# US 7,744,850 B2 · UZM-22 aluminosilicate zeolite, method of preparation and processes using UZM-22

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- Number: US 7,744,850 B2
- Document ID: US7744850B2
- Status: Granted
- Kind: B2
- Application number: 11/462,056
- Filed: 2006-08-03
- Published: 2008-02-07
- Granted: 2010-06-29
- Earliest claimed: 2006-08-03
- Assignees: Uop LLC
- Inventors: Mark A. Miller; Jaime G. Moscoso; Gregory J. Lewis
- Web page: https://patentgrep.com/patent/US7744850B2

## CPC

- B01J 29/70: of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- C01B 39/48: using at least one organic template directing agent
- C07C 2/58: Catalytic processes
- C07C 2/66: Catalytic processes
- C10G 29/205: {by reaction with hydrocarbons added to the hydrocarbon oil}
- C10G 45/64: containing crystalline alumino-silicates, e.g. molecular sieves
- C10G 50/00: Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- C07C 2529/70: of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- 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}
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES

## Abstract

A new family of crystalline aluminosilicate zeolites has been synthesized. These zeolites are represented by the empirical formula. Mmn+Rr+Al(1-x)ExSiyOz where M is an alkali, alkaline earth, or rare earth metal such as lithium and strontium, R is a singly charged organoammonium cation such as the choline cation and E is a framework element such as gallium. These zeolites are similar to ZSM-18 but 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 microporous crystalline zeolite having a three-dimensional framework of at least AlO2 and SiO2 tetrahedral units and an empirical composition in the as synthesized and anhydrous basis expressed by an empirical formula of:
Mmn+RrAl1-xExSiyOz
where M is at least one exchangeable cation selected from the group consisting of alkali, alkaline earth, and rare earth metals, “m” is the mole ratio of M to (Al+E) and varies from 0 to about 1.2, R is a singly charged organoammonium cation selected from the group of choline, ethyltrimethylammonium (ETMA), diethyldimethyl ammonium (DEDMA), tetraethyl ammonium (TEA), tetrapropylammonium (TPA), trimethylpropylammonium, trimethylbutylammonium, dimethyldiethanolammonium, and mixtures thereof, “r” is the mole ratio of R to (Al+E) and has a value of about 0.25 to about 2.0, “n” is the weighted average valence of M and has a value of about 1 to about 3, E is an element selected from the group consisting of gallium, iron, boron and mixtures thereof, “x” is the mole fraction of E and has a value from 0 to about 1.0, “y” is the mole ratio of Si to (Al+E) and varies from greater than 2 to about 12 and “z” is the mole ratio of O to (Al+E) and has a value determined by the equation:
z=(m·n+r+3+4·y)/2
and is characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table A:
TABLE A
2θ
d(Å)
I/I0 %
7.53-7.89
11.73-11.20
vs
9.35-9.71
9.45-9.10
w
11.01-11.37
8.03-7.78
m
13.22-13.53
6.69-6.54
w-m
13.41-13.77
6.60-6.43
w-m
15.35-15.63
5.77-5.66
w
17.28-17.68
5.13-5.01
w-m
18.32-18.72
4.84-4.74
w-m
18.89-19.33
4.69-4.59
m
20.33-20.69
4.36-4.29
w-m
21.07-21.51
4.21-4.13
s-vs
21.34-21.74
4.16-4.08
s-vs
22.24-22.67
3.99-3.92
w-m
22.71-23.15
3.91-3.84
w-m
23.21-23.65
3.83-3.76
m
25.58-26.19
3.48-3.40
w
26.38-26.89
3.38-3.31
m
26.73-27.17
3.33-3.28
w-m
27.41-27.77
3.25-3.21
w-m
28.49-28.85
3.13-3.09
m
29.10-29.47
3.07-3.03
m
30.09-30.51
2.97-2.93
w
30.42-30.82
2.94-2.90
w
31.06-31.54
2.88-2.83
w-m
32.15-32.54
2.78-2.75
w
32.31-32.82
2.77-2.73
w
32.69-33.13
2.74-2.70
w
32.98-33.49
2.71-2.67
w
33.80-34.36
2.65-2.61
w
34.82-35.35
2.57-2.54
w
35.73-36.17
2.51-2.48
w-m
37.91-38.56
2.37-2.33
w
and is thermally stable up to a temperature of at least 400° C.

### Claim 2 (depends on 1)

The zeolite of claim 1 where M is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, calcium, strontium, barium and mixtures thereof.

### Claim 3 (depends on 1)

The zeolite of claim 1 where “x” is zero.

### Claim 4 (depends on 1)

The zeolite of claim 1 where the zeolite is thermally stable up to a temperature of at least 600° C.

### Claim 5 (depends on 1)

The zeolite of claim 1 where R is choline.

### Claim 6 (depends on 1)

The zeolite of claim 1 where R is choline and M is selected from the group consisting of Li, Sr and mixtures thereof.

