# Patent

## Title
ITQ-26, new crystalline microporous material

## Abstract

ITQ-26 (INSTITUTO DE TECNOLOOIA QUIMICA number 26) is a new crystalline microporous material with a framework of tetrahedral atoms connected by atoms capable of bridging the tetrahedral atoms, the tetrahedral atom framework being defined by the interconnections between the tetrahedrally coordinated atoms in its framework, ITQ-26 can be prepared in silicate compositions with an organic structure directing agent. It has a unique X-ray diffraction pattern, which identifies it as a new material. ITQ-26 is stable to calcination in air, absorbs hydrocarbons, and is catalytically active for hydrocarbon conversion.

## Background
BACKGROUND OF THE INVENTION
Microporous materials, including zeolites and silicoaluminophosphates, are widely used in the petroleum industry as absorbents, catalysts and catalyst supports. Their crystalline structures consist of three-dimensional frameworks containing uniform pore openings, channels and internal cages of dimensions (<20 Å) similar to most hydrocarbons. The composition of the frameworks can be such that they are anionic, which requires the presence of non-framework cations to balance the negative charge. These non-framework cations, such as alkali or alkaline earth metal cations, are exchangeable, either entirely or partially with another type of cation utilizing ion exchange techniques in a conventional manner. If these non-framework cations are converted to the proton form by, for example, acid treatments or exchange with ammonium cations followed by calcination to remove the ammonia, it imparts the material with Brønsted acid sites having catalytic activity. The combination of acidity and restricted pore openings gives these materials catalytic properties unavailable with other materials due to their ability to exclude or restrict some of the products, reactants, and/or transition states in many reactions. Non-reactive materials, such as pure silica and aluminophosphate frameworks are also useful and can be used in absorption and separation processes of liquids, gases, and reactive molecules such as alkenes.
The family of crystalline microporous compositions known as molecular sieves, which exhibit the ion-exchange and/or adsorption characteristics of zeolites are the aluminophosphates, identified by the acronym AlPO, and substituted aluminophosphates as disclosed in U.S. Pat. Nos. 4,310,440 and 4,440,871. U.S. Pat. No. 4,440,871 discloses a class of silica aluminophosphates, which are identified by the acronym SAPO and which have different structures as identified by their X-ray diffraction pattern. The structures are identified by a numerical number after AlPO, SAPO, MeAPO (Me=metal), etc. (Flanigen et al., Proc. 7th Int. Zeolite Conf., p. 103 (1986) and may include Al and P substitutions by B, Si, Be, Mg, Ge, Zn, Fe, Co, Ni, etc. The present invention is a new molecular sieve having a unique framework structure.
ExxonMobil and others extensively use various microporous materials, such as faujasite, mordenite, and ZSM-5 in many commercial applications. Such applications include reforming, cracking, hydrocracking, alkylation, oligomerization, dewaxing and isomerization. Any new material has the potential to improve the catalytic performance over those catalysts presently employed.
There are currently over 150 known microporous framework structures as tabulated by the International Zeolite Association. There exists the need for new structures, having different properties than those of known materials, for improving the performance of many hydrocarbon processes. Each structure has unique pore, channel and cage dimensions, which gives its particular properties as described above. ITQ-26 is a new framework material.
SUMMARY OF THE INVENTION
ITQ-26 (INSTITUTO DE TECNOLOGÍA QUÍMICA number 26) is a new crystalline microporous material having a framework of tetrahedral atoms connected by bridging atoms, the tetrahedral atom framework being defined by the interconnections between the tetrahedrally coordinated atoms in its framework. ITQ-26 is stable to calcination in air, absorbs hydrocarbons, and is catalytically active for hydrocarbon conversion.
In one embodiment, the present invention is directed to a new crystalline material that is a silicate compound having a composition mR:aX2O3:YO2.nH2O where R is an organic compound, X is any metal capable of tetrahedral coordination such as one or more of B, Ga, Al, Fe, Li, Be, P, Zn, Cr, Mg, Co, Ni, Mn, As, In, Sn, Sb, Ti, and Zr, more preferably one or more trivalent metals capable of tetrahedral coordination, and even more preferably one or more of the elements B, Ga, Al, and Fe, and Y is Si alone or in combination with any other tetravalent metal capable of tetrahedral coordination such as Ge and Ti and where m=0.01-1, a=0.00-0.2, and n=0-10 and having a unique diffraction pattern as given in Table 2.
In a more specific embodiment, the present invention is directed to a calcined crystalline silicate compound that has a composition aX2O3:YO2.nH2O, where X is any metal capable of tetrahedral coordination such as one or more of B, Ga, Al, Fe, Li, Be, P, Zn, Cr, Mg, Co, Ni, Mn, As, In, Sn, Sb, Ti, and Zr, more preferably one or more trivalent metals capable of tetrahedral coordination, and even more preferably one or more of the elements B, Ga, Al, and Fe, and Y is Si alone or in combination with any other tetravalent metal capable of tetrahedral coordination such as Ge and Ti and where a=0.00-0.2 and n=0-10 and having a unique diffraction pattern as given in Table 3.
The present invention also includes a method of synthesizing a crystalline silicate compound having the diffraction pattern similar to Table 2, by mixing together a source of silica, organic structure directing agent (SDA), water, and optional metal and heating at a temperature and time sufficient to crystallize the silicate.
The invention includes the use of ITQ-26 to separate hydrocarbons from a hydrocarbon containing stream.
The invention also includes the use of ITQ-26 as a hydrocarbon conversion catalyst for converting an organic feedstock to conversion products.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a representation of 1,3-bis-(triethylphosphonium-methyl)-benzene the organic structure directing agent (SDA).
FIG. 2 shows the framework structure of ITQ-26 showing only the tetrahedral atoms. There is one unit cell, whose edges are defined by the gray box.
FIG. 3 shows the X-ray diffraction pattern of as-synthesized ITQ-26.
FIG. 4 shows the X-ray diffraction pattern of calcined/dehydrated ITQ-26.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is a new structure of crystalline material. As with any porous crystalline material, the structure of ITQ-26 can be defined by the interconnections between the tetrahedrally coordinated atoms in its framework. In particular, ITQ-26 has a framework of tetrahedral (T) atoms connected by bridging atoms, wherein the tetrahedral atom framework is defined by connecting the nearest tetrahedral (T) atoms in the manner given in Table 1.







