# US 9,580,328 B2 · Mesoporous framework-modified zeolites

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- Number: US 9,580,328 B2
- Document ID: US9580328B2
- Status: Granted
- Kind: B2
- Application number: 13/440,781
- Filed: 2012-04-05
- Published: 2012-10-11
- Granted: 2017-02-28
- Earliest claimed: 2011-04-08
- Assignees: Rive Technology, Inc.
- Applicants: Javier Garcia Martinez; Ernest Senderov; Richard Hinchey
- Inventors: Javier Garcia Martinez; Ernest Senderov; Richard Hinchey
- Web page: https://patentgrep.com/patent/US9580328B2

## CPC

- C01B 39/026: {After-treatment}
- B01J 29/041: {Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41}
- B01J 35/647: {2-50 nm}
- B01J 35/66: Pore distribution
- B01J 35/80: characterised by their amorphous structures
- 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 29/08: of the faujasite type, e.g. type X or Y
- B01J 29/084: {Y-type faujasite}
- B01J 29/18: of the mordenite type
- B01J 29/40: of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J 29/65: of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J 29/7003: {A-type}
- B01J 29/7007: {Zeolite Beta}
- B01J 29/7015: {CHA-type, e.g. Chabazite, LZ-218}
- B01J 29/7034: {MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3}
- B01J 35/60: characterised by their surface properties or porosity
- B01J 35/69: bimodal
- B01J 35/70: characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00)
- B01J 2229/16: to increase the Si/Al ratio; Dealumination
- B01J 2229/36: Steaming
- B01J 2229/37: Acid treatment
- B01J 2229/38: Base treatment
- B01J 2235/05: Nuclear magnetic resonance [NMR]
- B01J 2235/15: X-ray diffraction
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

Compositions and methods for preparing mesoporous and/or mesostructured materials from low Si/Al zeolites. Various embodiments described herein relate to preparation of mesoporous and/or mesostructured zeolites via a framework modification step followed by a mesopore introduction step.

## Claims

### Claim 1

A method of forming a material comprising at least one mesoporous zeolite, said method comprising:
(a) subjecting an initial zeolite to a framework modification process thereby producing a framework-modified zeolite, wherein said framework modification process comprises contacting at least a portion of said initial zeolite with an acid; and
(b) forming a plurality of mesopores in at least a portion of said framework-modified zeolite thereby forming said mesoporous zeolite, wherein said forming comprises contacting at least a portion of said framework-modified zeolite with a base;
wherein said forming of step (b) is performed in the substantial absence of a surfactant,
wherein said framework-modified zeolite has not been subjected to drying prior to said forming of step (b),
wherein said initial zeolite is selected from the group consisting of zeolite A, faujasites, mordenite, CHA, ZSM-5, ZSM-12, ZSM-22, beta zeolite, synthetic ferrierite (ZSM-35), synthetic mordenite, and mixtures of two or more thereof,
wherein said initial zeolite has a framework silicon-to-aluminum ratio (“Si/Al”) of less than 30, and
wherein said framework-modified zeolite has a crystalline content that is less than the crystalline content of said initial zeolite as measured by X-ray diffraction (“XRD”).

### Claim 2 (depends on 1)

The method of claim 1 wherein said initial zeolite has a framework Si/Al of less than 20.

### Claim 3 (depends on 1)

The method of claim 1 wherein said initial zeolite has a framework Si/Al of less than 10.

### Claim 4 (depends on 1)

The method of claim 1 wherein said acid has a pH of less than 4 and said acid is a dealuminating acid.

### Claim 5 (depends on 1)

The method of claim 1 wherein said acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, sulfonic acid, oxalic acid, citric acid, ethylenediaminetetraacetic acid, tartaric acid, malic acid, glutaric acid, succinic acid, and mixtures of two or more thereof.

### Claim 6 (depends on 1)

The method of claim 1 wherein said acid is present in an initial amount in the range of from about 1 to about 10 milliequivalents per gram (“meq/g”) of initial zeolite.

### Claim 7 (depends on 1)

The method of claim 1 wherein said contacting is performed for a time period in the range of from about 1 minute to about 4 hours and at a temperature from about room temperature to 200° C.

### Claim 8 (depends on 1)

The method of claim 1 wherein said framework-modified zeolite has a framework Si/Al that is at least 1 percent greater than the framework Si/Al of said initial zeolite.

### Claim 9 (depends on 1)

The method of claim 1 wherein said framework-modified zeolite has a crystalline content that is at least 5 percent less than the crystalline content of said initial zeolite as measured by XRD.

### Claim 10 (depends on 1)

The method of claim 1 wherein said framework-modified zeolite has a crystalline content that is at least 15 percent less than the crystalline content of said initial zeolite as measured by XRD.

### Claim 11 (depends on 1)

The method of claim 1 wherein said framework-modified zeolite has fewer Si—O—Al bonds in its zeolite framework than said initial zeolite.

