Zeolitic materials and methods for their preparation using alkenyltrialkylammonium compounds

Abstract

The present invention relates to a process for the preparation of a zeolitic material comprising the steps of: (1) providing a mixture comprising one or more sources for YO.sub.2 and one or more alkenyltrialkylammonium cation R.sup.1R.sup.2R.sup.3R.sup.4N.sup.+-containing compounds as structure directing agent; and (2) crystallizing the mixture obtained in step (1) to obtain a zeolitic material;
wherein Y is a tetravalent element, and wherein R.sup.1, R.sup.2, and R.sup.3 independently from one another stand for alkyl; and R.sup.4 stands for alkenyl, as well as to zeolitic materials which may be obtained according to the inventive process and to their use.

Claims

1. A synthetic zeolitic material having an MFI-type framework structure obtained by a process comprising: (1) providing a mixture comprising one or more sources for YO.sub.2 and one or more alkenyltrialkylammonium cation R.sup.1R.sup.2R.sup.3R.sup.4N.sup.+-containing compounds as structure directing agent; and (2) crystallizing the mixture obtained in (1) to obtain a zeolitic material; wherein Y is a tetravalent element, and wherein R.sup.1, R.sup.2, and R.sup.3 are each a propyl group; and R.sup.4 is a 2-propen-1-yl or 1-propen-1-yl group.

2. The synthetic zeolitic material of claim 1 comprising YO.sub.2, wherein Y is a tetravalent element, and X is a trivalent element, said material having an X-ray diffraction pattern comprising at least the following reflections: TABLE-US-00008 Intensity (%) Diffraction angle 2/ [Cu K(alpha 1)] 55-100 7.66-8.20 40-75 8.58-9.05 92-100 22.81-23.34 49-58 23.64-24.18 16-24 29.64-30.21 14-25 44.80-45.25 16-24 45.26-45.67 wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern.

3. The zeolitic material of claim 2, wherein the .sup.29Si MAS NMR of the zeolitic material comprises: a first peak (P1) in the range of from 110.4 to 114.0 ppm; and a second peak (P2) in the range of from 100.2 to 104.2 ppm.

4. The synthetic zeolitic material of claim 1 comprising YO.sub.2 and optionally comprising X.sub.2O.sub.3, wherein Y is a tetravalent element, and X is a trivalent element, said material having an X-ray diffraction pattern comprising at least the following reflections: TABLE-US-00009 Intensity (%) Diffraction angle 2/ [Cu K(alpha 1)] 15-55 7.88-8.16 11-35 8.83-9.13 100 23.04-23.46 27-40 23.68-23.89 21-66 23.90-24.23 22-44 24.29-24.71 wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern.

5. The zeolitic material of claim 4, wherein the .sup.29Si MAS NMR of the zeolitic material comprises: a first peak (P1) in the range of from 110.4 to 114.0 ppm.

6. The zeolitic material of claim 5, wherein the deconvoluted .sup.29Si MAS NMR spectrum comprises one additional peak comprised in the range of from 113.2 to 115.2 ppm.

7. The zeolitic material of claim 5, wherein at least a portion of the Y atoms and/or of the X atoms in the MFI-type framework structure is isomorphously substituted by one or more elements, wherein the one or more elements are selected from the group consisting of B, Fe, Ti, Sn, Ga, Ge, Zr, V, Nb, Cu, Zn, Li, Be, and mixtures of two or more thereof.

8. The zeolitic material of claim 7, wherein a molar ratio of YO.sub.2 to the one or more element ranges from 5 to 100.

9. The zeolitic material of claim 4, wherein the .sup.27AI MAS NMR of the zeolitic material comprises: a first peak (P1) in the range of from 50.00 to 53.50 ppm; and a second peak (P2) in the range of from 0.50 to 2.00 ppm; wherein the integration of the first and second peaks in the .sup.27AI MAS NMR of the zeolitic material offers a ratio of the integration values P1: P2 of 1: (0.5-1.2).

10. The zeolitic material of claim 4, wherein the YO.sub.2: X.sub.2O.sub.3 molar ratio ranges from 2 to 200.

11. The zeolitic material of claim 4, wherein the MFI-type framework structure of the zeolitic material does not contain X.sub.2O.sub.3.

