SOLIDOTHERMAL SYNTHESIS OF ZEOLITIC MATERIALS AND ZEOLITES OBTAINED THEREFROM

Abstract

The present invention relates to a process for the preparation of a zeolitic material comprising YO.sub.2 in its framework structure, wherein Y stands for a tetravalent element, wherein said process comprises the steps of: (1) providing a mixture comprising one or more sources for YO.sub.2, one or more fluoride containing compounds, and one or more structure directing agents; (2) crystallizing the mixture obtained in step (1) for obtaining a zeolitic material comprising YO.sub.2 in its framework structure;
wherein the mixture provided in step (1) and crystallized in step (2) contains 35 wt.-% or less of H.sub.2O based on 100 wt.-% of YO.sub.2 contained in the mixture provided in step (1) and crystallized in step (2), as well as to a zeolitic material comprising YO.sub.2 in its framework structure obtainable and/or obtained according to said process, and to a zeolitic material per se comprising SiO.sub.2 in its framework structure, wherein in the .sup.29Si MAS NMR spectrum of the as-synthesized zeolitic material the ratio of the total integration value of the peaks associated to Q3 signals to the total integration value of the peaks associated to Q4 signals is in the range of from 0:100 to 20:80, including the use of the aforementioned zeolitic materials.

Claims

1.-14. (canceled)

15. A process for the preparation of a zeolitic material comprising YO.sub.2 in its framework structure, wherein Y is a tetravalent element, wherein said process comprises the steps of: (1) providing a mixture comprising one or more sources for YO.sub.2, one or more fluoride containing compounds, and one or more structure directing agents; (2) crystallizing the mixture obtained in step (1) for obtaining a zeolitic material comprising YO.sub.2 in its framework structure; wherein the mixture provided in step (1) and crystallized in step (2) contains 35 wt.-% or less of H.sub.2O based on 100 wt.-% of YO.sub.2 contained in the mixture provided in step (1) and crystallized in step (2).

16. The process of claim 15, wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mixtures thereof.

17. The process of claim 15, wherein the one or more fluoride containing compounds comprise one or more fluoride salts and/or hydrogen fluoride.

18. The process of claim 15, wherein the one or more structure directing agents provided in step (1) comprise one or more organic compounds.

19. The process of claim 15, wherein the molar ratio of the one or more structure directing agents: YO.sub.2 in the mixture provided in step (1) and crystallized in step (2) ranges from 0.01:1 to 2:1.

20. The process of claim 15, wherein the molar ratio of fluoride: YO.sub.2 in the mixture provided in step (1) and crystallized in step (2) is in the range of from 0.01:1 to 5:1.

21. The process of claim 15, wherein seed crystals are further provided in step (1).

22. The process of claim 15, wherein one or more sources of X.sub.2O.sub.3 are further provided in step (1), wherein X is a trivalent element.

23. The process of claim 15, wherein crystallization in step (2) comprises heating of the mixture.

24. The process of claim 23, wherein in step (2) the mixture is crystallized under autogenous pressure.

25. A zeolitic material comprising YO.sub.2 in its framework structure obtained by the process of claim 15.

26. A zeolitic material comprising SiO.sub.2 in its framework structure, wherein in the .sup.29Si MAS NMR spectrum of the as-synthesized zeolitic material the ratio of the total integration value of the peaks associated to Q3 signals to the total integration value of the peaks associated to Q4 signals is in the range of from 0:100 to 20:80.

27. The zeolitic material of claim 26, wherein the peaks associated to Q3 signals refer to the peaks in the .sup.29Si MAS NMR spectrum located in the range of from −95 to −108.75 ppm, and wherein the peaks associated to Q4 signals refer to the peaks in the .sup.29Si MAS NMR spectrum located in the range of from −108.76 to −125 ppm.

28. Use of a zeolitic material according to claim 26 as a molecular sieve, as an adsorbent, for ion-exchange, as a catalyst and/or as a catalyst support.

Description

DESCRIPTION OF THE FIGURES

[0095] FIG. 1 shows the X-ray diffraction pattern (measured using Cu K alpha-1 radiation) of the crystalline material obtained according to Example 1. In the figure, the angle 2 theta in ° is shown along the abscissa and the intensities are plotted along the ordinate.