TABLE 1







ITQ-26 tetrahedral atom interconnections










T atom
Connected to:







T1
T2, T5, T56, T68



T2
T1, T4, T57, T69



T3
T4, T17, T24, T43



T4
T2, T3, T6, T75



T5
T1, T7, T116, T120



T6
T4, T20, T27, T44



T7
T5, T14, T34, T70



T8
T9, T12, T53, T65



T9
T8, T11, T54, T66



T10
T11, T17, T24, T49



T11
T9, T10, T13, T72



T12
T8, T14, T111, T115



T13
T11, T20, T27, T50



T14
T7, T12, T40, T67



T15
T16, T19, T62, T71



T16
T15, T18, T63, T72



T17
T3, T10, T18, T31



T18
T16, T17, T20, T69



T19
T15, T21, T106, T110



T20
T6, T13, T18, T32



T21
T19, T28, T52, T73



T22
T23, T26, T59, T74



T23
T22, T25, T60, T75



T24
T3, T10, T25, T37



T25
T23, T24, T27, T66



T26
T22, T28, T101, T105



T27
T6, T13, T25, T38



T28
T21, T26, T46, T76



T29
T30, T33, T56, T68



T30
T29, T32, T57, T69



T31
T17, T32, T43, T49



T32
T20, T30, T31, T63



T33
T29, T34, T95, T100



T34
T7, T33, T40, T58



T35
T36, T39, T53, T65



T36
T35, T38, T54, T66



T37
T24, T38, T43, T49



T38
T27, T36, T37, T60



T39
T35, T40, T89, T94



T40
T14, T34, T39, T55



T41
T42, T45, T59, T74



T42
T41, T44, T60, T75



T43
T3, T31, T37, T44



T44
T6, T42, T43, T57



T45
T41, T46, T83, T88



T46
T28, T45, T52, T61



T47
T48, T51, T62, T71



T48
T47, T50, T63, T72



T49
T10, T31, T37, T50



T50
T13, T48, T49, T54



T51
T47, T52, T77, T82



T52
T21, T46, T51, T64



T53
T8, T35, T54, T55



T54
T9, T36, T50, T53



T55
T40, T53, T100, T135



T56
T1, T29, T57, T58



T57
T2, T30, T44, T56



T58
T34, T56, T94, T133



T59
T22, T41, T60, T61



T60
T23, T38, T42, T59



T61
T46, T59, T82, T131



T62
T15, T47, T63, T64



T63
T16, T32, T48, T62



T64
T52, T62, T88, T129



T65
T8, T35, T66, T67



T66
T9, T25, T36, T65



T67
T14, T65, T120, T127



T68
T1, T29, T69, T70



T69
T2, T18, T30, T68



T70
T7, T68, T115, T125



T71
T15, T47, T72, T73



T72
T11, T16, T48, T71



T73
T21, T71, T105, T123



T74
T22, T41, T75, T76



T75
T4, T23, T42, T74



T76
T28, T74, T110, T121



T77
T51, T78, T123, T131



T78
T77, T80, T124, T132



T79
T80, T91, T97, T113



T80
T78, T79, T81, T136



T81
T80, T93, T99, T114



T82
T51, T61, T88, T105



T83
T45, T84, T121, T129



T84
T83, T86, T122, T130



T85
T86, T91, T97, T118



T86
T84, T85, T87, T134



T87
T86, T93, T99, T119



T88
T45, T64, T82, T110



T89
T39, T90, T127, T133



T90
T89, T92, T128, T134



T91
T79, T85, T92, T103



T92
T90, T91, T93, T132



T93
T81, T87, T92, T104



T94
T39, T58, T100, T120



T95
T33, T96, T125, T135



T96
T95, T98, T126, T136



T97
T79, T85, T98, T108



T98
T96, T97, T99, T130



T99
T81, T87, T98, T109



T100
T33, T55, T94, T115



T101
T26, T102, T123, T131



T102
T101, T104, T124, T132



T103
T91, T104, T113, T118



T104
T93, T102, T103, T128



T105
T26, T73, T82, T110



T106
T19, T107, T121, T129



T107
T106, T109, T122, T130



T108
T97, T109, T113, T118



T109
T99, T107, T108, T126



T110
T19, T76, T88, T105



T111
T12, T112, T125, T135



T112
T111, T114, T126, T136



T113
T79, T103, T108, T114



T114
T81, T112, T113, T124



T115
T12, T70, T100, T120



T116
T5, T117, T127, T133



T117
T116, T119, T128, T134



T118
T85, T103, T108, T119



T119
T87, T117, T118, T122



T120
T5, T67, T94, T115



T121
T76, T83, T106, T122



T122
T84, T107, T119, T121



T123
T73, T77, T101, T124



T124
T78, T102, T114, T123



T125
T70, T95, T111, T126



T126
T96, T109, T112, T125



T127
T67, T89, T116, T128



T128
T90, T104, T117, T127



T129
T64, T83, T106, T130



T130
T84, T98, T107, T129



T131
T61, T77, T101, T132



T132
T78, T92, T102, T131



T133
T58, T89, T116, T134



T134
T86, T90, T117, T133



T135
T55, T95, T111, T136



T136
T80, T96, T112, T135










Tetrahedral atoms are those capable of having tetrahedral coordination, including one or more of, but not limiting, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorous, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, gallium, germanium, arsenic, indium, tin, and antimony.
In one embodiment, this new crystalline silicate compound has a composition mR:aX2O3:YO2.nH2O where R is an organic compound, and X is any metal capable of tetrahedral coordination such as one or more of B, Al, Ga, Fe, Li, Be, P, Zn, Cr, Mg, Co, Ni, Mn, As, In, Sn, Sb, Ti, and Zr, more preferably one or more trivalent metals capable of tetrahedral coordination, and even more preferably one or more of the elements B, Ga, Al, and Fe, and Y is Si alone or in combination with any other tetravalent metal capable of tetrahedral coordination such as Ge and Ti and where m=0.01-1, a=0.00-0.2, and n=0-10. This compound has the unique diffraction pattern given in Table 2 and shown in FIG. 3.







TABLE 2







X-ray diffraction lines for as-synthesized ITQ-26











relative int.



d (Å)
(%)







13.8-13.0
60-100



12.3-11.6
5-40



9.09-8.73
30-80 



6.55-6.37
5-50



4.76-4.66
5-50



4.49-4.40
20-70 



4.20-4.12
50-100



3.81-3.75
5-50



3.69-3.63
5-50



3.36-3.31
30-80 



2.998-2.959
5-40



2.846-2.811
5-40



2.624-2.594
5-40



2.503-2.476
5-40



2.366-2.342
5-40










Other embodiments of the new structure include a calcined compound of composition aX2O2:YO2.nH2O, where X is any metal capable of tetrahedral coordination such as one or more of B, Ga, Al, Fe, Li, Be, P, Zn, Cr, Mg, Co, Ni, Mn, As, In, Sn, Sb, Ti, and Zr, more preferably one or more trivalent metals capable of tetrahedral coordination, and even more preferably one or more of the elements B, Ga, Al, Fe, and Y is Si alone or in combination with any other tetravalent metal capable of tetrahedral coordination such as Ge and Ti and where a=0.00-0.2, and n=0-10. This compound has the unique diffraction pattern given in Table 3 and FIG. 4.







TABLE 3







X-ray diffraction lines for calcined/dehydrated ITQ-26










d (Å)
relative int. (%)







