# US 8,486,369 B2 · Introduction of mesoporosity in low Si/Al zeolites

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- Number: US 8,486,369 B2
- Document ID: US8486369B2
- Status: Granted
- Kind: B2
- Application number: 12/689,127
- Filed: 2010-01-18
- Published: 2010-08-05
- Granted: 2013-07-16
- Earliest claimed: 2009-01-19
- Assignees: Rive Technology, Inc.
- Applicants: Javier Garcia-Martinez; Marvin M. Johnson; Ioulia Valla
- Inventors: Javier Garcia-Martinez; Marvin M. Johnson; Ioulia Valla
- Web page: https://patentgrep.com/patent/US8486369B2

## CPC

- C01B 39/026: {After-treatment}
- B01J 29/084: {Y-type faujasite}
- 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 materials from low Si/Al ratio zeolites. Such compositions can be prepared by acid wash and/or isomorphic substitution pretreatment of low Si/Al ratio zeolites prior to introduction of mesoporosity.

## Claims

### Claim 1

A method of forming a material comprising at least one mesoporous zeolite, said method comprising the steps of:
(a) acid washing a non-mesoporous initial zeolite with an acidic medium thereby forming an acid-washed zeolite, wherein said initial zeolite has a total silicon-to-aluminum ratio (Si/Al) of less than 30, wherein said initial zeolite has an extra-framework aluminum content from 25-100%, wherein said acid washing of step (a) removes aluminum atoms from said initial zeolite such that said acid-washed zeolite has a higher Si/Al ratio than said initial zeolite; and
(b) subsequent to step (a), contacting said acid-washed zeolite with a mesopore-forming medium different than said acidic medium, thereby forming at least one mesopore within said acid washed zeolite and providing said mesoporous zeolite.

### Claim 2 (depends on 1)

The method of claim 1, wherein said initial zeolite has an average unit cell size of at least 24.40 Å.

### Claim 3 (depends on 1)

The method of claim 1, wherein said acid-washed zeolite has an average unit cell size of at least 24.30 Å.

### Claim 4 (depends on 1)

The method of claim 1, wherein said initial zeolite is not steamed prior to said acid washing.

### Claim 5 (depends on 1)

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

### Claim 6 (depends on 1)

The method of claim 1, wherein said acid-washed zeolite has a greater number of Si—OH and/or Al—OH terminal groups than said initial zeolite.

### Claim 7 (depends on 1)

The method of claim 1, wherein said mesoporous zeolite is a one-phase hybrid single crystal having long range crystallinity.

### Claim 8 (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 9 (depends on 1)

The method of claim 1, wherein said mesoporous zeolite has a total 1 to 20 Å diameter micropore volume of less than 3.0 cc/g.

### Claim 10 (depends on 1)

The method of claim 1, wherein said initial zeolite has a total 1 to 20 Å diameter micropore volume of at least 0.3 cc/g.

### Claim 11 (depends on 1)

The method of claim 1, wherein said acid washing is performed at a temperature of not more than 100° C., wherein said acid washing is performed for a time period of not more than 12 hours, wherein said acidic medium has a pH in the range of from about 1 to about 6.

### Claim 12 (depends on 1)

The method of claim 1, wherein said acidic medium comprises an acid selected from the group consisting of hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, acetic acid, sulfonic acid, oxalic acid, citric acid, EDTA, and mixtures of two or more thereof.

### Claim 13 (depends on 1)

The method of claim 1, wherein said acidic medium comprises a chelating agent.

### Claim 14 (depends on 1)

The method of claim 1, wherein said acidic medium comprises an acid that is present in an amount in the range of from about 1 to about 10 milliequivalents per gram of initial zeolite.

### Claim 15 (depends on 1)

The method of claim 1, wherein said initial zeolite is a Y zeolite.

