Zeolitic microporous crystalline material with an LTA structure (ITQ-29), preparation method thereof and uses of same in organic compound separation and transformation processes
View Patent ↗The invention relates to a material which, once calcined and in the anhydrous state has general formula x (M 1/n XO 2 ):z ZO 2 :y GeO 2 :(1−y) SiO 2 , wherein x has a value of less than 0.2, preferably less than 0.15 and can equal zero; z has a value of between 0 and 0.1, preferably between 0 and 0.05; y has a value of between 0 and 1, preferably between 0 and 0.75; M represents one or more +n charged inorganic cations; X represents one or more +3 oxidation state chemical elements (Al, B, Ga, Fe); and Z represents one or more +4 oxidation state cations different from silicon and germanium, preferably Ti or Sn. Said material can be used as a component of catalysts in acid catalysis processes or as a metal or oxide support in separation and absorption/adsorption processes.
1. A crystalline material with LTA structure of zeolitic nature that in its calcined and anhydrous state, and in the absence of defects in its crystalline lattice has the following empirical formula: x(M 1 /nXO 2 ):z ZO 2 :y GeO 2 :(1−y) SiO 2 where M is H+ or at least one +n charged inorganic cation; X is at least one chemical element in +3 oxidation state; Z is at least one cation in an oxidation state of +4 different from Si and Ge; wherein x has a value between 0 and 0.15, y has a value between 0 and 1, and z has a value between 0 and 0.1.
2. A crystalline material according to claim 1 , wherein it has been prepared from a reaction mixture that has at least a 4-methyl-2,3,6,7,-tetrahydro-1H,5H-pyrido [3,2,1-ij] quinolinium cation as an organic compound source.
3. A crystalline material according to claim 1 , wherein in the state just as synthesized, the X-ray diffraction pattern, as measured by a fixed divergence slit and using the Ka-Cu radiation, is as follows:
d (Å) ± 0.4
I (I * 100/I 0 )
12.00
mf
8.48
m
6.92
100
5.99
md
3.99
f
3.61
d
3.32
md
3.20
md
2.90
md
2.55
md
where mf is a very strong relative intensity that corresponds to 99-80% of the peak of greatest intensity; f is a strong relative intensity that corresponds to 60-80% of the peak of greatest intensity; m is a medium relative intensity that corresponds to 40-60% of the peak of greatest intensity; d is a weak relative intensity that corresponds to 20-40% of the peak of greatest intensity; md is a very weak relative intensity that corresponds to less than 20% of the peak of greatest intensity.
4. A crystalline material according to claim 1 , wherein in its calcined and anhydrous state its x-ray diffraction pattern is:
d (Å) ± 0.4
I (I * 100/I 0 )
12.00
100
8.47
f
6.91
d
5.35
md
3.98
md
3.60
md
3.31
md
3.19
md
2.90
md
2.54
md
where, f is a strong relative intensity that corresponds to 60-80% of the peak of greatest intensity; d is a weak relative intensity that corresponds to 20-40% of the peak of greatest intensity; md is a very weak relative intensity that corresponds to less than 20% of the peak of greatest intensity.
5. A crystalline material according to claim 1 wherein Z is selected from the group consisting of Ti and Sn.
6. A crystalline material according to claim 5 , wherein in its calcined and anhydrous state its x-ray diffraction pattern is:
d (Å) ± 0.4
I (I * 100/I 0 )
12.00
100
8.47
f
6.91
d
5.35
md
3.98
md
3.60
md
3.31
md
3.19
md
2.90
md
2.54
md
where mf is a very strong relative intensity that corresponds to 99-80% of the peak of greatest intensity; f is a strong relative intensity that corresponds to 60-80% of the peak of greatest intensity; m is a medium relative intensity that corresponds to 40-60% of the peak of greatest intensity; d is a weak relative intensity that corresponds to 20-40% of the peak of greatest intensity; md is a very weak relative intensity that corresponds to less than 20% of the peak of greatest intensity.