13.7-13.0
60-100



12.2-11.6
20-70 



9.63-9.27
1-10



9.03-8.72
20-70 



6.55-6.39
1-10



5.01-4.91
1-10



4.75-4.66
1-20



4.50-4.42
1-20



4.39-4.32
1-10



4.21-4.14
1-20



4.17-4.10
1-20



3.82-3.76
1-10



3.70-3.65
1-20



3.37-3.32
1-20



3.33-3.29
1-10



3.14-3.10
1-10










This new compound is made by the method of mixing together a source of silica, organic structure directing agent (SDA), water, and optional source of metal and heating at a temperature and time sufficient to crystallize the silicate. The method is described below.
The synthetic porous crystalline material of this invention, ITQ-26, is a crystalline phase which has a unique 3-dimensional channel system comprising intersecting 12-membered rings of tetrahedrally coordinated atoms. The 12-membered ring channels have cross-sectional dimensions between the bridging oxygen atoms of about 7.8 Ångströms by about 6.8 Ångströms along one direction and about 7.1 Ångströms by about 6.6 Ångströms along the other two directions.
Variations in the X-ray diffraction pattern may occur between the different chemical composition forms of ITQ-26, such that the exact ITQ-26 structure can vary due its particular composition and whether or not it has been calcined and rehydrated.
In the as-synthesized form ITQ-26 has a characteristic X-ray diffraction pattern, the essential lines of which are given in Table 2 measured with Cu Kα radiation. Variations occur as a function of specific composition and its loading in the structure. For this reason the intensities and d-spacings are given as ranges.
The ITQ-26 material of the present invention may be calcined to remove the organic templating agent without loss of crystallinity. This is useful for activating the material for subsequent absorption of other guest molecules such as hydrocarbons. The essential lines, which uniquely define calcined/dehydrated ITQ-26 are shown in Table 3 measured with synchrotron radiation. Variations occur as a function of specific composition, temperature and the level of hydration in the structure. For this reason the intensities and d-spacings are given as ranges.
In addition, to describing the structure of ITQ-26 by the interconnections of the tetrahedral atoms as in Table 1 above, it may be defined by its unit cell, which is the smallest repeating unit containing all the structural elements of the material. The pore structure of ITQ-26 is illustrated in FIG. 2 (which shows only the tetrahedral atoms) down the direction of the 12-membered ring channels. There is a single unit cell unit in FIG. 2, whose limits are defined by the box. Table 4 lists the typical positions of each tetrahedral atom in the unit cell in units of Ångströms. Each tetrahedral atom is bonded to bridging atoms, which are also bonded to adjacent tetrahedral atoms. Tetrahedral atoms are those capable of having tetrahedral coordination, including one or more of, but not limiting, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorous, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, gallium, germanium, arsenic, indium, tin, and antimony. Bridging atoms are those capable of connecting two tetrahedral atoms, examples which include, but not limiting, oxygen, nitrogen, fluorine, sulfur, selenium, and carbon atoms.
In the case of oxygen, it is also possible that the bridging oxygen is also connected to a hydrogen atom to form a hydroxyl group (—OH—). In the case of carbon it is also possible that the carbon is also connected to two hydrogen atoms to form a methylene group (—CH2—). For example, bridging methylene groups have been seen in the zirconium diphosphonate, MIL-57. See: C. Serre, G. Férey, J. Mater. Chem. 12, p. 2367 (2002). Bridging sulfur and selenium atoms have been seen in the UCR-20-23 family of microporous materials. See: N. Zheng, X. Bu, B. Wang, P. Feng, Science 298, p. 2366 (2002). Bridging fluorine atoms have been seen in lithium hydrazinium fluoroberyllate, which has the ABW structure type. See: M. R. Anderson, I. D. Brown, S. Vilminot, Acta Cryst. B29, p. 2626 (1973). Since tetrahedral atoms may move about due to other crystal forces (presence of inorganic or organic species, for example), or by the choice of tetrahedral and bridging atoms, a range of ±1.0 Ångström is implied for the x and y coordinate positions and a range of ±0.5 Ångström for the z coordinate positions.







TABLE 4







Positions of tetrahedral (T) atoms for the ITQ-26 structure. Values, in


units of Ångströms, are approximate and are typical when T =


silicon and the bridging atoms are oxygen.












Atom
x (Å)
y (Å)
z (Å)
