### Claim 16 (depends on 1)

The method of claim 1, wherein said formation of at least one mesopore within said acid-washed zeolite is accomplished by contacting said acid-washed zeolite with at least one pH controlling medium and at least one surfactant thereby forming said mesoporous zeolite.

### Claim 17 (depends on 16)

The method of claim 16, wherein said acid-washed zeolite is not dried prior to said contacting with said pH controlling medium and said surfactant.

### Claim 18 (depends on 1)

The method of claim 1, wherein said acidic medium is in liquid form during said acid-washing.

### Claim 19 (depends on 1)

The method of claim 1, wherein said forming of step (b) comprises contacting said acid-washed zeolite with a medium comprising at least one base.

### Claim 20 (depends on 19)

The method of claim 19, wherein said medium further comprises at least one surfactant.

### Claim 21 (depends on 1)

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

### Claim 22 (depends on 1)

The method of claim 1, further comprising blending said mesoporous zeolite with a binder, a matrix, and/or an additive to thereby form a blended material.

### Claim 23 (depends on 22)

The method of claim 22, further comprising shaping said blended material into a shaped material.

### Claim 24 (depends on 23)

The method of claim 23, wherein said shaped material is a catalyst.

### Claim 25 (depends on 24)

The method of claim 24, wherein said catalyst is a fluid catalytic cracking (FCC) catalyst.

### Claim 26

A method of forming a material comprising at least one mesoporous zeolite, said method comprising the steps of:
(a) acid washing a non-mesoporous initial zeolite with an acidic medium thereby forming an acid-washed zeolite, wherein said initial zeolite has an average unit size of at least 24.40 Å, wherein said initial zeolite has an extra-framework aluminum content from 25-100%, wherein said acid washing of step (a) removes aluminum atoms from said initial zeolite such that said acid-washed zeolite has a higher Si/Al ratio than said initial zeolite; and
(b) subsequent to step (a), forming at least one mesopore within said acid washed zeolite and providing said mesoporous zeolite.

### Claim 27 (depends on 26)

The method of claim 26, wherein said initial zeolite is not steamed prior to said acid washing.

### Claim 28 (depends on 26)

The method of claim 26, wherein said acid-washed zeolite has fewer Si—O—Al bonds in its zeolite framework than said initial zeolite, wherein said acid-washed zeolite has a greater number of Si—OH and/or Al—OH terminal groups than said initial zeolite.

### Claim 29 (depends on 26)

The method of claim 26, wherein said mesoporous zeolite is a one-phase hybrid single crystal having long range crystallinity, wherein said mesoporous zeolite has a total 20 to 80 Å diameter mesopore volume of at least 0.05 cc/g, wherein said mesoporous zeolite has a total 1 to 20 Å diameter micropore volume of less than 3.0 cc/g.

### Claim 30 (depends on 26)

The method of claim 26, wherein said formation of at least one mesopore within said acid-washed zeolite is accomplished by contacting said acid-washed zeolite with at least one pH controlling medium and at least one surfactant thereby forming said mesoporous zeolite, wherein said acid-washed zeolite is not dried prior to said contacting with said pH controlling medium and said surfactant.

### Claim 31 (depends on 26)

The method of claim 26, wherein said acidic medium is in liquid form during said acid-washing.

### Claim 32 (depends on 26)

The method of claim 26, wherein said forming of step (b) comprises contacting said acid-washed zeolite with a medium comprising at least one base.

### Claim 33 (depends on 32)

The method of claim 32, wherein said medium further comprises at least one surfactant.

### Claim 34 (depends on 26)

The method of claim 26, wherein said mesoporous zeolite comprises a mesostructured zeolite.

### Claim 35 (depends on 26)

The method of claim 26, wherein said acid washing of step (a) is performed at a temperature of not more than 100° C. and for a time period of not more than 12 hours.

