# US 2016/0257573 A1 · High surface area pentasil zeolite and process for making same

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- Number: US 2016/0257573 A1
- Document ID: US20160257573A1
- Status: Published application
- Kind: A1
- Application number: 14/636,898
- Filed: 2015-03-03
- Published: 2016-09-08
- Earliest claimed: 2015-03-03
- Assignees: Uop LLC
- Applicants: Uop LLC
- Inventors: Jaime G. Moscoso; Deng-Yang Jan
- Web page: https://patentgrep.com/patent/US20160257573A1

## CPC

- C01B 39/38: Type ZSM-5
- 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 29/90: Regeneration or reactivation
- B01J 35/45: Nanoparticles
- B01J 35/643: {less than 2 nm}
- B01J 35/647: {2-50 nm}
- B01J 35/70: characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00)
- C01B 39/36: Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- B01J 2229/186: not in framework positions
- B01J 2229/42: Addition of matrix or binder particles
- B01J 2235/15: X-ray diffraction
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- C01P 2006/12: Surface area
- C01P 2006/14: Pore volume
- Y02P 20/584: Recycling of catalysts
- 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A family of crystalline aluminosilicate zeolites has been synthesized that is a layered pentasil zeolite. These zeolites are represented by the empirical formula: Mmn+Rrp+ Al1-xExSiyOz where M is an alkali, alkaline earth, or rare earth metal such as sodium or strontium, R can be a mixture of organoammonium cations and E is a framework element such as gallium, iron, boron, or indium. These zeolites are characterized by unique x-ray diffraction patterns and compositions and have catalytic properties for carrying out various hydrocarbon conversion processes.

## Claims

### Claim 1

A pentasil-layered zeolite having a microporous crystalline structure comprising a framework of AlO2 and SiO2 tetrahedral units, and an empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of:
Mmn+Rrp+ AlSiyOz
where M is at least one exchangeable cation selected from the group consisting of alkali and alkaline earth metals, “m” is the mole ratio of M to Al and varies from 0 to 3, R is at least one organo cation selected from the group consisting of quaternary ammonium cations, diquaternary ammonium cations, quaternary phosphonium cations, and methonium cations, “r” is the mole ratio of R to Al and has a value of about 0.1 to about 30, “n” is the weight average valence of M and has a value of about 1 to about 2, “p” is the weighted average valence of R and has a value of about 1 to about 2, “y” is the mole ratio of Si to Al and varies from greater than 32 to about 200 and “z” is the mole ratio of O to Al and has a value determined by the equation:
z=(m·n+r·p+3+4·y)/2.

### Claim 2 (depends on 1)

The zeolite of claim 1 further characterized by the x-ray diffraction pattern having at least the d spacing and intensities set forth in the following Table A:
TABLE A
2Θ
d(Å)
I/Io
7.92-7.99
11.04-11.31
m
8.79-8.88
9.94-11.09
m
20.28-20.56
4.31-4.35
w
23.10-23.18
3.83-3.84
vs
23.86-24.05
3.69-3.72
m
29.90-30.05
2.97-2.98
w
45.02-45.17
2.00-2.01
w

### Claim 3 (depends on 1)

The zeolite of claim 1 wherein the zeolite has a microporous crystalline structure comprising a framework of AlO2 and SiO2 tetrahedral units, further including the element E and having the empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of:
Mmn+Rro+Al1-xExSiyOz
where “m” is the mole ratio of M to (Al+E) and varies from 0 to 3, “r” is the mole ratio of R to (Al+E) and has a value between 0.1 and 30, E is an element selected from the group consisting of gallium, iron, boron, indium and mixtures thereof, “x” is the mole fraction of E and has a value from 0 to 1.0, “y” is the mole ratio of Si to (Al+E) and varies from greater than 32 to 200 and “z” is the mole ratio of O to (Al+E) and has a value determined by the equation:
z=(m·n+r·p+3+4·y)/2.

### Claim 4 (depends on 1)

The zeolite of claim 1 wherein the zeolite has a mesopore surface area between 140 m2/g and 400 m2/g.

### Claim 5 (depends on 1)

The zeolite of claim 1 wherein M is selected from the group consisting of lithium, sodium, potassium, and mixtures thereof.

### Claim 6 (depends on 1)

The zeolite of claim 1 wherein M is a mixture of an alkali metal and an alkaline earth metal.

### Claim 7 (depends on 1)

The zeolite of claim 1 wherein R is selected from the group consisting of where R is selected from the group consisting of tetrabutylammonium hydroxide, tetrabutylphosphonium hydroxide, hexamethonium dihydroxide and mixtures thereof.

### Claim 8 (depends on 1)

The zeolite of claim 1 wherein R is a halide or hydroxide compound of an organoammonium cation.

### Claim 9 (depends on 1)

The zeolite of claim 1 wherein R is a mixture of tetrabutylammonium cation and a quaternary ammonium cation.

