# US 11,897,779 B2 · Microporous aluminotitanosilicate crystalline zeolite, method of preparation and applications thereof

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- Number: US 11,897,779 B2
- Document ID: US11897779B2
- Status: Granted
- Kind: B2
- Application number: 17/269,795
- Filed: 2019-08-06
- Published: 2021-10-28
- Granted: 2024-02-13
- Earliest claimed: 2018-08-24
- Assignees: East China Normal University; Rhodia Operations
- Applicants: Rhodia Operations; East China Normal University
- Inventors: Fangzheng Su; Stéphane Streiff; Laurent Garel; Peng Wu; Jianyong Yin; Xinqing Lu
- Web page: https://patentgrep.com/patent/US11897779B2

## CPC

- C01B 39/023: {Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48}
- 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 29/70: of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J 35/77: Compounds characterised by their crystallite size
- C01B 39/065: {Galloaluminosilicates; Group IVB- metalloaluminosilicates; Ferroaluminosilicates}
- B01J 2235/00: Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J 2235/15: X-ray diffraction
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- C01P 2006/14: Pore volume
- C01P 2006/16: Pore diameter
- 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

It relates to a microporous aluminotitanosilicate crystalline zeolite, method of preparation and applications thereof. It extends to a catalytic hydroxylation, by reaction of a compound of formula (I) with H2O2 in the presence of a catalyst comprising the zeolite.

## Claims

### Claim 1

A microporous aluminotitanosilicate crystalline zeolite having a three-dimensional framework of A1O2, SiO2 and TiO2 tetrahedral units and an empirical composition in the as synthesized and anhydrous basis expressed by an empirical formula of:
TipMmn+AlxSiOy
wherein:
p is the mole ratio of Ti to Si and has a value from 0.005 to about 0.1,
M represents a potassium ion and/or sodium ion, or their exchangeable cations,
m is the mole ratio of M to Si and varies from about 0.001 to about 0.05,
n is the valence of M,
x is the mole ratio of Al to Si and varies from 0.0025 to about 0.1; and
y has a value determined by the equation:
y=(4·p+m·n+3·x+4)/2
and is characterized in that it has the x-ray diffraction pattern having at least the intensities set forth in Table A:
TABLE A
2θ(Degree)
I/Io %
6.45-6.8
m
6.75-7.13
m-vs
7.86-8.26
m
8.64-9.04
m
9.51-10.09
m-vs
10.62-11.23
w-m
13.4-14.22
w-m
14.76-15.55
w
17.63-18.37
m
19.17-19.91
w-m
19.64-20.56
m
20.18-21.05
w-m
20.7-21.57
w-m
21.36-22.28
vs
22.17-23.6
m-s
22.7-23.8
w-m
24.12-25.23
w
25.6-26.94
m
26.37-27.79
m
27.02-28.42
m
27.53-28.89
m
28.7-30.09
m
29.18-30.72
w-m
30.19-31.73
m
30.83-32.2
w
32.81-34.22
w
35.63-36.99
w
41.03-42.86
w
44.18-45.83
w
44.87-46.57
w
46.07-47.35
w
48.97-50.42
w
wherein: the ratio of MSE framework characteristic peak intensity at a 2θ angle equal to 21.7 degree, to MFI framework characteristic peak intensity at a 2θ angle equal to 23.3 degree ranges from 80:1 to 1:1 in x-ray diffraction pattern.

### Claim 2 (depends on 1)

The zeolite according to claim 1, wherein p is from 0.008 to 0.1.

### Claim 3 (depends on 1)

The zeolite according to claim 1, wherein m is from 0.001 to 0.01.

### Claim 4 (depends on 1)

The zeolite according to claim 1, wherein x is from 0.0025 to 0.02.

### Claim 5 (depends on 1)

The zeolite according to claim 1, wherein y is from 2 to 3.

### Claim 6 (depends on 1)

The zeolite according to claim 1, wherein the zeolite has both MSE-type framework and MFI-type framework and the weight ratio of the crystalline zeolite existing in the form of MSE-type framework is in the range of 50% to 99% based on total weight of the zeolite and the weight ratio of the crystalline zeolite existing in the form of MFI-type framework is in the range of 1% to 50% based on total weight of the zeolite.