### Claim 36

A method of forming a material comprising at least one mesoporous zeolite, said method comprising the steps of:
(a) acid washing a non-mesoporous initial zeolite having a low silicon-to-aluminum ratio with an acidic medium thereby forming an acid-washed zeolite, wherein said acid washing is carried out at a temperature of not more than 100° C. and for a time period of not more than 12 hours, wherein said initial zeolite has an extra-framework aluminum content from 25-100%, wherein said acid washing of step (a) removes aluminum atoms from said initial zeolite such that said acid-washed zeolite has a higher Si/Al ratio than said initial zeolite; and
(b) subsequent to step (a), forming at least one mesopore within said acid-washed zeolite thereby forming said mesoporous zeolite, wherein said mesoporous zeolite has an increased mesoporosity and a decreased microporosity relative to said acid treated zeolite.

### Claim 37 (depends on 36)

The method of claim 36, wherein said acid-washed zeolite has fewer Si—O—Al bonds in its zeolite framework than said initial zeolite, wherein said acid-washed zeolite has a greater number of Si—OH and/or Al—OH terminal groups than said initial zeolite.

### Claim 38 (depends on 36)

The method of claim 36, wherein said acidic medium comprises an acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, sulfonic acid, oxalic acid, citric acid, EDTA, and mixtures of two or more thereof.

### Claim 39 (depends on 36)

The method of claim 36, wherein said acidic medium comprises a chelating agent.

### Claim 40 (depends on 36)

The method of claim 36, wherein said initial zeolite is a Y zeolite.

### Claim 41 (depends on 36)

The method of claim 36, wherein said mesoporous zeolite is a one-phase hybrid single crystal having long range crystallinity.

### Claim 42 (depends on 36)

The method of claim 36, wherein said formation of at least one mesopore within said acid-washed zeolite is accomplished by contacting said acid-washed zeolite with at least one pH controlling medium and at least one surfactant thereby forming said mesoporous zeolite.

### Claim 43 (depends on 36)

The method of claim 36, wherein said acidic medium is in liquid form during said acid washing.

### Claim 44 (depends on 36)

The method of claim 36, wherein said forming of step (b) comprises contacting said acid-washed zeolite with a medium comprising at least one base.

### Claim 45 (depends on 44)

The method of claim 44, wherein said medium further comprises at least one surfactant.

### Claim 46 (depends on 36)

The method of claim 36, wherein said mesoporous zeolite comprises a mesostructured zeolite.

### Claim 47

A method of forming a material comprising at least one mesoporous zeolite, said method comprising the steps of:
(a) contacting a non-mesoporous initial zeolite with an acidic medium at a temperature of not more than 100° C. and for a time period of not more than 12 hours to thereby form an acid-treated zeolite having reduced crystallinity relative to said initial zeolite, wherein said initial zeolite has an extra-framework aluminum content from 25-100%, wherein said acid washing of step (a) removes aluminum atoms from said initial zeolite such that said acid-washed zeolite has a higher Si/Al ratio than said initial zeolite; and
(b) subsequent to step (a), contacting said acid-treated zeolite with a basic medium to thereby form said mesoporous zeolite.

### Claim 48 (depends on 47)

The method of claim 47, wherein said acidic medium has a pH in the range of 1 to 6.

### Claim 49 (depends on 47)

The method of claim 47, wherein said basic medium has a pH in the range of 9 to 11.

### Claim 50 (depends on 47)

The method of claim 47, wherein the total pore volume of said mesoporous zeolite is greater that the total pore volume of said acid-treated zeolite.

### Claim 51 (depends on 47)

The method of claim 47, further comprising, prior to said contacting of step (b), drying said acid-treated zeolite at a drying temperature greater than 20° C. for a drying time greater than 1 hour.

### Claim 52 (depends on 51)

The method of claim 51, wherein said drying time is less than 24 hours.

### Claim 53 (depends on 47)

The method of claim 47, wherein said acidic medium comprises an acid selected from the group consisting of chlorhidric acid, sulphuric acid, nitric acid, acetic acid, sulfonic acid, oxalic acid, ethylenediaminetetraacetic acid (EDTA), and citric acid.