12. The zeolitic material of claim 4, wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof.

13. The zeolitic material of claim 4, wherein X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof.

14. The zeolitic material of claim 4, wherein the zeolitic material comprises one or more cation and/or cationic elements as ionic non-framework elements.

15. The zeolitic material of claim 4, wherein the BET surface area of the zeolitic material determined according to DIN 66135 ranges from 50 to 700 m.sup.2/g.

16. The zeolitic material of claim 1, wherein the zeolitic material is effective in converting at least 80% isopropanol in catalytic decomposition at 200 C.

17. A process for the preparation of a zeolitic material comprising: (1) providing a mixture comprising one or more sources for YO.sub.2 and one or more alkenyltrialkylammonium cation R.sup.1R.sup.2R.sup.3R.sup.4N.sup.+-containing compounds as structure directing agent; and (2) crystallizing the mixture obtained in (1) to obtain a zeolitic material; wherein Y is a tetravalent element, and wherein R.sup.1, R.sup.2, and R.sup.3 are each a propyl group; and R.sup.4 is a 2-propen-1-yl or 1-propen-1-yl group.

18. The process of claim 17, wherein the structure directing agent comprises a hydroxide anion.

19. The process of claim 17, wherein the mixture provided in (1) comprises two R.sup.1R.sup.2R.sup.3R.sup.4N.sup.+-containing compounds, wherein R.sup.4 of the first compound is a 2-propen-1-yl group and R.sup.4 of the second compound is a 1-propen-1-yl group.

20. The process of claim 10, wherein a molar ratio of 2-propen-1-yl to 1-propen-1-yl is from 25:75 to 99:1.

21. The process of claim 17, wherein Y is at least one selected from the group consisting of Si, Sn, Ti, Zr and Ge.

22. The process of claim 17, wherein the one or more sources for YO.sub.2 comprises one or more compounds selected from the group consisting of fumed silica, silica hydrosols, reactive amorphous solid silicas, silica gel, silicic acid, water glass, sodium metasilicate hydrate, sesquisilicate, disilicate, colloidal silica, pyrogenic silica, silicic acid esters, and mixtures of two or more thereof.

23. The process of claim 17, wherein the mixture provided in (1) further comprises one or more sources for X.sub.2O.sub.3, wherein X is a trivalent element.

24. The process of claim 23, wherein X is at least one selected from the group consisting of Al, B, In and Ga.

25. The process of claim 23 or 24, wherein the one or more sources for X.sub.2O.sub.3 comprises one or more compounds selected from the group consisting of aluminum, aluminum alkoxides and alumina.

26. The process of claim 23, wherein the YO.sub.2:X.sub.2O.sub.3 molar ratio of the mixture according to (1) is from 0.5 to 500.

27. The process of claim 23, wherein the mixture of (1) further comprises one or more sources of one or more elements suitable for isomorphous substitution of at least a portion of the Y atoms and/or of the X atoms in the zeolite framework structure.

28. The process of claim 27, wherein the one or more sources for isomorphous substitution comprises one or more titania precursor compounds.

29. The process of claim 27 or 28, wherein the molar ratio of YO.sub.2 to the one or more elements suitable for isomorphous substitution of at least a portion of the Y atoms and/or of the X atoms in the zeolite framework structure is from 1 to 300.

30. The process of claim 17, wherein the mixture provided in (1) does not comprise a source for X.sub.2O.sub.3, wherein X is a trivalent element.

31. The process of claim 17, wherein the mixture according to (1) further comprises one or more solvents, wherein said one or more solvents comprises water.

32. The process of claim 31, wherein a H.sub.2O:YO.sub.2 molar ratio of the mixture is from 3 to 100.

33. The process of claim 17, wherein a molar ratio of the one or more alkenyltrialkylammonium cations R.sup.1R.sup.2R.sup.3R.sup.4N.sup.30 :YO.sub.2 in the mixture is from 0.01 to 5.

34. The process of claim 17, wherein the crystallization in (2) comprises heating of the mixture at a temperature of from 90 to 210 C.

35. The process of claim 34, wherein the crystallization in (2) is conducted under solvothermal conditions.

36. The process of claim 34, wherein the crystallization in (2) comprises heating the mixture for a period of time of from 5 to 120 h.