T1
1.559
8.591
1.558



T2
1.559
5.478
1.559



T3
1.559
1.559
5.056



T4
2.791
2.791
2.490



T5
2.352
11.023
3.307



T6
1.531
1.531
0.000



T7
0.000
11.844
5.084



T8
25.191
18.159
1.558



T9
25.191
21.272
1.559



T10
25.191
25.191
5.056



T11
23.959
23.959
2.490



T12
24.398
15.727
3.307



T13
25.219
25.219
0.000



T14
0.000
14.906
5.084



T15
18.159
1.559
1.558



T16
21.272
1.559
1.559



T17
25.191
1.559
5.056



T18
23.959
2.791
2.490



T19
15.727
2.352
3.307



T20
25.219
1.531
0.000



T21
14.906
0.000
5.084



T22
8.591
25.191
1.558



T23
5.478
25.191
1.559



T24
1.559
25.191
5.056



T25
2.791
23.959
2.490



T26
11.023
24.398
3.307



T27
1.531
25.219
0.000



T28
11.844
0.000
5.084



T29
25.191
8.591
11.672



T30
25.191
5.478
11.671



T31
25.191
1.559
8.174



T32
23.959
2.791
10.740



T33
24.398
11.023
9.922



T34
0.000
11.844
8.146



T35
1.559
18.159
11.672



T36
1.559
21.272
11.671



T37
1.559
25.191
8.174



T38
2.791
23.959
10.740



T39
2.352
15.727
9.922



T40
0.000
14.906
8.146



T41
8.591
1.559
11.672



T42
5.478
1.559
11.671



T43
1.559
1.559
8.174



T44
2.791
2.791
10.740



T45
11.023
2.352
9.922



T46
11.844
0.000
8.146



T47
18.159
25.191
11.672



T48
21.272
25.191
11.671



T49
25.191
25.191
8.174



T50
23.959
23.959
10.740



T51
15.727
24.398
9.922



T52
14.906
0.000
8.146



T53
25.191
18.159
11.672



T54
25.191
21.272
11.671



T55
24.398
15.727
9.922



T56
1.559
8.591
11.672



T57
1.559
5.478
11.671



T58
2.352
11.023
9.922



T59
8.591
25.191
11.672



T60
5.478
25.191
11.671



T61
11.023
24.398
9.922



T62
18.159
1.559
11.672



T63
21.272
1.559
11.671



T64
15.727
2.352
9.922



T65
1.559
18.159
1.558



T66
1.559
21.272
1.559



T67
2.352
15.727
3.307



T68
25.191
8.591
1.558



T69
25.191
5.478
1.559



T70
24.398
11.023
3.307



T71
18.159
25.191
1.558



T72
21.272
25.191
1.559



T73
15.727
24.398
3.307



T74
8.591
1.559
1.558



T75
5.478
1.559
1.559



T76
11.023
2.352
3.307



T77
14.934
21.966
8.173



T78
14.934
18.853
8.174



T79
14.934
14.934
11.671



T80
16.166
16.166
9.105



T81
14.906
14.906
6.615



T82
13.375
25.219
11.699



T83
11.816
4.784
8.173



T84
11.816
7.897
8.174



T85
11.816
11.816
11.671



T86
10.584
10.584
9.105



T87
11.844
11.844
6.615



T88
13.375
1.531
11.699



T89
4.784
14.934
8.173



T90
7.897
14.934
8.174



T91
11.816
14.934
11.671



T92
10.584
16.166
9.105



T93
11.844
14.906
6.615



T94
1.531
13.375
11.699



T95
21.966
11.816
8.173



T96
18.853
11.816
8.174



T97
14.934
11.816
11.671



T98
16.166
10.584
9.105



T99
14.906
11.844
6.615



T100
25.219
13.375
11.699



T101
11.816
21.966
5.057



T102
11.816
18.853
5.056



T103
11.816
14.934
1.559



T104
10.584
16.166
4.125



T105
13.375
25.219
1.531



T106
14.934
4.784
5.057



T107
14.934
7.897
5.056



T108
14.934
11.816
1.559



T109
16.166
10.584
4.125



T110
13.375
1.531
1.531



T111
21.966
14.934
5.057



T112
18.853
14.934
5.056



T113
14.934
14.934
1.559



T114
16.166
16.166
4.125



T115
25.219
13.375
1.531



T116
4.784
11.816
5.057



T117
7.897
11.816
5.056



T118
11.816
11.816
1.559



T119
10.584
10.584
4.125



T120
1.531
13.375
1.531



T121
11.816
4.784
5.057



T122
11.816
7.897
5.056



T123
14.934
21.966
5.057



T124
14.934
18.853
5.056



T125
21.966
11.816
5.057



T126
18.853
11.816
5.056



T127
4.784
14.934
5.057



T128
7.897
14.934
5.056



T129
14.934
4.784
8.173



T130
14.934
7.897
8.174



T131
11.816
21.966
8.173



T132
11.816
18.853
8.174



T133
4.784
11.816
8.173



T134
7.897
11.816
8.174



T135
21.966
14.934
8.173



T136
18.853
14.934
8.174










The complete structure of ITQ-26 is built by connecting multiple unit cells as defined above in a fully-connected three-dimensional framework. The tetrahedral atoms in one unit cell are connected to certain tetrahedral atoms in all of its adjacent unit cells. While Table 1 lists the connections of all the tetrahedral atoms for a given unit cell of ITQ-26, the connections may not be to the particular atom in the same unit cell but to an adjacent unit cell. All of the connections listed in Table 1 are such that they are to the closest tetrahedral (T) atoms, regardless of whether they are in the same unit cell or in adjacent unit cells.
Although the Cartesian coordinates given in Table 4 may accurately reflect the positions of tetrahedral atoms in an idealized structure, the true structure can be more accurately described by the connectivity between the framework atoms as shown in Table 1 above.
Another way to describe this connectivity is by the use of coordination sequences as applied to microporous frameworks by W. M. Meier and H. J. Moeck, in the Journal of Solid State Chemistry 27, p. 349 (1979). In a microporous framework, each tetrahedral atom, No, (T-atom) is connected to N1=4 neighboring T-atoms through bridging atoms (typically oxygen). These neighboring T-atoms are then connected to N2 T-atoms in the next shell. The N2 atoms in the second shell are connected to N3 T-atoms in the third shell, and so on. Each T-atom is only counted once, such that, for example, if a T-atom is in a 4-membered ring, at the fourth shell the No atom is not counted second time, and so on. Using this methodology, a coordination sequence can be determined for each unique T-atom of a 4-connected net of T-atoms. The following line lists the maximum number of T-atoms for each shell.

N0=1 N1≦4 N2≦12 N3≦36 Nk≦4·3k-1 








TABLE 5







Coordination sequence for ITQ-26 structure.