### Claim 7

A process for preparing a microporous crystalline zeolite having a three-dimensional framework of at least AlO2 and SiO2 tetrahedral units and an empirical composition in the as synthesized and anhydrous basis expressed by an empirical formula of:
Mmn+RrAl1-xExSiyOz
where M is at least one exchangeable cation selected from the group consisting of alkali, alkaline earth, and rare earth metals, “m” is the mole ratio of M to (Al+E) and varies from 0 to about 1.2, R is a singly charged organoammonium cation selected from the group choline, ethyltrimethylammonium (ETMA), diethyldimethyl ammonium (DEDMA), tetraethyl ammonium (TEA), tetrapropylammonium (TPA), trimethylpropylammonium, trimethylbutylammonium, dimethyldiethanolammonium cations and mixtures thereof “r” is the mole ratio of R to (Al+E) and has a value of about 0.25 to about 2.0, “n” is the weighted average valence of M and has a value of about 1 to about 3, E is an element selected from the group consisting of gallium, iron, boron and mixtures thereof, “x” is the mole fraction of E and has a value from 0 to about 1.0, “y” is the mole ratio of Si to (Al+E) and varies from greater than 2 to about 12 and “z” is the mole ratio of O to (Al+E) and has a value determined by the equation:
z=(m·n+r+3+4·y)/2
and is characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table A:
TABLE A
2θ
d (Å)
I/Io %
7.53-7.89
11.73-11.20
vs
9.35-9.71
9.45-9.10
w
11.01-11.37
8.03-7.78
m
13.22-13.53
6.69-6.54
w-m
13.41-13.77
6.60-6.43
w-m
15.35-15.63
5.77-5.66
w
17.28-17.68
5.13-5.01
w-m
18.32-18.72
4.84-4.74
w-m
18.89-19.33
4.69-4.59
m
20.33-20.69
4.36-4.29
w-m
21.07-21.51
4.21-4.13
s-vs
21.34-21.74
4.16-4.08
s-vs
22.24-22.67
3.99-3.92
w-m
22.71-23.15
3.91-3.84
w-m
23.21-23.65
3.83-3.76
m
25.58-26.19
3.48-3.40
w
26.38-26.89
3.38-3.31
m
26.73-27.17
3.33-3.28
w-m
27.41-27.77
3.25-3.21
w-m
28.49-28.85
3.13-3.09
m
29.10-29.47
3.07-3.03
m
30.09-30.51
2.97-2.93
w
30.42-30.82
2.94-2.90
w
31.06-31.54
2.88-2.83
w-m
32.15-32.54
2.78-2.75
w
32.31-32.82
2.77-2.73
w
32.69-33.13
2.74-2.70
w
32.98-33.49
2.71-2.67
w
33.80-34.36
2.65-2.61
w
34.82-35.35
2.57-2.54
w
35.73-36.17
2.51-2.48
w-m
37.91-38.56
2.37-2.33
w
and is thermally stable up to a temperature of at least 400° C.; the process comprising forming a reaction mixture containing reactive sources of M, R, Al, Si and optionally E and heating the reaction mixture at a temperature of about 60° C. to about 175° C., for a time sufficient to form the zeolite, the reaction mixture having a composition expressed in terms of mole ratios of the oxides of:
aM2/nO:bR2/pO:1−cAl2O3:cE2O3:dSiO2:eH2O
where “a” has a value of about 0.05 to about 1.25, “b” has a value of about 1.5 to about 40, “c” has a value of 0 to about 1.0, “d” has a value of about 4 to about 40, “e” has a value of about 25 to about 4000.

### Claim 8 (depends on 7)

The process of claim 7 where M is selected from the group consisting of lithium, cesium, sodium, potassium, rubidium, strontium, barium and mixtures thereof.

### Claim 9 (depends on 7)

The process of claim 7 where the source of M is selected from the group consisting of halide salts, nitrate salts, acetate salts, hydroxides, sulfate salts and mixtures thereof.

### Claim 10 (depends on 7)

The process of claim 7 where the source of E is selected from the group consisting of alkali borates, boric acid, precipitated gallium oxyhydroxide, gallium sulfate, ferric sulfate, ferric chloride and mixtures thereof.

### Claim 11 (depends on 7)

The process of claim 7 where the aluminum source is selected from the group consisting of aluminum isopropoxide, aluminum sec-butoxide, precipitated alumina, Al(OH)3, aluminum metal and aluminum salts.

### Claim 12 (depends on 7)

The process of claim 7 where the silicon source is selected from the group consisting of tetraethylorthosilicate, fumed silica, colloidal silica and precipitated silica.

### Claim 13 (depends on 7)

The process of claim 7 where the reaction mixture is reacted at a temperature of about 80° C. to about 125° C. for a time of about 1 day to about 3 weeks.

### Claim 14 (depends on 7)

The process of claim 7 where R is choline.

### Claim 15 (depends on 7)

The process of claim 7 where R is choline and M is selected from the group consisting of Li, Sr and mixtures thereof.

### Claim 16 (depends on 7)

The process of claim 7 where R is a combination of choline and at least one singly charged organoammonium cation selected from the group consisting of TEA, TPA, ETMA, DEDMA, trimethylpropylammonium, trimethylbutylammonium, or dimethyldiethanolammonium.

### Claim 17 (depends on 7)

The process of claim 7 further comprising adding UZM-22 seeds to the reaction mixture.