[0096] FIG. 2 shows the (deconvoluted) .sup.29Si CP-MAS NMR obtained from the sample from Example 1 as spectrum “A” in the lower portion of the figure. For comparative purposes, the (deconvoluted) .sup.29Si CP MAS NMR of a sample obtained from synthesis of Silicalite-1 in the presence of crystallization water is displayed as comparative spectrum “B” in the upper portion of the figure. In the figure, the values in ppm are plotted along the abscissa.

[0097] FIGS. 3-7 and 12 show the X-ray diffraction patterns (measured using Cu K alpha-1 radiation) of the crystalline materials obtained according to Examples 2-5, 8, and 10, respectively. In the respective figures, the angle 2 theta in ° is shown along the abscissa and the intensities in arbitrary units are plotted along the ordinate.

[0098] FIGS. 8 and 11 show the .sup.29Si MAS NMR obtained from the samples from Example 8 and 9, respectively, wherein the values in ppm are plotted along the abscissa.

[0099] FIG. 9 shows the (deconvoluted) .sup.29Si CP-MAS NMR obtained from the sample from Example 8, wherein the values in ppm are plotted along the abscissa.

[0100] FIG. 10 shows the X-ray diffraction pattern (measured using Cu K alpha-1 radiation) of the crystalline material obtained according to Example 9. The diffraction pattern displayed with a solid black line was obtained from the crystalline material as-synthesized, whereas the diffraction pattern displayed with a solid grey line was obtained from the calcined product. In the figures, the angle 2 theta in ° is shown along the abscissa, and the intensity in arbitrary units is plotted along the ordinate.

EXAMPLES

[0101] X-ray diffraction experiments on the powdered materials were performed using a Rigaku Ultimate VI X-ray diffractometer using the Cu K alpha-1 radiation (λ=1.5406 Å).

[0102] .sup.29Si MAS solid-state NMR experiments with (.sup.1H-.sup.29Si) cross polarization were performed using a Bruker AVANCE 500 spectrometer with 500 MHz .sup.1H Larmor frequency. Samples were packed in 4 mm ZrO.sub.2 rotors, and measured under 10 kHz Magic Angle Spinning at room temperature. .sup.29Si spectra were obtained using .sup.29Si (π/2)-pulse excitation with 4 μs pulse width, a .sup.29Si carrier frequency corresponding to −95.6 ppm in the spectrum, and a scan recycle delay of 10 s. Signal was acquired for 10 ms under 27.78 kHz high-power proton decoupling, and accumulated for up to 17 hours. Spectra were processed using Bruker Topspin with 30 Hz exponential line broadening, manual phasing, and manual baseline correction over the full spectrum width. Deconvolution of the spectra was achieved using the PeakFit software (Version 4.11, Systat Software Inc., San Jose, Calif.), wherein the baseline setting “Linear, D2” was employed with a tolerance (“Tol %”) of 3.0%, smoothing (“Sm %”) was set to a value of 1.00%, the peak type settings “Spectroscopy” and “Lorentz Area” were used, and the autoscan was set to an amplitude (“Amp %”) of 1.50% using the “Vary Widths” option. Spectra were referenced with Kaolinite as an external secondary standard, by setting the resonance of silica to −91.5 ppm.

Example 1

Solidothermal Synthesis of Silicalite-1

[0103] 1.6 g of solid silica gel (Qingdao Haiyang Chemical Reagent Co., Ltd.), 0.15 g of NH.sub.4F (98%, Aladdin Chemistry Co., Ltd.), and 0.25 g of tetrapropylammonium bromide (98%, Aladdin Chemistry Co., Ltd.) were added into a mortar one by one and mixed together. After grinding for 5 minutes, the powder mixture was transferred to an autoclave and sealed. After heating at 180° C. for 15 h, the sample was fully crystallized.

[0104] The XRD pattern of the zeolite product obtained in Example 1 which displays the MFI-type framework structure is shown in FIG. 1.

[0105] Furthermore, the deconvoluted .sup.29Si CP-MAS NMR spectrum of the crystalline product is displayed in spectrum “A” of FIG. 2. More specifically, the deconvolution afforded peaks assigned to Q4 signals at −117.3 ppm (16%), −115.4 ppm (19%), −113.3 ppm (20%), −112.5 ppm (10%), and −110.4 ppm (23%), wherein the integration value for the respective peak is indicated in parentheses, and a single Q3 signal at −107.1 ppm (12%).