37. The process of claim 17, wherein the crystallization in (2) comprises agitating the mixture.

38. The process of claim 17 further comprising one or more of the following: (3) isolating the zeolitic material, by filtration, (4) washing the zeolitic material, (5) drying the zeolitic material, 6) subjecting the zeolitic material to an ion-exchange procedure, wherein the isolating, washing, drying and ion exchange can be conducted in any order.

39. The process of claim 38, comprising (6) wherein one or more ionic non-framework elements contained in the zeolite framework is ion-exchanged.

40. The process of claim 17, wherein the zeolitic material formed in (2) comprises one or more zeolites having the MFI-type framework structure.

Description

DESCRIPTION OF THE FIGURES

(1) FIGS. 1a, 2a, 3, 4, and 7 respectively show the X-ray diffraction pattern (measured using Cu K alpha-1 radiation) of the crystalline materials obtained according to Examples 1, 2, 4, 5, and 7. In the figure, the angle 2 theta in is shown along the abscissa and the intensities are plotted along the ordinate.

(2) FIGS. 1b and 2b respectively show the water adsorption/desorption isotherms obtained for the crystalline materials obtained according to Examples 1 and 2, wherein the solid line indicates the adsorption of water into the material, and the dotted line shows the desorption of water from the material. In the figure, the relative humidity in % is shown along the abscissa, whereas the weight-% of water contained in the material based on 100 wt.-% of the sample is plotted along the ordinate.

(3) FIGS. 5 and 6 display the temperature-programmed desorption (NH.sub.3-TPD) obtained for the crystalline material obtained according to Example 5 as well as for a commercial ZSM-5 material, respectively. In the figure, the temperature in C. is shown along the abscissa, and the concentration of desorbed ammonia as measured by the thermal conductivity detector (TCD) is plotted along the ordinate.

(4) FIG. 8 displays the results for the chemical conversion of isopropanol over the crystalline materials obtained according to Examples 4, 5, and 6 compared to commercial ZSM-materials. In the figure, the temperature in C. is shown along the abscissa, and the conversion of isopropanol in % is plotted along the ordinate.

EXAMPLES

(5) X-ray diffraction experiments on the powdered materials were performed using an Advance D8 Series 2 Diffractometer (Bruker/AXS) equipped with a Sol-X detector using the Cu K alpha-1 radiation.

(6) The water adsorption isotherms of the samples were obtained using a VTI SA instrument from TA Instruments following a step-isotherm program. The experiment consisted of a run or a series of runs performed on a sample material that has been placed on the microbalance pan inside of the instrument. Before the measurement were started, the residual moisture of the sample was removed by heating the sample to 100 C. (heating ramp of 5 C./min) and holding it for 6 h under a N.sub.2 flow. After the drying program, the temperature in the cell was decreased to 25 C. and kept isothermal during the measurements. The micro-balance was calibrated, and the weight of the dried sample was balanced (maximum mass deviation 0.01 wt. %). Water uptake by the sample was measured as the increase in weight over that of the dry sample. First, an adsorption curve was measured by increasing the relative humidity (RH) (expressed as weight-% water in the atmosphere inside of the cell) to which the samples was exposed and measuring the water uptake by the sample at equilibrium. The RH was increased with a step of 10 wt. % from 5 to 85% and at each step the system controlled the RH and monitored the sample weight until reaching the equilibrium conditions and recording the weight uptake. The total adsorbed water amount by the sample was taken after the sample was exposed to the 85 weight-% RH. During the desorption measurement the RH was decreased from 85 wt. % to 5 wt. % with a step of 10% and the change in the weight of the sample (water uptake) was monitored and recorded.

(7) .sup.29Si CP-MAS solid-state NMR experiments were performed using a Bruker Avance spectrometer with 300 MHz .sup.1H Larmor frequency (Bruker Biospin, Germany). Samples were packed in 7 mm ZrO.sub.2 rotors, and measured under 5 kHz Magic Angle Spinning at room temperature. .sup.29Si spectra were obtained using .sup.29Si (/2)-pulse excitation with 5 s pulse width, a .sup.29Si carrier frequency corresponding to 62 to 64 ppm in the spectrum, and a scan recycle delay of 120 s. Signal was acquired for 25 ms under 45 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. Spectra were referenced with the polymer Q8M8 as an external secondary standard, by setting the resonance of the trimethylsilyl M group to 12.5 ppm.

(8) BET and pore volume (N.sub.2) of the samples as indicated below were measured following the DIN 66134 procedure and the Hg-porosimetry following the DIN 66133 procedure.

