# US 2016/0167973 A1 · Preparation of mesoporous zeolites with reduced processing

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- Number: US 2016/0167973 A1
- Document ID: US20160167973A1
- Status: Published application
- Kind: A1
- Application number: 14/966,674
- Filed: 2015-12-11
- Published: 2016-06-16
- Earliest claimed: 2014-12-11
- Assignees: Rive Technology, Inc.
- Applicants: Rive Technology, Inc.
- Inventors: R. Samuel Boorse; Kunhao Li
- Web page: https://patentgrep.com/patent/US20160167973A1

## CPC

- C01B 39/24: Type Y {(C01B39/205 takes precedence)}
- B01J 29/084: {Y-type faujasite}
- C01B 39/026: {After-treatment}
- C01B 39/20: Faujasite type, e.g. type X or Y
- B01J 35/647: {2-50 nm}
- B01J 35/69: bimodal
- B01J 2029/081: {Increasing the silica/alumina ratio; Desalumination}
- B01J 2229/37: Acid treatment
- B01J 2229/38: Base treatment
- C01P 2006/17: Pore diameter distribution
- 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
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

Methods for introducing mesoporosity into zeolitic materials are described herein that employ an acid treatment, an optional surfactant treatment, and a base treatment without filtration or purification steps between the steps. In particular, the process generally involves subjecting a zeolitic material to an acid treatment followed by a surfactant treatment and base treatment. The methods can efficiently introduce mesoporosity into various zeolitic materials, such as zeolites.

## Claims

### Claim 1

A method for producing a material comprising a mesoporous zeolite, said method comprising:
(a) contacting an initial zeolitic material with an acid to produce an acid-treated zeolitic material, wherein said contacting of step (a) is carried out in a first slurry comprising a first solid phase and a first liquid phase; and
(b) subsequent to step (a), contacting said acid-treated zeolitic material with a base to thereby provide a base-treated zeolitic material, wherein said contacting of step (b) is carried out in a second slurry comprising a second solid phase and a second liquid phase, wherein at least 30 weight percent of said first liquid phase is also present in said second liquid phase,
wherein the 20 to 80 Å diameter mesopore volume of said base-treated zeolitic material is greater than the mesopore volume of said initial zeolitic material,
wherein the pH of said second liquid phase is higher than the pH of said first liquid phase.

### Claim 2 (depends on 1)

The method of claim 1, further comprising contacting a surfactant with at least one of said initial zeolitic material, said acid-treated zeolitic material, and/or said base-treated zeolitic material.

### Claim 3 (depends on 2)

The method of claim 2, wherein the amount of said surfactant contacted with said initial zeolitic material, said acid-treated zeolitic material, and/or said base-treated zeolitic material is in the range of 0.01 to 0.2 grams of surfactant per gram of dry zeolitic material.

### Claim 4 (depends on 2)

The method of claim 2, wherein said surfactant is contacted with said initial zeolitic material and/or said acid-treated zeolitic material.

### Claim 5 (depends on 2)

The method of claim 2, wherein said surfactant is contacted with said acid-treated zeolitic material.

### Claim 6 (depends on 2)

The method of claim 2, wherein said surfactant and said acid are simultaneously contacted with said initial zeolitic material.

### Claim 7 (depends on 1)

The method of claim 1, wherein at least 90 weight percent of said first liquid phase is also present in said second liquid phase.

### Claim 8 (depends on 1)

The method of claim 1, further comprising, subsequent to step (b), separating said second solid phase from said second liquid phase, wherein the separated second solid phase comprises said base-treated zeolitic material.

### Claim 9 (depends on 8)

The method of claim 8, wherein said separated second liquid phase comprises a surfactant in an amount less than 5,000 ppmw.

### Claim 10 (depends on 8)

The method of claim 8, further comprising, subsequent to said separating, reducing the sodium oxide content of said base-treated zeolitic material to less than 5 weight percent.

### Claim 11 (depends on 8)

The method of claim 8, further comprising, subsequent to said separating, contacting said separated second solid phase with an acid.

### Claim 12 (depends on 1)

The method of claim 1, wherein steps (a) and (b) are carried out in a common reaction zone within a single continuously stirred-tank reactor.

### Claim 13 (depends on 1)

The method of claim 1, wherein steps (a) and (b) are carried out in multiple reaction zones in a continuous flow pipe reactor.

### Claim 14 (depends on 1)

The method of claim 1, wherein said first liquid phase has a final pH in the range of 1.5 to 4.

### Claim 15 (depends on 1)

The method of claim 1, wherein said second liquid phase has a final pH in the range of 5 to 11.

### Claim 16 (depends on 1)

The method of claim 1, wherein said first and second liquid phases each comprise at least 50 weight percent of water.

### Claim 17 (depends on 1)

The method of claim 1, wherein said first and second slurries each have a solids content in the range of 5 to 60 weight percent.

### Claim 18 (depends on 1)

The method of claim 1, wherein the 20 to 80 Å diameter mesopore volume of said base-treated zeolitic material is at least 20 percent greater than the mesopore volume of said initial zeolitic material.

### Claim 19 (depends on 1)

The method of claim 1, wherein said initial zeolitic material comprises a faujasite.

### Claim 20 (depends on 1)

The method of claim 1, wherein said initial zeolitic material comprises a composite shaped article comprising a zeolite.

