# US 10,118,152 B2 · Zeolite material based on mesoporous zeolite

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- Number: US 10,118,152 B2
- Document ID: US10118152B2
- Status: Granted
- Kind: B2
- Application number: 14/914,220
- Filed: 2014-08-06
- Published: 2016-07-21
- Granted: 2018-11-06
- Earliest claimed: 2013-09-02
- Assignees: Arkema France
- Applicants: Arkema France
- Inventors: Ludivine Bouvier; Cecile Lutz; Serge Nicolas
- Web page: https://patentgrep.com/patent/US10118152B2

## CPC

- B01J 20/18: Synthetic zeolitic molecular sieves
- B01J 20/12: Naturally occurring clays or bleaching earth
- B01J 20/186: {Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity}
- B01J 20/28004: {Sorbent size or size distribution, e.g. particle size}
- B01J 20/28011: {Other properties, e.g. density, crush strength}
- B01J 20/28083: {being in the range 2-50 nm, i.e. mesopores}
- B01J 20/3028: {Granulating, agglomerating or aggregating}
- B01J 20/3042: {Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent}
- B01J 20/3078: {Thermal treatment, e.g. calcining or pyrolizing}
- B01J 20/3085: {Chemical treatments not covered by groups B01J20/3007 - B01J20/3078}
- B01J 29/041: {Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41}
- B01J 29/084: {Y-type faujasite}
- B01J 35/37: Crush or impact strength
- B01J 35/40: characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77)
- B01J 35/633: {less than 0.5 ml/g}
- B01J 35/643: {less than 2 nm}
- B01J 35/647: {2-50 nm}
- B01J 37/0009: {Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst}
- B01J 37/06: Washing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- C01B 39/026: {After-treatment}
- C01B 39/24: Type Y {(C01B39/205 takes precedence)}
- B01J 29/005: {Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89}
- B01J 2229/42: Addition of matrix or binder particles
- B01J 2235/15: X-ray diffraction
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}

## Abstract

The present invention relates to zeolite materials in the form of agglomerates comprising at least one mesoporous Faujasite zeolite with an Si/Al ratio which is strictly greater than 1.4 and having both the characteristics of mesoporous zeolites, the properties associated with microporosity and the mechanical properties of zeolite agglomerates without mesoporous zeolite. The invention also relates to the process for preparing the said zeolite materials in the form of agglomerates.

## Claims

### Claim 1

An agglomerated zeolite material comprising at least one mesoporous zeolite, wherein:
(1) the mesoporous zeolite has an Si/Al atomic ratio of greater than 1.4 and less than or equal to 6,
(2) the agglomerated zeolite material has a total zeolite content of at least 30% by weight relative to the total weight of the agglomerated zeolite material,
(3) the agglomerated zeolite material has a content of mesoporous zeolite of greater than or equal to 30% by weight relative to the total weight of the agglomerated zeolite material,
(4) the agglomerated zeolite material has a binder content, after calcinations performed at 950° C. for 1 hour, of less than or equal to 70% by weight relative to the total weight of the agglomerated zeolite material,
(5) the agglomerated zeolite material has a mean volume diameter (D50), or a length (largest dimension when the agglomerated zeolite material is not spherical) of less than 7 mm, and
either
(a) the agglomerated zeolite material has a bulk crushing strength (BCS) measured according to standard ASTM 7084-04 of between 0.5 MPa and 6 MPa for an agglomerated zeolite material with a mean volume diameter (D50), or a length (largest dimension when the agglomerated zeolite material is not spherical), of less than 1 mm, limits inclusive, or
(b) the agglomerated zeolite material has a grain crushing strength, measured according to standards ASTM D 4179 (2011) and ASTM D 6175 (2013), of 0.5 daN to 30 daN for an agglomerated zeolite material with a mean volume diameter (D50), or a length (largest dimension when the agglomerated zeolite material is not spherical), of greater than or equal to 1 mm, limits inclusive,
wherein the mesoporous zeolite has a mesoporous outer surface area of between 40 m2·g−1 and 400 m2·g−1 as defined by the t-plot method.

### Claim 2 (depends on 1)

The agglomerated zeolite material of claim 1, further comprising one or more non-mesoporous zeolites.

### Claim 3 (depends on 1)

The agglomerated zeolite material of claim 1, which has an apparent mass per unit volume of 0.4 g·cm−3 to 1 g·cm−3.

### Claim 4 (depends on 1)

The agglomerated zeolite material of claim 1, wherein the mesoporous zeolite has an Si/Al atomic ratio of 1.5 to 5.

### Claim 5 (depends on 1)

The agglomerated zeolite material of claim 1, in which the zeolite crystals are agglomerated with a binder comprising a clay or a mixture of clays selected from the group consisting of kaolins, kaolinites, nacrites, dickites, halloysites, attapulgites, sepiolites, montmorillonites, bentonites, illites, metakaolins, mixtures thereof, and the silica or alumina sols thereof.

### Claim 6 (depends on 1)

The agglomerated zeolite material of claim 1, which has both the characteristics of mesoporous zeolites, but also the mechanical properties of conventional zeolite agglomerates in which the zeolite is non-mesoporous.