atom
atom



number
label
coordination sequence
























1
T(1)
4
9
18
31
47
66
94
127
159
188
226
287
345


2
T(2)
4
9
17
29
44
68
97
125
154
190
240
292
338


3
T(3)
4
9
18
30
42
60
89
126
162
188
222
281
349


4
T(4)
4
12
18
27
48
69
94
124
160
201
237
285
330


5
T(5)
4
12
17
30
46
67
90
124
158
186
230
279
344


6
T(6)
4
11
20
24
36
72
110
126
136
182
256
306
326


7
T(7)
4
11
20
28
42
70
100
120
146
186
232
291
349









One way to determine the coordination sequence for a given structure is from the atomic coordinates of the framework atoms using the computer program zeoTsites (see G. Sastre, J. D. Gale, Microporous and mesoporous Materials 43, p. 27 (2001).
The coordination sequence for the ITQ-26 structure is given in Table 5. The T-atom connectivity as listed in Table 1 and is for T-atoms only. Bridging atoms, such as oxygen usually connects the T-atoms. Although most of the T-atoms are connected to other T-atoms through bridging atoms, it is recognized that in a particular crystal of a material having a framework structure, it is possible that a number of T-atoms may not connected to one another. Reasons for non-connectivity include, but are not limited by; T-atoms located at the edges of the crystals and by defects sites caused by, for example, vacancies in the crystal. The framework listed in Table 1 and Table 5 is not limited in any way by its composition, unit cell dimensions or space group symmetry.
While the idealized structure contains only 4-coordinate T-atoms, it is possible under certain conditions that some of the framework atoms may be 5- or 6-coordinate. This may occur, for example, under conditions of hydration when the composition of the material contains mainly phosphorous and aluminum T-atoms. When this occurs it is found that T-atoms may be also coordinated to one or two oxygen atoms of water molecules (—OH2), or of hydroxyl groups (—OH). For example, the molecular sieve AlPO4-34 is known to reversibly change the coordination of some aluminum T-atoms from 4-coordinate to 5- and 6-coordinate upon hydration as described by A. Tuel et al. in J. Phys. Chem. B 104, p. 5697 (2000). It is also possible that some framework T-atoms can be coordinated to fluoride atoms (—F) when materials are prepared in the presence of fluorine to make materials with 5-coordinate T-atoms as described by H. Koller in J. Am. Chem. Soc. 121, p. 3368 (1999).
The invention also includes a method of synthesizing a crystalline silicate composition of ITQ-26 having the diffraction pattern similar to Table 2 by mixing together a source of silica, organic structure directing agent (SDA), water, and optional metal, X, with a composition, in terms of mole ratios, within the following ranges:
















R/YO2
0.01-1   



H2O/YO2
2-50



X/YO2
0-.2 










and preferably within the following ranges:

















R/YO2
0.1-.5 



H2O/YO2
5-20



X/YO2
0-.1 










and X is any metal capable of tetrahedral coordination such as one or more of B, Ga, Al, Fe, Li, Be, P, Zn, Cr, Mg, Co, Ni, Be, Mn, As, In, Sn, Sb, Ti, and Zr, more preferably one or more trivalent metals capable of tetrahedral coordination, and even more preferably one or more of the elements B, Ga, Al, and Fe, and Y is Si alone or in combination with any other tetravalent metal capable of tetrahedral coordination such as Ge and Ti.

Said organic structure directing agent (SDA) is preferably 1,3-bis-(triethylphosphoniummethyl)-benzene. See FIG. 1. Sources of silica can be colloidal, fumed or precipitated silica, silica gel, sodium or potassium silicates, or organic silicon such as tetraethylorthosilicate, etc. Sources of metal can be boric acid, germanium (IV) ethoxide, germanium oxide, germanium nitrate, aluminum nitrate, sodium aluminate, aluminum sulfate, aluminum hydroxide, aluminum chloride and various salts of the metals X such as iron nitrate, iron chloride, and gallium nitrate, etc. The mixture is then heated at a temperature and time sufficient to crystallize the silicate.
To the extent desired and depending on the X2O3/YO2 molar ratio of the material, any cations present in the as-synthesized ITQ-26 can be replaced in accordance with techniques well known in the art by ion exchange with other cations. Preferred replacing cations include metal ions, hydrogen ions, and hydrogen precursor, e.g., ammonium ions and mixtures thereof. Particularly preferred cations are those which tailor the catalytic activity for certain hydrocarbon conversion reactions. These include hydrogen, rare earth metals and metals of Groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII of the Periodic Table of the Elements.
The crystalline material of this invention can be used to catalyze a wide variety of chemical conversion processes, particularly organic compound conversion processes, including many of present commercial/industrial importance. Examples of chemical conversion processes which are effectively catalyzed by the crystalline material of this invention, by itself or in combination with one or more other catalytically active substances including other crystalline catalysts, include those requiring a catalyst with acid activity.
