silicate structures are known and identified by Strucuture Commission of International Zeo