### Claim 21

A method for forming a mesoporous zeolitic material, said method comprising:
(a) contacting an initial zeolitic material with an acid to thereby form a first mixture comprising at least a portion of said acid, an acid-treated zeolitic material, and a liquid;
(b) contacting said first mixture with a surfactant to thereby form a second mixture comprising at least a portion of said surfactant, at least a portion of said acid, at least 30 weight percent of said liquid from said first mixture, and a surfactant-treated zeolitic material;
(c) contacting said second mixture with a base to thereby form a third mixture comprising at least a portion of said acid, at least a portion of said surfactant, at least a portion of said base, at least 30 weight percent of said liquid from said first mixture, and a base-treated zeolitic material; and
(d) recovering at least a portion of said base-treated zeolitic material from said third mixture to thereby form said mesoporous zeolitic material.

### Claim 22 (depends on 21)

The method of claim 21, wherein at least a portion of said contacting of step (a) and said contacting of step (b) occur simultaneously.

### Claim 23 (depends on 21)

The method of claim 21, wherein at least a portion of said contacting of step (b) and said contacting of step (c) occur simultaneously.

### Claim 24 (depends on 21)

The method of claim 21, wherein the amount of said surfactant contacted with said first mixture is in the range of 0.01 to 0.2 grams of surfactant per gram of dry zeolitic material.

### Claim 25 (depends on 21)

The method of claim 21, wherein at least 90 weight percent of said liquid from said first mixture is also present in said second mixture.

### Claim 26 (depends on 21)

The method of claim 21, wherein at least 90 weight percent of said liquid from said second mixture is also present in said third mixture.

### Claim 27 (depends on 21)

The method of claim 21, further comprising reducing the sodium oxide content of said mesoporous zeolitic material to less than 5 weight percent.

### Claim 28 (depends on 21)

The method of claim 21, further comprising contacting said mesoporous zeolitic material with an acid.

### Claim 29 (depends on 21)

The method of claim 21, wherein steps (a)-(c) are carried out in a common reaction zone within a single continuously stirred-tank reactor.

### Claim 30 (depends on 21)

The method of claim 21, wherein steps (a) and (b) are carried out in multiple reaction zones in a continuous flow pipe reactor.

### Claim 31 (depends on 21)

The method of claim 21, wherein said first mixture has a final pH in the range of 1.5 to 4.

### Claim 32 (depends on 21)

The method of claim 21, wherein said third mixture has a final pH in the range of 5 to 11.

### Claim 33 (depends on 21)

The method of claim 21, wherein said first mixture, second mixture, and third mixture have a solids content in the range of 5 to 60 weight percent.

### Claim 34 (depends on 21)

The method of claim 21, wherein the 20 to 80 Å diameter mesopore volume of said mesoporous zeolitic material is at least 20 percent greater than the mesopore volume of said initial zeolitic material.

### Claim 35 (depends on 21)

The method of claim 21, wherein said initial zeolitic material comprises a faujasite.

### Claim 36 (depends on 21)

The method of claim 21, wherein said initial zeolitic material comprises a composite shaped article comprising a zeolite.

### Claim 37

A method for producing a material comprising a mesoporous zeolite, said method comprising:
(a) contacting an initial zeolite with an acid to produce an acid-treated zeolite, wherein said contacting of step (a) is carried out in a first slurry comprising a first solid phase and a first liquid phase; and
(b) subsequent to step (a), contacting said acid-treated zeolite with a base and a surfactant to thereby provide a base-treated zeolite, wherein said contacting of step (b) is carried out in a second slurry comprising a second solid phase and a second liquid phase, wherein at least 30 weight percent of said first liquid phase is also present in said second liquid phase,
wherein the 20 to 80 Å diameter mesopore volume of said base-treated zeolite is greater than the mesopore volume of said initial zeolite,
wherein the pH of said second liquid phase is higher than the pH of said first liquid phase.

### Claim 38 (depends on 37)

The method of claim 37, wherein the amount of said surfactant contacted with said acid-treated zeolitic material is in the range of 0.01 to 0.2 grams of surfactant per gram of dry zeolitic material.

### Claim 39 (depends on 37)

The method of claim 37, wherein at least 90 weight percent of said first liquid phase is also present in said second liquid phase.

### Claim 40 (depends on 37)

The method of claim 37, further comprising, subsequent to step (b), separating said second solid phase from said second liquid phase, wherein the separated second solid phase comprises said base-treated zeolitic material.

### Claim 41 (depends on 40)

The method of claim 40, further comprising, subsequent to said separating, reducing the sodium oxide content of said base-treated zeolitic material to less than 5 weight percent.

### Claim 42 (depends on 40)

The method of claim 40, further comprising, subsequent to said separating, contacting said separated second solid phase with an acid.

### Claim 43 (depends on 37)

The method of claim 37, wherein steps (a) and (b) are carried out in a common reaction zone within a single continuously stirred-tank reactor.

### Claim 44 (depends on 37)

The method of claim 37, wherein steps (a) and (b) are carried out in multiple reaction zones in a continuous flow pipe reactor.

### Claim 45 (depends on 37)

The method of claim 37, wherein said first liquid phase has a final pH in the range of 1.5 to 4.

### Claim 46 (depends on 37)

The method of claim 37, wherein said second liquid phase has a final pH in the range of 5 to 11.

### Claim 47 (depends on 37)

The method of claim 37, wherein said first and second liquid phases each comprise at least 50 weight percent of water.

### Claim 48 (depends on 37)

The method of claim 37, wherein said first and second slurries each have a solids content in the range of 5 to 60 weight percent.

### Claim 49 (depends on 37)

The method of claim 37, wherein the 20 to 80 Å diameter mesopore volume of said base-treated zeolitic material is at least 20 percent greater than the mesopore volume of said initial zeolitic material.

### Claim 50 (depends on 37)

The method of claim 37, wherein said initial zeolitic material comprises a faujasite.

### Claim 51 (depends on 37)

The method of claim 37, wherein said initial zeolitic material comprises a composite shaped article comprising a zeolite.