(9) Synthesis of Allyltripropylammoniumhydroxide (ATPAOH)

(10) The synthesis of the organic template ATPAOH was conducted in two steps, wherein in a first step tripropylamine was alkylated with allylchloride. To this effect, 1716 g tripropylamine were placed in an a 6 l glass reactor (HWS) to which 829 g was then added methanol and the mixture heated to 60 C. under stirring. 984 g allylchloride in 300 g methanol was then added over a period of 1.75 h. The reaction mixture was then stirred at 60-70 C. for 24 h.

(11) The solvent was removed by heating at 70 C. under reduced pressure (1 mbar) for obtaining 2495 g of a pale yellowish solid. The product was identified as allyltripropylammonium chloride by .sup.1H, .sup.13C and elementary analysis. The residual content of methanol was determined to be 4.3 wt %, thus affording a yield of 91%. The allyltripropylammonium chloride was then dissolved in 6238 g of distilled water yielding an aqueous solution with a solid content of 40 wt. %.

(12) The aqueous solution thus obtained was then portioned and diluted to a concentration of 8 wt.-%. 5463 g thereof were run through a column which was filled with 3750 ml of a strong base ion exchange resin (Ambersep 900 OH from Dow). The anion of the product was thus changed from chloride to hydroxide. After the loading step, the ion exchange resin was then washed with distilled water (11,456 g) to minimize product loss.

(13) Both, the treated product (now in hydroxide form) and the washing water were collected and then concentrated by evaporation to afford a 40 wt.-% aqueous allytripropylammonium hydroxide solution.

Example 1

Synthesis of TS-1 with ATPAOH (Isomer Ratio 95:5)

(14) In a round bottom flask 500 g of tetraethylorthosilicat (TEOS) was added together with 15 g or tetraethylorthotitanat (TEOTi). 220 g of a solution of ATPAOH (40 wt. %; N-(2-propen-1-yl)-tri-n-propylammonium:N-(1-propen-1-yl)-tri-n-propylammonium molar ratio of 95:5) and 300 g of distilled water were added under stirring to the flask containing the Si and Ti source. A yellow blurry solution is obtained after mixing all the components. After 10 min of stirring the temperature of the slurry was 35 C. and the color of the solution became clear yellow. After 20 min of stirring the temperature reaches 44 C. and the solution became blurry again. After 30 min of stirring the temperature of the slurry reaches 54 C. and it became again a clear yellow solution. After 1 h the hydrolysis of the silica and titanium sources was finished and the temperature of the mixture was constant at 54 C. The ethanol resulted from the hydrolysis of TEOS and TEOTi was than separated by distillation from the synthesis mixture at 95 C. for 2 h. During the distillation procedure, the solution was continuously stirred with 100 U/min, wherein 538 g of ethanol-distillate were obtained.

(15) After the distillation, 603 g of distilled water were added to the synthesis mixture and the solution was stirred for another hour at room temperature. Finally, the suspension was transferred in a 2.5 L stainless steel autoclave equipped with mechanical stirring. The autoclave was heated to 175 C. and kept for 16 h under continuous stirring (200 U/min).

(16) After 16 h the autoclave was cooled to room temperature and distilled water was added to the suspension in a volumetric ratio of 1:1 (pH of the solution 12.1). The pH was reduced to 7.2 by adding a solution of 5 wt. % HNO.sub.3. The suspension was than filtered on a Bchner filter and the solid was washed several times with water. The white solid was dried for 4 h at 120 C. and calcined for 5 h at 490 C. under air, using the following calcination program: heating within 60 min to 120 C., temperature held for 240 min at 120 C., then heating within 370 min from 120 to 490 C. and temperature held for 300 min at 490 C.

(17) The characterization of the final product by XRD as shown in FIG. 1 a shows that the product has the typical MFI structure characteristic of the TS-1 (100% crystallinity and less than 0.5% Anatas crystallites). The ICP analysis indicated an elemental composition of Si (43 wt. %) and Ti (1.9 wt. %). The N.sub.2 adsorption isotherm measurements indicated that the material has Langmuir surface area of 584 m.sup.2/g and BET surface area of 429 m.sup.2/g and a pore volume of 0.94 mL/g (based on Hg-porosimetry).

(18) The water adsorption isotherm of the sample is shown in FIG. 1b.