7. A procedure to synthesize the microporous crystalline material of claim 5 in which a reaction mixture contains a source of SiO 2 , optionally, a source of GeO 2 , optionally, a source of one or several tetravalent elements Z different from Si and Ge, at least one source of the organic compound R, a source of fluoride, and water, is heated at a temperature between 80 and 200° C., until crystallization is achieved, wherein the reaction mixture has a composition, in terms of molar relationships between the following ranges:
R/(SiO 2 + GeO 2 ):
0.05-1.0
ZO 2 /(SiO 2 + GeO 2 ):
0-1.0
GeO 2 /(SiO 2 + GeO 2 ):
0-1.0
F/(SiO 2 + GeO 2 ):
0.1-3.0
H 2 O/(SiO 2 + GeO 2 ):
1-50.
8. A procedure according to claim 7 wherein Z is Ti or Sn.
9. A procedure according to claim 7 wherein R is 4-methyl-2,3,6,7,-tetrahydro -1H,5H-pyrido [3,2,1-ij] quinolinium cation or a mixture of said cation with the tetramethylammonium cation or with ethylenglycol.
10. A procedure according to claim 7 wherein the temperature is between 100° and 200° C.
11. A crystalline material according to claim 1 , wherein in the state just as synthesized, the X-ray diffraction pattern, as measured by a fixed divergence slit and using the Ka-Cu radiation, is as follows:
d (Å) ± 0.4
I (I * 100/I 0 )
12.00
mf
8.48
m
6.92
100
5.99
md
3.99
f
3.61
d
3.32
md
3.20
md
2.90
md
2.55
md
where mf is a very strong relative intensity that corresponds to 99-80% of the peak of greatest intensity; f is a strong relative intensity that corresponds to 60-80% of the peak of greatest intensity; d is a weak relative intensity that corresponds to 20-40% of the peak of greatest intensity; md is a very weak relative intensity that corresponds to less than 20% of the peak of greatest intensity.
12. A procedure to synthesize the microporous crystalline material of claim 1 , in which a reaction mixture that contains a source of SiO 2 , optionally, a source of GeO 2 , optionally, a source of one or more of several trivalent elements X, optionally, a source of +n inorganic cations M, at least one source of organic compound R, a source of fluoride, and water, is heated at a temperature between 80 and 200° C., until crystallization is achieved, wherein the reaction mixture has a composition, in terms of molar relationships between the following ranges:
R/(SiO 2 + GeO 2 ):
0.05-1.0
M 1 /nOH/(SiO 2 + GeO 2 ):
0-1.0
X 2 O 3 /(SiO 2 + GeO 2 ):
0-1.0
GeO 2 /(SiO 2 + GeO 2 ):
0-1.0
F/(SiO 2 + GeO 2 ):
0.1-3.0
H 2 O/(SiO 2 + GeO 2 ):
1-50.
13. A procedure according to claim 12 , wherein that a quantity of crystalline material is added to the reaction mixture as crystallization promoter, said quantity being up to 20% by weight in relation to the total of inorganic oxides added.
14. A procedure according to claim 12 wherein X is selected from the group consisting of Al, B, Ga and Fe.
15. A procedure according to claim 12 wherein R is 4-methyl-2,3,6,7,-tetrahydro -1H,5H-pyrido [3,2,1-ij] quinolinium cation or a mixture of said cation with tetramethylammonium cation or with ethylenglycol.
16. A procedure according to claim 15 , wherein the 4-methyl-2,3,6,7, -tetrahydro-1H,5 H-pyrido [3,2,1 -ij] quinolinium and the tetramethylammonium organic cations are added as hydroxides or as salts, or as a mixture of both.
17. A procedure according to claim 16 wherein the organic cations are added as a halide.
18. A procedure according to claim 12 wherein the temperature is between 100° and 200° C.
19. A method to convert feedings formed by organic compounds in the presence of a catalyst comprising adding a catalytically active form of the material described in claim 1 as a catalyst.
20. A method to separate gases in the presence of an adsorbent comprising adding a catalytically active form of the material described in claim 1 as an adsorbent.
21. An adsorbent for gases and vapours comprising an active form of the material described in claim 1 .
22. A crystalline material according to claim 1 wherein X is selected from the group consisting of Al, B, Ga and Fe.
23. A crystalline material according to claim 1 wherein y has a value lower than 0.75.
24. A crystalline material according to claim 1 wherein z has a value lower than 0.05.