### Claim 7 (depends on 1)

A method for synthesizing a microporous aluminotitanosilicate crystalline zeolite according to claim 1, the method comprising at least the following steps:
(i) preparing a mixture comprising at least water and
an aluminum source,
an alkali source,
a structure directing agent,
a silicon source,
a crystalline aluminosilicate zeolite having a three-dimensional framework of AlO2 and SiO2 tetrahedral units and having an MSE framework type,
(ii) heating the reaction mixture at a temperature from 100° C. to 200° C., for a time sufficient to form a zeolite,
(iii) dealuminating of the zeolite with an acid,
(iv) optionally calcining the dealuminated zeolite at a temperature from 500 to 1000° C.,
(v) contacting the zeolite with a titanium source; and
(vi) calcining the zeolite at a temperature from 500 to 1000° C.

### Claim 8 (depends on 7)

The method according to claim 7, wherein the structure directing agent in step (i) is an organic compound having an organoammonium cation selected from the group consisting of dimethyldipropylammonium, choline, ethyltrimethylammonium(ETMA), diethyldimethylammonium(DEDMA), tetraethylammonium(TEA), tetrapropylammonium(TPA), trimethylpropylammonium, trimethylbutylammonium, dimethyldiethanolammonium and mixtures thereof.

### Claim 9 (depends on 7)

The method according to claim 7, wherein the structure directing agent in step (i) is hydroxide compound, chloride compound, bromide compound, iodide compound or fluoride compound.

### Claim 10 (depends on 7)

The method according to claim 7, wherein the structure directing agent in step (i) is selected from the group consisting of be dimethyldipropylammonium hydroxide, dimethyldipropylammonium chloride, dimethyldipropylammonium bromide, ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrapropylammonium chloride.

### Claim 11 (depends on 7)

The method according to claim 7, wherein the crystalline aluminosilicate zeolite having a three-dimensional framework of AlO2 and SiO2 tetrahedral units and having an MSE framework type in step (i) is MCM-68, YNU-2 or UZM-35.

### Claim 12 (depends on 7)

The method according to claim 7, wherein the weight ratio of silicon source to the crystalline aluminosilicate zeolite having a three-dimensional framework of AlO2 and SiO2 tetrahedral units and having an MSE framework type is in the range of 3:1 to 40:1.

### Claim 13 (depends on 7)

The method according to claim 7, wherein the alkali source comprises potassium hydroxide and/or potassium salts.

### Claim 14 (depends on 13)

The method according to claim 13, wherein the alkali source comprises potassium hydroxide and/or potassium salts, and sodium hydroxide and/or sodium salts; wherein the molar ratio of K+/Na+is in the range of 2 to 5.

### Claim 15 (depends on 7)

The method according to claim 7, wherein atomic Si/Al ratio is from 50 to 400 after step (iii).

### Claim 16 (depends on 7)

The method according to claim 7, wherein the titanium source is introduced in gas phase in step (v).

### Claim 17 (depends on 1)

A catalyst composition comprising a microporous aluminotitanosilicate crystalline zeolite according to claim 1.

### Claim 18 (depends on 17)

The catalyst composition according to claim 17, wherein the catalyst composition comprises 50 wt. % to 100 wt. % microporous aluminotitanosilicate crystalline zeolite based on total weight of the catalyst.

### Claim 19 (depends on 1)

A catalytic hydroxylation reaction, comprising reacting a compound of formula (I) with H2O2 in the presence of a catalyst comprising a microporous aluminotitanosilicalite crystalline zeolite according to claim 1,
wherein:
n is a number from 0 to 4;
R1, which are identical or different, represent an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a haloalkyl group or a perhaloalkyl group;
R2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.

### Claim 20 (depends on 19)

The catalytic hydroxylation reaction according to claim 19, wherein the compound of formula (I) is selected from the group consisting of phenol, m-cresol, o-cresol, 2-methoxyphenol, 2-ethoxyphenol, anisole and phenetol; or wherein the ortho/para molar ratio is lower or equal to 1.