Example 2

Synthesis of TS-1 with ATPAOH (Isomer Ratio 50:50)

(19) The procedure of Example 1 was repeated, wherein 520 g of a 20 wt.-% of ATPAOH solution was employed having a N-(2-propen-1-yl)-tri-n-propylammonium:N-(1-propen-1-yl)-tri-n-propylannmonium molar ratio of 50:50, and no distilled water was added for providing the initial mixture in the round bottom flask prior to the distillation of ethanol.

(20) The characterization of the final product by XRD as shown in FIG. 2a shows that the product has the typical MFI structure characteristic of the TS-1 (91% crystallinity). The ICP analysis indicated an elemental composition of Si (44 wt. %) and Ti (2.0 wt. %). The N.sub.2 adsorption isotherm measurements indicated that the material has a BET surface area of 436 m.sup.2/g.

(21) The water adsorption isotherm of the sample is shown in FIG. 2b.

Example 3

Synthesis of TS-1 with ATPAOH (Isomer Ratio 50:50)

(22) The procedure of Example 1 was repeated, wherein 327 g of a 27 wt.-% of ATPAOH solution was employed having a N-(2-propen-1-yl)-tri-n-propylammonium:N-(1-propen-1-yl)-tri-n-propylammonium molar ratio of 50:50, and 193 g of distilled water were added for providing the initial mixture in the round bottom flask prior to the distillation of ethanol.

(23) The characterization of the final product by XRD revealed that the product has the typical MFI structure characteristic of the TS-1 (92% crystallinity). The ICP analysis indicated an elemental composition of Si (44 wt. %) and Ti (2.0 wt. %). The N.sub.2 adsorption isotherm measurements indicated that the material has a BET surface area of 437 m.sup.2/g.

Example 4

Synthesis of High-Silica ZSM-5 with ATPAOH (Isomer Ratio 95:5)

(24) 137.6 ml of 20 wt-% ATPAOH (N-(2-propen-1-yl)-tri-n-propylammonium:N-(1-propen-1-yl)-tri-n-propylammonium molar ratio of 95:5) in distilled H.sub.2O was mixed in a 600 ml flask with Aerosil 200 (32.38 g). The mixture was stirred for 15 minutes. The dispersion was then transferred to a 0.25 L autoclave with a teflon inlay, which was afterwards heated to 150 C. for 120 h. After cooling, the solid formed was repeatedly washed with distilled water and dried at 120 C. for 16 h, for obtaining 31.2 g of a white powder which was then calcined 490 C. for 5 h. The molar yield based on SiO.sub.2 was calculated to 95%.

(25) The characterization of the material with a an average crystal size of 100 nm +/20 nm by means of XRD as displayed in FIG. 3 shows a pure MFI structured material (100% crystallinity). The material has a BET surface area of 406 m.sup.2/g, a Langmuir surface area of 556 m.sup.2/g, a pore volume of 0.178 cm.sup.3/g and a median pore width of 0.58 nm. The elemental analysis showed a carbon content of 0.063 wt-% sample. By means of SEM no side phase could be observed in the product.

(26) The .sup.29Si MAS NMR of the zeolitic material displays peaks at 102.4 and 112.1 ppm, wherein the integration of the peaks offers relative intensities of 0.575 and 1 for the signals, respectively. In the .sup.29Si CP-MAS NMR of the zeolitic material, peaks are observed at 92.4, 102.4 and 111.8 ppm, wherein the integration of the peaks offers relative intensities of 0.176, 1.869 and 1 for the signals, respectively.

Example 5

Synthesis of ZSM-5 with ATPAOH (Isomer Ratio 95:5) Using Sodium Aluminate

(27) 136.9 ml of 20 wt-% ATPAOH (N-(2-propen-1-yl)-tri-n-propylammonium:N-(1-propen-1-yl)-tri-n-propylammonium molar ratio of 95:5) in distilled H.sub.2O was mixed in a 600 ml flask with Aerosil 200 (32.00 g) and NaAlO.sub.2 (2.02 g). The mixture was stirred for 15 minutes. The dispersion was transferred to a 0.25 L autoclave with a teflon inlay, which was afterwards heated to 150 C. for 120 h. After cooling, the formed solid was repeatedly washed with distilled water and dried at 120 C. for 16 h, for obtaining 30.2 g of a yellowish powder which was then calcined at 490 C. for 5 h. The molar yield based on SiO.sub.2 was calculated to 92%.