[0106] For comparative purposes, the deconvoluted .sup.29Si CP-MAS NMR spectrum obtained for Sili-calite-1 prepared in the presence of cristallyzation water contained in the reaction mixture is displayed in comparative spectrum “B” of FIG. 2, wherein deconvolution affords peaks as-signed to Q4 signals at −116.1 ppm (23%) and −112.8 ppm (56%), and two Q3 signals at −106.0 ppm (9%) and −101.7 ppm (12%).

[0107] Thus, as may be taken from a comparison of the .sup.29Si NMR spectra in FIG. 2, a considerably larger amount of Q3 signals are observed in comparative spectrum “B” which displays a ratio of the total integration value of the peaks associated to Q3 signals to the total integration value of the peaks associated to Q4 signals of 21:79. As opposed thereto, the .sup.29Si NMR spectrum of the inventive material only displays a ratio of the total integration value of the peaks associated to Q3 signals to the total integration value of the peaks associated to Q4 signals of 12:88. Accordingly, Silicatlite-1 obtained according to the inventive method in the absence of water in the reaction mixture displays clearly less structural defects in the framework structure due to a portion of the SiO.sub.4-tetrahedra not being linked to four neighboring SiO.sub.4-tetrahedra, which may accordingly be detected as Q3 signals in the .sup.29Si NMR spectrum.

Example 2

Solidothermal Synthesis of Zeolite Beta

[0108] 1.6 g of solid silica gel (Qingdao Haiyang Chemical Reagent Co., Ltd.), 1.25 g of NH.sub.4F (98%, Aladdin Chemistry Co., Ltd.), 1.75 g of tetraethylammonium bromide (98%, Aladdin Chemistry Co., Ltd.), and 0.16 g of zeolite beta seeds (Si/Al molar ratio=12.5) were added into a mortar one by one and mixed together. After grinding for 5 minutes, the powder mixture was transferred to an autoclave and sealed. After heating at 140° C. for 5 d, the sample was fully crystallized.

[0109] The XRD pattern of the zeolite product obtained in Example 2 which displays the BEA-type framework structure is shown in FIG. 3.

Example 3

Solidothermal Synthesis of EU-1

[0110] 1.6 g of solid silica gel (Qingdao Haiyang Chemical Reagent Co., Ltd.), 1.0 g of NH.sub.4F (98%, Aladdin Chemistry Co., Ltd.), 1.0 g of hexamethonium bromide (J&K Scientific Co., Ltd.), and 0.1 g of EU-1 seeds (Si/Al molar ratio=25) were added into a mortar one by one and mixed together. After grinding for 5 minutes, the powder mixture was transferred to an autoclave and sealed. After heating at 180° C. for 3 d, the sample was fully crystallized.

[0111] The XRD pattern of the zeolite product obtained in Example 3 which displays the EUO-type framework structure is shown in FIG. 4.

Example 4

Solidothermal Synthesis of ZSM-22

[0112] 1.6 g of solid silica gel (Qingdao Haiyang Chemical Reagent Co., Ltd.), 1.0 g of NH.sub.4F (98%, Aladdin Chemistry Co., Ltd.), and 0.51 g of 1-ethyl-3-methylimidazolium (98%, Shanghai Cheng Jie Chemical Co., Ltd.) were added into a mortar one by one and mixed together. After grinding for 5 minutes, the powder mixture was transferred to an autoclave and sealed. After heating at 180° C. for 3 d, the sample was fully crystallized.

[0113] The XRD pattern of the zeolite product obtained in Example 4 which displays the TON-type framework structure is shown in FIG. 5.

Example 5

Solidothermal Synthesis of ZSM-39

[0114] 1.6 g of solid silica gel (Qingdao Haiyang Chemical Reagent Co., Ltd.), 1.0 g of NH.sub.4F (98%, Aladdin Chemistry Co., Ltd.), and 0.8; g of triethylenediamine (98%, Aladdin Chemistry Co., Ltd.) were added into a mortar one by one and mixed together. After grinding for 5 minutes, the powder mixture was transferred to an autoclave and sealed. After heating at 180° C. for 3 d, the sample was fully crystallized.

[0115] The XRD pattern of the zeolite product obtained in Example 5 which displays the MTN-type framework structure is shown in FIG. 6.