### Claim 7 (depends on 1)

The agglomerated zeolite material of claim 1, wherein the total zeolite content is at least 70% by weight relative to the total weight of the agglomerated zeolite material.

### Claim 8 (depends on 1)

The agglomerated zeolite material of claim 1, wherein the content of mesoporous zeolite is greater than or equal to 90% relative to the total weight of the agglomerated zeolite material.

### Claim 9 (depends on 1)

The agglomerated zeolite material of claim 1, wherein the binder content, after calcinations performed at 950° C. for 1 hour, is less than or equal to 30% relative to the total weight of the agglomerated zeolite material.

### Claim 10 (depends on 1)

The agglomerated zeolite material of claim 1, wherein the mean volume diameter (D50), or a length (largest dimension when the agglomerated zeolite material is not spherical), is 1 mm to 2.5 mm.

### Claim 11 (depends on 1)

The agglomerated zeolite material of claim 1, the mesoporous zeolite has an Si/Al atomic ratio of 1.5 to 3.

### Claim 12 (depends on 1)

The agglomerated zeolite material of claim 1, wherein the mesoporous zeolite is a Y-type FAU zeolite.

### Claim 13 (depends on 1)

The agglomerated zeolite material of claim 1, wherein the mesoporous zeolite is in the form of crystals having a mean numerical diameter of less than 20 μm as measured with a scanning electron microscope.

### Claim 14 (depends on 1)

The agglomerated zeolite material of claim 1, which has a grain crushing strength, measured according to standards ASTM D 4179 (2011) and ASTM D 6175 (2013), of between 1 daN and 20 daN.

### Claim 15 (depends on 1)

The agglomerated zeolite material of claim 1, wherein the binder content, after calcinations performed at 950° C. for 1 hour, is less than or equal to 60% relative to the total weight of the agglomerated zeolite material.

### Claim 16 (depends on 1)

The agglomerated zeolite material of claim 1, wherein the mesoporous zeolite has an Si/Al atomic ratio of greater than 1.4 to 3.

### Claim 17 (depends on 1)

The agglomerated zeolite material of claim 1, wherein (a) the agglomerated zeolite material has a mean volume diameter (D50), or a length (largest dimension when the agglomerated zeolite material is not spherical) of 1 mm to 7 mm.

### Claim 18 (depends on 1)

The agglomerated zeolite material of claim 1, wherein the mesoporous zeolite has a mesoporous outer surface area of between 60 m2·g−1 and 200 m2·g−1 as defined by the t-plot method.

### Claim 19 (depends on 1)

The agglomerated zeolite material of claim 1, which (a) has a bulk crushing strength (BCS) measured according to standard ASTM 7084-04 of between 0.5 MPa and 6 MPa for an agglomerated zeolite material with a mean volume diameter (D50), or a length (largest dimension when the agglomerated zeolite material is not spherical), of less than 1 mm, limits inclusive.

### Claim 20 (depends on 1)

The agglomerated zeolite material of claim 1, which (b) has a grain crushing strength, measured according to standards ASTM D 4179 (2011) and ASTM D 6175 (2013), of 0.5 daN to 30 daN for an agglomerated zeolite material with a mean volume diameter (D50), or a length (largest dimension when the agglomerated zeolite material is not spherical), of greater than or equal to 1 mm, limits inclusive.

### Claim 21 (depends on 1)

A process for preparing the agglomerated zeolite material of claim 1, comprising:
a) forming an agglomerated material by agglomerating crystals of at least one mesoporous zeolite with an Si/Al atomic ratio which is greater than 1.4 and less than or equal to 6, with a number-average diameter of 0.1 μm to 20 μm and with a mesopore outer surface area of 40 m2·g−1 to 400 m2·g−1, with a binder comprising at least 80% clay or a mixture of clays and/or of the silica or alumina sols which are then dried or gelled in order to make them set, the clay or clays being optionally zeolitizable, and with up to 5% of additives, and optionally at least one non-mesoporous zeolite, and with an amount of water that allows the shaping of the agglomerated material;
b) drying the agglomerated material from a) at a temperature of between 50° C. and 150° C. to obtain dried agglomerates;
c) calcining the dried agglomerates from b) with flushing with an oxidizing and/or inert gas, which is optionally dried and/or decarbonated, at a temperature above 150° C.;
d) optionally zeolitizing the binder by placing the calcined agglomerates obtained in c) in contact with an alkaline basic solution;
e) optionally cation exchanging the agglomerates from c) or d) by placing the agglomerates in contact with a solution of at least one alkali metal or alkaline-earth metal salt;
f) washing and drying the agglomerates obtained in d) or e) at a temperature of between 50° C. and 150° C., and
g) producing the agglomerated zeolite material by activating the agglomerates obtained in f) under the conditions described in c).

### Claim 22 (depends on 21)

The process of claim 21, wherein, in a), agglomeration of crystals of a zeolite prepared in the presence of a sacrificial template is performed.

### Claim 23 (depends on 22)

The process of claim 22, wherein the sacrificial template is selected from the group consisting of organosilane compounds and oligomers.

### Claim 24 (depends on 23)

The process of claim 23, wherein removal of the sacrificial template is performed by calcination of the zeolite crystals before the agglomeration a), or concomitantly with c).