### Claim 12 (depends on 1)

The method of claim 1 wherein said framework-modified zeolite has a greater number of Si—OH and Al—OH terminal groups than said initial zeolite.

### Claim 13 (depends on 1)

The method of claim 1 wherein said base is selected from the group consisting of ammonium hydroxide, tetraalkyl ammonium hydroxides, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, amines, and mixtures of two or more thereof.

### Claim 14 (depends on 1)

The method of claim 1 wherein said step (b) increases the crystalline content of said framework-modified zeolite and said mesoporous zeolite has a crystalline content that is at least 5 percent greater than said framework-modified zeolite.

### Claim 15 (depends on 1)

The method of claim 1 wherein said mesoporous zeolite has a crystalline content that is at least 60 percent of the crystalline content of said initial zeolite.

### Claim 16 (depends on 1)

The method of claim 1 wherein said mesoporous zeolite has a total 20 to 80 Å diameter mesopore volume of at least 0.05 cc/g.

### Claim 17 (depends on 1)

The method of claim 1 wherein said mesoporous zeolite has a total 20 to 80 Å diameter mesopore volume that is at least 20 percent greater than the 20 to 80 Å diameter mesopore volume of said initial zeolite.

### Claim 18 (depends on 1)

The method of claim 1 wherein said mesoporous zeolite has a total 20 to 80 Å diameter mesopore volume that is at least 0.02 cc/g greater than the 20 to 80 Å diameter mesopore volume of said initial zeolite.

### Claim 19 (depends on 1)

The method of claim 1 wherein said initial zeolite comprises a zeolite Y selected from the group consisting of USY, NH4Y, NaY, a rare earth ion zeolite Y, or mixtures thereof.

### Claim 20 (depends on 1)

The method of claim 1 wherein said mesoporous zeolite is subjected to one or more post-formation treatments selected from the group consisting of calcination, ion exchange, steaming, incorporation into an adsorbent, incorporation into a catalyst, re-alumination, silicon incorporation, incorporation into a membrane, and combinations thereof.

### Claim 21 (depends on 20)

The method of claim 20 wherein said ion exchange is selected from the group consisting of ammonium ion exchange, rare earth ion exchange, lithium ion exchange, potassium ion exchange, calcium ion exchange, and combinations of two or more thereof.

### Claim 22 (depends on 1)

The method of claim 1 wherein said mesoporous zeolite is a mesostructured zeolite.

### Claim 23

A method of forming a material comprising at least one desilicated mesoporous zeolite, said method comprising:
(a) contacting an initial zeolite with an acid thereby forming an acid-pretreated zeolite; and
(b) contacting at least a portion of said acid-pretreated zeolite with a base to at least partially desilicate said acid-pretreated zeolite thereby producing said desilicated mesoporous zeolite,
wherein said initial zeolite is selected from the group consisting of zeolite A, faujasites, mordenite, CHA, ZSM-5, ZSM-12, ZSM-22, beta zeolite, synthetic ferrierite (ZSM-35), synthetic mordenite, and mixtures of two or more thereof,
wherein said contacting of step (b) is performed in the substantial absence of a surfactant,
wherein said acid-treated zeolite has not been subjected to drying prior to said contacting of step (b),
wherein said initial zeolite has a framework silicon-to-aluminum ratio (“Si/Al”) of less than 30.

### Claim 24 (depends on 23)

The method of claim 23 wherein said initial zeolite has a framework Si/Al of less than 10.

### Claim 25 (depends on 23)

The method of claim 23 further comprising (c) subjecting at least a portion of said desilicated mesoporous zeolite to thermal treatment.

### Claim 26 (depends on 25)

The method of claim 25 wherein said thermal treatment comprises contacting at least a portion of said desilicated mesoporous zeolite with steam, wherein said steam has a temperature in the range of from about 450 to about 1,000° C.

### Claim 27 (depends on 23)

The method of claim 23 wherein said acid-pretreated zeolite has a framework Si/Al that is at least 10 percent greater than the framework Si/Al of said initial zeolite.

### Claim 28 (depends on 23)

The method of claim 23 wherein said acid-pretreated zeolite has a crystalline content that is at least 10 percent less than the crystalline content of said initial zeolite as measured by XRD.

### Claim 29 (depends on 23)

The method of claim 23 wherein said acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, sulfonic acid, oxalic acid, citric acid, ethylenediaminetetraacetic acid, tartaric acid, malic acid, glutaric acid, succinic acid, and mixtures of two or more thereof.

### Claim 30 (depends on 23)

The method of claim 23 wherein said acid is present in an initial amount of at least 2.5 meq/g of initial zeolite.

### Claim 31 (depends on 23)

The method of claim 23 wherein said acid is present in an initial amount of at least 4.0 meq/g of initial zeolite.