(28) The characterization of the material with a an average crystal size of 48.5 nm +/10 nm by means of XRD as displayed in FIG. 4 shows a pure MFI structured material (100% crystallinity). The material has a BET surface area of 392 m.sup.2/g, a Langmuir surface area of 534 m.sup.2/g, a pore volume of 0.171 cm.sup.3/g and a median pore width of 0.77 nm. The elemental analysis showed 40wt-% Si, 1.6 wt-% Al, 0.069 wt-% C and 0.46 wt-% Na in the sample, thus affording an Si:Al atomic ratio (SAR) of 24. By means of SEM no side phase could be observed in the product.

(29) The .sup.29Si MAS NMR of the zeolitic material displays peaks at 107.0 and 113.5 ppm, wherein the integration of the peaks offers relative intensities of 0.155 and 1 for the signals, respectively. In the .sup.29Si CP-MAS NMR of the zeolitic material, peaks are observed at 91.6, 102.0 and 111.3 ppm, wherein the integration of the peaks offers relative intensities of 0.122, 1.663 and 1 for the signals, respectively.

(30) The .sup.27Al MAS NMR of the zeolitic material displays peaks at 50.9 and 1.3 ppm, wherein the integration of the peaks offers relative intensities of 1 and 0.453 for the signals, respectively.

(31) The ammonia temperature-programmed desorption (NH.sub.3-TPD) of the material obtained was measured and the results are displayed in FIG. 5, affording a value of 0.71 mmol H.sup.+/g. For comparison, the NH.sub.3-TPD of a commercial ZSM-5 zeolite (PZ2-50/H obtained from Zeochem) having a similar Si:Al atomic ratio of 25 is displayed in FIG. 6, and affords a value of 0.93 mmol H.sup.+/g. As may be taken from FIGS. 5 and 6, the samples display similar types of acid sites, yet quite surprisingly the inventive material displays an overall lower number of acidic sites although the alumina content of both materials is comparable.

Example 6

Synthesis of ZSM-5 with ATPAOH (Isomer Ratio 95:5) Using Aluminum Hydroxide

(32) 136.9 ml of 20 wt-% ATPAOH (N-(2-propen-1-yl)-tri-n-propylammonium:N-(1-propen-1-yl)-tri-n-propylammonium molar ratio of 95:5) in distilled H.sub.2O was mixed in a 600 ml flask with Aerosil 200 (32.00 g) and Al(OH)3 (0.84 g). The mixture was stirred for 15 minutes. The dispersion was transferred to a 0.25 L autoclave with a teflon inlay, which was afterwards heated to 150 C. for 120 h. After cooling, the formed solid was repeatedly washed with distilled water and dried at 120 C. for 16 h. 30.5 g of a yellowish powder was received which was calcined at 490 C. for 5 h. The molar yield based on SiO.sub.2 was calculated to 93%.

(33) The characterization of the powder with an average crystal size of 87 nm +/17 nm by means of XRD a pure MFI structured material (97% crystallinity). The material has a BET surface area of 430 m.sup.2/g, a Langmuir surface area of 574 m.sup.2/g, a pore volume of 0.178 cm.sup.3/g and a median pore width of 0.63 nm. The elemental analysis showed 40wt-% Si, 0.67 wt-% Al and 0.22 wt-% C in the sample, thus affording an Si:Al atomic ratio (SAR) of 57. By means of SEM no other side phases could be observed in the product.

(34) The .sup.29Si MAS NMR of the zeolitic material displays peaks at 105.0 and 113.5 ppm, wherein the integration of the peaks offers relative intensities of 0.156 and 1 for the signals, respectively. In the .sup.29Si CP-MAS NMR of the zeolitic material, peaks are observed at 91.1, 102.1 and 111.8 ppm, wherein the integration of the peaks offers relative intensities of 0.148, 1.919 and 1 for the signals, respectively.

(35) The .sup.27Al MAS NMR of the zeolitic material displays peaks at 52.3 and 1.1 ppm, wherein the integration of the peaks offers relative intensities of 1 and 0.008 for the signals, respectively.