Thus, in its active form ITQ-26 can exhibit a high acid activity, which can be measured with the alpha test. Alpha value is an approximate indication of the catalytic cracking activity of the catalyst compared to a standard catalyst and it gives the relative rate constant (rate of normal hexane conversion per volume of catalyst per unit time). It is based on the activity of silica-alumina cracking catalyst taken as an Alpha of 1 (Rate Constant=0.016 sec−1). The Alpha Test is described in U.S. Pat. No. 3,354,078; in the Journal of Catalysis 4, 527 (1965); 6, 278 (1966); and 61, 395 (1980), each incorporated herein by reference as to that description. The experimental conditions of the test used herein include a constant temperature of 538° C. and a variable flow rate as described in detail in the Journal of Catalysis 61, 395 (1980).
When used as a catalyst, the crystalline material of the invention may be subjected to treatment to remove part or all of any organic constituent. This is conveniently effected by thermal treatment in which the as-synthesized material is heated at a temperature of at least about 370° C. for at least 1 minute and generally not longer than 20 hours. While subatmospheric pressure can be employed for the thermal treatment, atmospheric pressure is desired for reasons of convenience. The thermal treatment can be performed at a temperature up to about 927° C. The thermally treated product, especially in its metal, hydrogen and ammonium forms, is particularly useful in the catalysis of certain organic, e.g., hydrocarbon, conversion reactions.
When used as a catalyst, the crystalline material can be intimately combined with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as, but not limited to, platinum or palladium where a hydrogenation-dehydrogenation function is to be performed. Such component can be in the composition by way of co-crystallization, exchanged into the composition to the extent a Group IIIA element, e.g., aluminum, is in the structure, impregnated therein or intimately physically admixed therewith. Such component can be impregnated in or on to it such as, for example, by, in the case of platinum, treating ITQ-26 with a solution containing a platinum metal-containing ion. Thus, suitable platinum compounds for this purpose include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex.
The crystalline material of this invention, when employed either as an adsorbent or as a catalyst in an organic compound conversion process should be dehydrated, at least partially. This can be done by heating to a temperature in the range of 100° C. to about 370° C. in an atmosphere such as air, nitrogen, etc., and at atmospheric, subatmospheric or superatmospheric pressures for between 30 minutes and 48 hours. Dehydration can also be performed at room temperature merely by placing the ITQ-26 in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration.
As in the case of many catalysts, it may be desirable to incorporate the new crystal with another material resistant to the temperatures and other conditions employed in organic conversion processes. Such materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of a material in conjunction with the new crystal, i.e., combined therewith or present during synthesis of the new crystal, which is active, tends to change the conversion and/or selectivity of the catalyst in certain organic conversion processes. Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate of reaction. These materials may be incorporated into naturally occurring clays, e.g., bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions. Said materials, i.e., clays, oxides, etc., function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in commercial use it is desirable to prevent the catalyst from breaking down into powder-like materials. These clay and/or oxide binders have been employed normally only for the purpose of improving the crush strength of the catalyst.
Naturally occurring clays which can be composited with the new crystal include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. Binders useful for compositing with the present crystal also include inorganic oxides, such as silica, zirconia, titania, magnesia, beryllia, alumina, and mixtures thereof.
In addition to the foregoing materials, the new crystal can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia.
The relative proportions of finely divided crystalline material and inorganic oxide matrix vary widely, with the crystal content ranging from about 1 to about 90 percent by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of about 2 to about 80 weight percent of the composite.
In order to more fully illustrate the nature of the invention and the manner of practicing same, the following example is presented.
EXAMPLE 1
Synthesis of ITQ-26
The germanium containing gel was prepared, according to the following description: 0.62 of germanium oxide were dissolved in 24.19 g of a solution of 1,3-bis-(triethylphosphoniummethyl)-benzene hydroxide (FIG. 1) with a concentration of 0.62 mol of OH− in 1000 g of solution. Then, 5.02 g of tetraethylorthosilicate were hydrolyzed in that solution and the mixture was left to evaporate under stirring until complete evaporation of the ethanol formed was achieved. When the weight reached 8.62 g of gel, 0.62 g of HF (48.1% wt.) were added and the mixture was homogenized. The final composition of the gel was:

0.80Si02: 0.20Ge02: 0.25 m-B(Et3P)2(OH)2: 0.50 HF: 7.50H20

The mixture was transferred to Teflon-lined stainless steel autoclaves and heated under stirring for 6 days at 175° C. Longer crystallization times gave impure ITQ-26 with a small amount of polymorph C of Beta zeolite.
The powder X-ray diffractogram of the sample as made and calcined is shown in FIG. 3 and FIG. 4 below. The sample was calcined in air to 550° C. for 3 hours, cooled down to 300° C., and then sealed under vacuum in a 2 mm quartz capillary tube to minimize structural damage.
The X-ray diffraction patterns are given in Table 6 and Table 7, respectively.
The porosity of the calcined material was measured by adsorbing nitrogen and argon. Adsorption measurements were carried out by manipulating the sample in an inert atmosphere. The results obtained are:

    
    
        BET surface area: 257 m2/g
        Micropore area: 243 m2/g
        Micropore volume: 0.12 cm3/g
        Pore diameter: 7.1 Å
    
    


That data suggest that ITQ-26 is a large pore (12-ring pore aperture) zeolite. This is confirmed by the structure discussed above.
EXAMPLE 2
Synthesis of ITQ-26
The germanium containing gel was prepared, according to the following description: 0.75 of germanium oxide were dissolved in 22.5 g of a solution of 15% wt. 1,3-bis-(triethylphosphoniummethyl)-benzene hydroxide. Then, 6.01 g of tetraethylorthosilicate were hydrolyzed in that solution and the mixture was left to evaporate under stirring until complete evaporation of the ethanol formed was achieved. When the weight reached 10.3 g of gel, 0.74 g of HF (49% wt.) were added and the mixture was homogenized. The final composition of the gel was:

0.80 Si02: 0.20 Ge02: 0.25 m-B(Et3P)2(OH)2: 0.50 HF: 7.50H20

The mixture was transferred to a Teflon-lined stainless steel autoclave and heated for 6 days at 175° C. with a tumbling rate of 20 rpm. The sample was recovered by filtration, washed with deionized water and then dried in an 115° C. oven. The X-ray diffraction pattern was measured with Cu Kα radiation and is similar to that given in Table 6 and FIG. 3. Analysis of the X-ray diffraction pattern showed the sample to be pure ITQ-26.







TABLE 6







X-ray powder diffraction lines of as-made ITQ-26


(Cu Kα radiation)









2-Theta
d (Å)
I %












4.63
19.086
3


6.62
13.348
100


7.40
11.944
19


9.43
9.376
8


9.92
8.907
60


10.47
8.440
3


11.94
7.407
6


13.70
6.460
29


14.11
6.273
9


15.21
5.819
1


16.29
5.437
2


16.96
5.224
6


17.87
4.960
10


18.83
4.709
25


19.98
4.441
37


20.26
4.379
5


21.34
4.160
79


22.99
3.866
1


23.30
3.815
5


23.39
3.801
1


23.53
3.779
23


24.29
3.661
30


25.30
3.518
6


26.08
3.414
5


26.72
3.334
54


27.57
3.233
8


28.54
3.125
6


29.98
2.979
19


31.61
2.828
16


33.08
2.705
7


33.65
2.661
5


34.34
2.609
13


36.04
2.490
14


37.08
2.423
8


38.20
2.354
16


40.65
2.218
8


43.52
2.078
8


46.32
1.959
6


48.38
1.880
4
















TABLE 7







X-ray powder diffraction lines of calcined/dehydrated ITQ-26


(Synchrotron radiation, λ = 0.8702 Å)