### Claim 54 (depends on 47)

The method of claim 47, wherein said acidic medium comprises a chelating agent.

### Claim 55 (depends on 54)

The method of claim 54, wherein said chelating agent is selected from the group consisting of oxalic acid, citric acid, and ethylenediaminetetraacetic acid (EDTA).

### Claim 56 (depends on 54)

The method of claim 54, wherein said basic medium comprises said chelating agent.

### Claim 57 (depends on 47)

The method of claim 47, wherein said basic medium comprises a pore forming agent.

### Claim 58 (depends on 57)

The method of claim 57, wherein said pore forming agent comprises a surfactant.

### Claim 59 (depends on 47)

The method of claim 47, further comprising realuminating said mesoporous zeolite to thereby lower the Si/Al ratio of said mesoporous zeolite.

### Claim 60 (depends on 47)

The method of claim 47, wherein said material is a catalyst composition.

### Claim 61 (depends on 60)

The method of claim 60, wherein said catalyst composition is a cracking catalyst.

### Claim 62 (depends on 61)

The method of claim 61, wherein said cracking catalyst is a fluid catalytic cracking (FCC) catalyst.

### Claim 63 (depends on 60)

The method of claim 60, wherein said catalyst composition further comprises a binder and a metal.

### Claim 64 (depends on 63)

The method of claim 63, wherein said metal is a rare earth metal.

### Claim 65 (depends on 47)

The method of claim 47, wherein said mesoporous zeolite is a mesostructured zeolite.

### Claim 66 (depends on 65)

The method of claim 65, wherein said mesostructured zeolite comprises a one-phase hybrid single crystal having long-range crystallinity.

### Claim 67 (depends on 47)

The method of claim 47, wherein said acid-treated zeolite is non-mesoporous.

### Claim 68 (depends on 47)

The method of claim 47, wherein said initial zeolite has a total 20 to 80 Å diameter mesopore volume of less than 0.05 cc/g and said mesoporous zeolite has a total 20 to 80 Å diameter mesopore volume of at least 0.1 cc/g.

### Claim 69 (depends on 47)

The method of claim 47, wherein said initial zeolite has a total 20 to 80 Å diameter mesopore volume of less than 0.01 cc/g and said mesoporous zeolite has a total 20 to 80 Å diameter mesopore volume of at least 0.2 cc/g.

### Claim 70 (depends on 47)

The method of claim 47, wherein the total 1 to 20 Å diameter micropore volume of said mesoporous zeolite is less than the total 1 to 20 Å diameter micropore volume of said acid-treated zeolite.

### Claim 71 (depends on 47)

The method of claim 47, wherein said acidic medium comprises an acid in an amount in the range of from about 1 to about 10 milliequivalents per grain of initial zeolite.

### Claim 72 (depends on 47)

The method of claim 47, wherein said acid-treated zeolite has at least 1 percent fewer Si—O—Al bonds that said initial zeolite.

### Claim 73 (depends on 47)

The method of claim 47, wherein said initial zeolite has an average unit cell size of at least 24.45 Å and said acid-treated zeolite has an average unit cell size of at least 24.35 Å.

### Claim 74 (depends on 47)

The method of claim 47, further comprising, prior to said contacting of step (b), drying said acid-treated zeolite at a drying temperature in the range of 50 to 120° C. for a drying time in the range of 15 minutes to 2 hours.

### Claim 75 (depends on 74)

The method of claim 74, wherein said drying temperature is in the range of 70 to 90° C. and said drying time is in the range of 30 minutes to 2 hours.

### Claim 76 (depends on 47)

The method of claim 47, further comprising heat treating said mesoporous zeolite at a temperature in the range of 500 to 600° C. for a time in the range of 1 to 12 hours.