### Claim 10 (depends on 1)

The zeolite of claim 1 wherein the silica/alumina (Si/Al2) ratio is between 32 and 400.

### Claim 11

A process for the production of a pentasil-layered zeolite catalyst, comprising:
forming a reaction mixture comprising reactive compounds M, R, Al and Si; and
reacting the mixture at reaction conditions, wherein the reaction conditions include a temperature between 80° C. and 150° C., and a reaction time between 10 hours and 5 days, to form a microporous crystalline structure comprising a framework of AlO2 and SiO2 tetrahedral units, and an empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of:
Mmn+Rrp+ AlSiyOz;
wherein the reactive compounds include M, a cation selected from the group consisting of alkali and alkaline earth metals; R, an organoammonium cation selected from the group consisting of quaternary ammonium cations, diquaternary ammonium cations; and wherein “m” is the mole ratio of M to Al and varies from 0 to 3, “r” is the mole ratio of R to Al and has a value of between 0.1 and 30, “n” is the weight average valence of M and has a value of 1 to 2, “p” is the weighted average valence of R and has a value of 1 to 2, “y” is the mole ratio of Si to Al and varies from greater than 32 to 200 and “z” is the mole ratio of O to Al and has a value determined by the equation:
z=(m·n+r·p+3+4·y)/2.

### Claim 12 (depends on 11)

The process of claim 11 further comprising the addition of reactive source E, wherein E is an element selected from the group consisting of gallium, iron, boron, indium and mixtures thereof, to form a microporous crystalline structure comprising a framework of AlO2 and SiO2 tetrahedral units, and an empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of:
Mmn+Rrp+ Al1-xExSiyOz;
wherein m″ is the mole ratio of M to (Al+E) and varies from 0 to 1, “r” is the mole ratio of R to (Al+E) and has a value between 0.1 and 30, “n” is the weight average valence of M and has a value of 1 to 2, “p” is the weighted average valence of R and has a value of 1 to 2, “x” is the mole fraction of E and has a value from 0 to 1.0, “y” is the mole ratio of Si to (Al+E) and varies from greater than 32 to 200 and “z” is the mole ratio of O to (Al+E) and has a value determined by the equation:
z=(m·n+r·p+3+4·y)/2.

### Claim 13 (depends on 11)

The process of claim 11 where R is selected from the group consisting of tetrabutylammonium hydroxide, tetrabutylphosphonium hydroxide, hexamethonium dihydroxide and mixtures thereof.

### Claim 14 (depends on 11)

The process of claim 11 wherein R is a halide or hydroxide compound of an organoammonium cation.

### Claim 15 (depends on 11)

The process of claim 11 where R is a mixture of tetrabutylammonium hydroxide and a quaternary ammonium cation.

### Claim 16 (depends on 11)

The process of claim 11 where M is selected from the group consisting of sodium, potassium, and mixtures thereof.

### Claim 17 (depends on 11)

The process of claim 11 where the reaction mixture is reacted at a temperature between 100° C. and 125° C.

### Claim 18 (depends on 11)

The process of claim 11 where the reaction mixture is reacted at a temperature between 110° C. and 150° C.

### Claim 19

A process for the production of an MFI-layered zeolite catalyst having a 2-D structure, comprising:
forming a reaction mixture containing reactive sources of M, R, Al, and Si; and
reacting the reaction mixture at reaction conditions of 80° C. to 150° C. for a period of time of between 10 hours and 5 days the reaction mixture having the a composition expressed in terms of mole ratios of the oxides of:
aM2/nO:bR1 2/nO:cR2 2/n:Al2O3:eSiO2:hH2O;
wherein the reactive compounds include M, a cation selected from the group consisting of alkali, alkaline earth metals and mixtures thereof; R, an organoammonium cation selected from the group consisting of quaternary ammonium cations, diquaternary ammonium cations and mixtures thereof; Al in the form of Al2O3; and Si in the form of SiO2; and wherein “a” has a value of 0.1 to 3, “b” has a value of 1 to 30, “c” has a value of 0 to 1, “e” has a value of 64 to 400 and “h” has a value of 50 to 1000.

### Claim 20 (depends on 19)

The process of claim 19 further comprising:
forming the reaction mixture with reactive source E, wherein E is an element selected from the group consisting of gallium, iron, boron, indium and mixtures thereof; and
reacting the reaction mixture at reaction conditions of 85° C. to 225° C. for a period of time of 1 day to 15 days the reaction mixture having the a composition expressed in terms of mole ratios of the oxides of:
aM2/nO:bR1 2/nO:cR2 2/n:1-dAl2O3:dE2O3:eSiO2:hH2O;
wherein “a” has a value of 0.1 to 3, “b” has a value of 1 to 30, “c” has a value of 0 to 1, “d” has a value of 0 to 1, “e” has a value of 64 to 400 and “h” has a value of 50 to 1000.