Example 7

Synthesis of ZSM-5 with ATPAOH Using Aluminum Sulfate

(36) 333 ml of 40 wt-% ATPAOH (N-(2-propen-1-yl)-tri-n-propylammonium:N-(1-propen-1-yl)-tri-n-propylammonium molar ratio of 95:5) in H.sub.2O was stirred with tetraethylorthosilicate (757 g) and distilled H.sub.2O (470 g) for 60 min at room temperature. Afterwards 746 g of ethanol were removed at 95 C. from the reaction gel by distillation. After cooling down, 746 g H.sub.2O as well as Al.sub.2(SO.sub.4).sub.3* 18 H.sub.2O (24.3 g) dissolved in 20 ml distilled H.sub.2O were added. The dispersion was transferred into a 2.5 L autoclave, which was then heated to 155 C. for 24 h. After cooling down to room temperature, the formed solid was repeatedly washed with distilled water and dried at 120 C. for 16 h, 210 g of a white powder was obtained. The organic residuals were removed by calcination at 500 C. for 6 h.

(37) The characterization of the material with a an average crystal size of 83 nm +/20 nm by means of XRD as displayed in FIG. 7 shows a pure MFI structured material. The material has a surface area of 407 m.sup.2/g (BET), a pore volume of 0.190 cm.sup.3/g and a median pore width of 0.59 nm. The elemental analysis showed 41wt-% Si, 0.76wt-% Al in the sample. By means of SEM and XRD no other side phases could be observed in the product.

(38) Hydrophobic/Hydrophilic Properties

(39) For the TS-1 materials of Examples 1, 2, and 3, the water adsorption isotherms were determined, wherein the adsorption/desorption isotherms for the samples of Examples 1 and 2 are displayed in FIGS. 1b and 2b, respectively. As may be taken from the figures, the water adsorption reaches 2.9 wt.-% for the sample of Example 1, and 8.3 wt.-% for the sample of Example 2. Measurement of the water adsorption isotherm for the sample of Example 3 displays an adsorption reaching 8.7 wt.-%.

(40) For comparison, the water adsorption isotherm was determined for a comparable TS-1 sample (Ti: 1.9 wt.-%; Si: 43 wt.-%; BET surface area: 471 m.sup.2/g) obtained using tetrapropyl ammonium as the organotemplate and afforded a water adsorption reaching 10.2 wt.-%. Accordingly, it has quite unexpectedly been found that the materials of the present invention obtained by using the ATPAOH organotemplate are considerably more hydrophobic than a comparable material obtained using tetrapropyl ammonium hydroxide (TPAOH). Furthermore, it may be observed that a higher value of the N-(2-propen-1-yl)-tri-n-propylammonium:N-(1-propen-1-yl)-tri-n-propylammonium molar ratio used in the synthesis of the inventive samples leads to a higher hydrophobicity of the resulting zeolitic material. Thus, the present invention quite unexpectedly provides a material which may be clearly distinguished by its chemical and physical properties from materials obtained using a corresponding alkenyltrialkylammonium organotemplate having only saturated alkyl groups. Furthermore, it has quite surprisingly been found that even a controlled variation of the unique chemical and physical properties of the inventive materials is possible according to the inventive process for their production, offering a unique versatility for chemical applications, in particular in the field of catalysis.

(41) Catalytic Testing

(42) For testing the catalytic behavior of the inventive materials, isopropanol decomposition reactions were performed on the inventive ZSM-5 materials of Examples 4, 5, and 6 as well as on the commercial ZSM-5 materials PZ2-25/H and PZ2-50/H displaying Si:Al atomic ratios (SAR) of 17 and 25, respectively. The test runs were performed at room temperature (no activity) and at temperatures in the range of from 200 to 350 C.

(43) The results from the respective test runs are shown in FIG. 8. In particular, it is apparent from the test results that based on the SAR of the samples, the inventive samples display a considerably higher activity than commercial samples obtained from syntheses using other organotemplates than according to the present invention. This is particularly apparent when comparing the results for Example 5 and PZ2-50/H, the inventive example displaying practically complete conversion at a temperature of around 200 C., wherein the same result is only achieved by the commercial sample at 300 C.

(44) Cited Prior Art Documents U.S. Pat. No. 3,702,886 U.S. Pat. No. 4,410,501 US 2007/0135637 A1 US 2008/0000354 A1 U.S. Pat. No. 8,007,763 B2 WO 2008/083045 A2 WO 2007/021404 A1 U.S. Pat. No. 4,544,538