2-Theta
d (A)
I %












2.64
18.907
1


3.73
13.376
100


4.20
11.864
41


5.28
9.449
4


5.62
8.873
42


6.75
7.390
1


7.46
6.692
1


7.54
6.622
2


7.71
6.469
4


7.97
6.259
1


9.58
5.210
2


10.07
4.959
4


10.60
4.709
8


11.20
4.459
7


11.47
4.353
3


11.80
4.232
2


11.97
4.173
9


12.07
4.139
9


13.00
3.845
1


13.09
3.819
1


13.20
3.787
4


13.61
3.672
5


14.23
3.514
1


14.70
3.402
2


14.95
3.344
9


15.12
3.307
4


15.23
3.284
1


15.46
3.236
2


15.58
3.211
2


16.05
3.117
3


16.74
2.989
2


16.89
2.963
3


17.67
2.832
3


19.20
2.608
3


21.31
2.353
2

## Claims

1. A synthetic crystalline material having a framework of tetrahedral atoms (T) connected by bridging atoms, the tetrahedral atom framework being defined by connecting the nearest tetrahedral (T) atoms in the manner shown in Table 1 of the specification.

2. The crystalline material of claim 1 wherein said tetrahedral atoms include one or more elements selected from the group consisting of Li, Be, Al, P, Si, Ga, Ge, Zn, Cr, Mg, Fe, Co, Ni, Mn, As, In, Sn, Sb, Ti, and Zr.

3. The crystalline material of claims 1 or 2 wherein said bridging atoms include one or more elements selected from the group consisting of O, N, F, S, Se, and C.

4. A synthetic porous crystalline material, as synthesized, characterized by an X-ray diffraction pattern including the peaks as substantially set forth in Table 2 of the specification.

5. The crystalline material of claim 4 wherein said crystalline material has a composition mR:aX2O3:YO2.nH2O where R is an organic compound, X is one or more metals selected from the group consisting of B, Ga, Al and Fe, and Y is one or more metals selected from the group consisting of Si, Ge and Ti, and m is a real number less than or equal to 1, a is a real number less than or equal to 0.2 and n is a real number less than or equal to 10.

6. A calcined dehydrated material characterized by an X-ray diffraction pattern including the most significant lines substantially, as set forth in Table 3 of the specification.

7. The calcined dehydrated material of claim 6 wherein said crystalline material has a composition aX2O3:YO2.nH2O where X is one or more metals selected from the group consisting of B, Ga, Al and Fe, and Y is one or more metals selected from the group consisting of Si, Ge and Ti, and a is a real number less than or equal to 0.2 and n is a real number less than or equal to 10.

8. A process for the separation of hydrocarbons from a hydrocarbon-containing stream using the material of claim 6.

9. A process for converting a feedstock comprising organic compounds to at least one conversion product which comprises contacting said feedstock at organic compound conversion conditions with a catalyst comprising an active form of the material of claim 6.

10. The process for converting a feedstock of claim 9 wherein the catalyst is combined with a hydrogenating metal.

11. The process for converting a feedstock of claim 10 wherein said hydrogenating metal is one or more metals selected from the group consisting of tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal.

12. A method of synthesizing a crystalline silicate composition of ITQ-26 having the diffraction pattern substantially as set forth in Table 2 of the specification by mixing together at least one source of silica, at least one organic structure directing agent (R), water, and optionally a source of metal (X) to form a mixture having a composition, in terms of mole ratios, within the following ranges:
















R/YO2
0.01-1   



H2O/YO2
2-50



X/YO2
0-.2 









wherein X is any trivalent metal capable of tetrahedral coordination and Y is silicon and optionally any other tetravalent metal capable of tetrahedral coordination.

13. The method according to claim 12 wherein X is one or more metals selected from the group consisting of B, Ga, Al or Fe and Y is silicon and may include one or more metals selected from the group consisting of Ge and Ti.

14. The method of claim 12 wherein said molar ratio ranges are
















R/YO2
0.1-.5 



H2O/YO2
5-20



X/YO2
0-.1

15. A method of synthesizing a crystalline silicate composition of claim 12 wherein said organic structure directing agent (SDA) is 1,3-bis-(triethylphosphoniummethyl)-benzene.

16. The crystalline silicate composition produced using the method of claim 12.

17. A method of synthesizing a crystalline silicate composition of ITQ-26 having the diffraction pattern substantially as set forth in Table 2 of the specification by mixing together a source of silica, organic structure directing agent (R), water, and optionally a source of metal (X), to form a mixture having a composition, in terms of mole ratios, within the following ranges:
















R/YO2
0.01-1   



H2O/YO2
2-50



X/YO2
0-.2 









and wherein X is one or more metals selected from the group consisting of B, Ga, Al, Fe, Li, Be, P, Zn, Cr, Mg, Co, Ni, Mn, As, In, Sn, Sb, Ti, and Zr, and Y is silicon and may include one or more metals selected from the group consisting of Ge and Ti.