Example 6

Solidothermal Synthesis of B-ZSM-5

[0116] 1.6 g of solid silica gel (Qingdao Haiyang Chemical Reagent Co., Ltd.), 0.15 g of NH.sub.4F (98%, Aladdin Chemistry Co., Ltd.), 0.03 g B.sub.2O.sub.3, and 0.25 g of tetrapropylammonium bromide (98%, Aladdin Chemistry Co., Ltd.) were added into a mortar one by one and mixed together. After grinding for 5 minutes, the powder mixture was transferred to an autoclave and sealed. After heating at 180° C. for 15 h, the sample was fully crystallized. Analysis of the sample via inductively couples plasma (ICP) afforded a silicon to boron molar ratio of 31 for the product.

Example 7

Solidothermal Synthesis of Fe-ZSM-5

[0117] 1.6 g of solid silica gel (Qingdao Haiyang Chemical Reagent Co., Ltd.), 0.3 g of NH.sub.4F (98%, Aladdin Chemistry Co., Ltd.), 0.07 g FeCl.sub.3,and 0.3 g of tetrapropylammonium bromide (98%, Aladdin Chemistry Co., Ltd.) were added into a mortar one by one and mixed together. After grinding for 5 minutes, the powder mixture was transferred to an autoclave and sealed. After heating at 180° C. for 15 h, the sample was fully crystallized. Analysis of the sample via inductively couples plasma (ICP) afforded a silicon to iron molar ratio of 80 for the product.

Example 8

Solidothermal Synthesis of ITQ-13

[0118] 1.6 g of SiO.sub.2, 1.0 g of NH.sub.4F, 0.3 g of hexamethonium bromide, and 0.05 g of ITQ-13 seeds were added into a mortar one by one and mixed together. After grinding for 5 minutes, the powder mixture was transferred to an autoclave and sealed. After heating at 180° C. for 18 h, the sample was fully crystallized. The BET surface area of the product as determined according to ISO 9277:2010 afforded a value of 325 m.sup.2/g, wherein the t-plot of the micropore area afforded a value of 319 m.sup.2/g and the t-plot of the micropore volume a value of 0.15 cm.sup.3/g.

[0119] The XRD pattern of the zeolite product obtained in Example 8 which displays the ITH-type framework structure is shown in FIG. 7.

[0120] Furthermore, the .sup.29Si MAS NMR spectrum as well as the deconvoluted .sup.29Si CP-MAS NMR spectrum of the crystalline product is displayed in FIGS. 8 and 9, respectively. In FIG. 8, peaks are found in the .sup.29Si MAS NMR spectrum at −107,3, −112.5, and −116.3 ppm, respectively.

[0121] In FIG. 9, the deconvolution of the .sup.29Si CP-MAS NMR spectrum afforded peaks at −108.8 ppm (34.6%), −113.6 ppm (58.5%), −117.9 ppm (5.7%), and −103.5 ppm (1.2%), wherein the integration value for the respective peak is indicated in parentheses.

Example 9

Solidothermal Synthesis of ITQ-17

[0122] 1.6 g of SiO.sub.2, 0.5 g of NH.sub.4F, and 1.1 g of triethylenediamine were added into a mortar one by one and mixed together. After grinding for 5 minutes, the powder mixture was transferred to an autoclave and sealed. After heating at 140° C. for 9 d, the sample was fully crystallized. The BET surface area of the product as determined according to ISO 9277:2010 afforded a value of 541 m.sup.2/g, wherein the t-plot of the micropore area afforded a value of 508 m.sup.2/g and the t-plot of the micropore volume a value of 0.24 cm.sup.3/g.

[0123] The XRD pattern of the zeolite product obtained in Example 8 which displays the BEG-type framework structure is shown in FIG. 10, wherein the diffractogram obtained from the product as synthesized is shown as solid black line and the diffractogram obtained from the calcined product is shown as solid grey line.

[0124] Furthermore, the .sup.29Si MAS NMR spectrum of the crystalline product is displayed in FIG. 11.

Example 10

Solidothermal Synthesis of ITQ-12

[0125] 1.6 g of SiO.sub.2, 1.5 g of NH.sub.4F, and 1.5 g of 1,2,3-trimethylimidazolium iodide were added into a mortar one by one and mixed together. After grinding for 5 minutes, the powder mixture was transferred to an autoclave and sealed. After heating at 180° C. for 3 d, the sample was fully crystallized.

[0126] The XRD pattern of the zeolite product obtained in Example 10 which displays the ITW-type framework structure is shown in FIG. 12.