### Claim 32 (depends on 23)

The method of claim 23 wherein said base is selected from the group consisting of ammonium hydroxide, tetraalkyl ammonium hydroxides, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, amines, and mixtures of two or more thereof.

### Claim 33 (depends on 23)

The method of claim 23 wherein said mesoporous zeolite has a crystalline content that is at least 10 percent greater than said acid-pretreated zeolite.

### Claim 34 (depends on 23)

The method of claim 23 wherein said mesoporous zeolite has a crystalline content that is at least 80 percent of the crystalline content of said initial zeolite.

### Claim 35 (depends on 23)

The method of claim 23 wherein said desilicated mesoporous zeolite has a total 20 to 80 Å diameter mesopore volume of at least 0.1 cc/g.

### Claim 36 (depends on 23)

The method of claim 23 wherein said desilicated mesoporous zeolite has a total 20 to 80 Å diameter mesopore volume that is at least 50 percent greater than the 20 to 80 Å diameter mesopore volume of said initial zeolite.

### Claim 37 (depends on 23)

The method of claim 23 wherein said desilicated mesoporous zeolite has a total 20 to 80 Å diameter mesopore volume that is at least 0.05 cc/g greater than the 20 to 80 Å diameter mesopore volume of said initial zeolite.

### Claim 38 (depends on 23)

The method of claim 23 wherein said initial zeolite comprises a zeolite Y selected from the group consisting of USY, NH4Y, NaY, a rare earth ion zeolite Y, or mixtures thereof.

### Claim 39 (depends on 23)

The method of claim 23 wherein said desilicated mesoporous zeolite is a mesostructured zeolite.

### Claim 40

A method of forming a mesoporous material, said method comprising
(a) subjecting an initial zeolite to a framework modification process thereby producing a framework-modified zeolite, wherein said framework modification process comprises contacting at least a portion of said initial zeolite with an acid; and
(b) forming a plurality of mesopores in at least a portion of said framework-modified zeolite thereby forming said mesoporous material, wherein said forming comprises contacting at least a portion of said framework-modified zeolite with a base;
wherein said forming of step (b) is performed in the substantial absence of a surfactant,
wherein said framework-modified zeolite has not been subjected to drying prior to said forming of step (b),
wherein said initial zeolite is selected from the group consisting of zeolite A, faujasites, mordenite, CHA, ZSM-5, ZSM-12, ZSM-22, beta zeolite, synthetic ferrierite (ZSM-35), synthetic mordenite, and mixtures of two or more thereof,
wherein said initial zeolite has a framework silicon-to-aluminum ratio (“Si/Al”) of less than 30, and
wherein said mesoporous material has a crystalline content that is at least 90 percent less than the crystalline content of said initial zeolite as measured by X-ray diffraction (“XRD”).

### Claim 41 (depends on 40)

The method of claim 40 wherein said mesoporous material has substantially no crystalline content as measured by XRD.

### Claim 42 (depends on 40)

The method of claim 40 wherein said initial zeolite has a framework Si/Al of less than 10.

### Claim 43 (depends on 40)

The method of claim 40 wherein said framework-modified zeolite has a framework Si/Al that is at least 20 percent greater than the framework Si/Al of said initial zeolite.

### Claim 44 (depends on 40)

The method of claim 40 wherein said acid is present in an initial amount of at least 2.0 meq/g of initial zeolite.

### Claim 45 (depends on 40)

The method of claim 40 wherein said acid is present in an initial amount of at least 3.5 meq/g of initial zeolite.

### Claim 46 (depends on 40)

The method of claim 40 wherein said mesoporous material has a total 20 to 80 Å diameter mesopore volume of at least 0.1 cc/g.

### Claim 47 (depends on 40)

The method of claim 40 wherein said mesoporous material has a total 20 to 80 Å diameter mesopore volume that is at least 40 percent greater than the 20 to 80 Å diameter mesopore volume of said initial zeolite.

### Claim 48 (depends on 40)

The method of claim 40 wherein said mesoporous material has a total 20 to 80 Å diameter mesopore volume that is at least 0.1 cc/g greater than the 20 to 80 Å diameter mesopore volume of said initial zeolite.

### Claim 49 (depends on 40)

The method of claim 40 wherein said initial zeolite comprises a zeolite Y selected from the group consisting of USY, NH4Y, NaY, a rare earth ion zeolite Y, or mixtures thereof.

### Claim 50 (depends on 40)

The method of claim 40 wherein said mesoporous material is subjected to one or more post-formation treatments selected from the group consisting of calcination, ion exchange, steaming, incorporation into an adsorbent, incorporation into a catalyst, re-alumination, silicon incorporation, incorporation into a membrane, and combinations thereof.

### Claim 51 (depends on 40)

The method of claim 40 wherein said mesoporous material is a mesostructured material.