PROCESS FOR THE PREPARATION OF A DEALUMINATED ZEOLITIC MATERIAL HAVING THE BEA FRAMEWORK STRUCTURE

Abstract

The present invention relates to a method for the preparation of a treated zeolitic material having a BEA framework structure comprising the steps of: (i) providing a zeolitic material having a BEA framework structure, wherein the BEA framework structure comprises YO2 and X2O3, wherein Y is a tetravalent element, and X is a trivalent element, and wherein the zeolitic material having a BEA framework structure is obtainable and/or obtained from an organotemplate-free synthetic process; (ii) calcining the zeolitic material provided in step (i) at a temperature of 650 C. or more; and (iii) treating the calcined zeolitic material obtained from step (ii) with an aqueous solution having a pH of 5 or less, as well as to zeolitic materials per se preferably obtainable according to the inventive method and to their use, and to a process for converting oxygenates to olefins employing the inventive zeolitic materials.

Claims

1. A method for the preparation of a treated zeolitic material having a BEA framework structure comprising the steps of: (i) providing a zeolitic material having a BEA framework structure, wherein the BEA framework structure comprises YO.sub.2 and X.sub.2O.sub.3, wherein Y is a tetravalent element, and X is a trivalent element, and wherein the zeolitic material having a BEA framework structure is obtainable and/or obtained from an organotemplate-free synthetic process; (ii) calcining the zeolitic material provided in step (i) at a temperature of 650 C. or more; and (iii) treating the calcined zeolitic material obtained from step (ii) with an aqueous solution having a pH of 5 or less.

2. The method of claim 1, wherein in step (ii) the zeolitic material provided in step (i) is calcined at a temperature comprised in the range of from 680 C. to 1000 C.

3. The method of claim 1, wherein calcining in step (ii) is conducted in an atmosphere containing 10 wt.-% or less of water.

4. The method of claim 1, wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ta, Fe, Ge, and combinations of two or more thereof.

5. The method of claim 1, wherein X is selected from the group consisting of Al, B, In, Ga, and combinations of two or more thereof.

6. The method of claim 1, wherein the zeolitic material provided in step (i) is non-calcined.

7. A zeolitic material having a BEA framework structure obtainable and/or obtained according to a method as defined in claim 1.

8. A zeolitic material having a BEA framework structure having an X-ray diffraction pattern comprising at least the following reflections: TABLE-US-00022 Intensity (%) Diffraction angle 2/ [Cu K(alpha 1)] [8-46] [21.49-21.79] 100 [22.55-22.85] [7-37] [25.45-25.75] [5-30] [27.10-27.40] [4-23] [28.96-29.26] [4-23] [29.75-30.05] [2-14] [33.64-33.94] wherein 100% relates to the intensity of the maximum peak in the X-ray diffraction pattern, and wherein the BEA framework structure comprises YO.sub.2 and X.sub.2O.sub.3, wherein Y is a tetravalent element, and X is a trivalent element.

9. The zeolitic material of claim 8, wherein the .sup.29Si MAS NMR spectrum of the zeolitic material comprises: one or more peaks (P1) in the range of from 95 to 104.5 ppm; and one or more peaks (P2) in the range of from 105 to 116 ppm; wherein the ratio of the total integration value of the one or more peaks (P1) to the one or more peaks (P2) is comprised in the range of from 19:81 to 35:65.

10. A zeolitic material having a BEA framework structure, wherein the BEA framework structure comprises YO.sub.2 and X.sub.2O.sub.3, wherein Y is a tetravalent element, and X is a trivalent element, and wherein the .sup.27Al MAS NMR of the zeolitic material comprises: a first peak (P1) in the range of from 45 to 65 ppm; a second peak (P2) in the range of from 11 to 44 ppm; and a third peak (P3) in the range of from 10 to 10 ppm; wherein the integration of the first, second, and third peaks in the .sup.27Al MAS NMR of the zeolitic material offers ratios of the integration values P1:P2:P3 comprised in the range of from 1:(0.1-0.8):(0.4-0.9).

11. The zeolitic material of claim 10, wherein the zeolitic material is obtainable and/or obtained according to the steps of: (i) providing a zeolitic material having a BEA framework structure, wherein the BEA framework structure comprises YO.sub.2 and X.sub.2O.sub.3, wherein Y is a tetravalent element, and X is a trivalent element, and wherein the zeolitic material having a BEA framework structure is obtainable and/or obtained from an organotemplate-free synthetic process; and (ii) calcining the zeolitic material provided in step (i) at a temperature of 650 C. or more.

12. The zeolitic material of claim 8, wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ta, Fe, Ge, and combinations of two or more thereof.

13. The zeolitic material of claim 8, wherein X is selected from the group consisting of Al, B, In, Ga, and combinations of two or more thereof.

14. A process for converting oxygenates to olefins, comprising: (1) providing a gas stream comprising one or more oxygenates; (2) contacting the gas stream with a catalyst comprising a zeolitic material according to claim 7.

15. (canceled)

Description

DESCRIPTION OF THE FIGURES

[0143] FIGS. 1, 2a, 3a, 4a, 5a, 6a, 7a, 8a, 9a, 10a, 11a, 12a, 13a, 14a, 15a, and 16a respectively display the X-ray diffractions pattern using the samples from Reference Examples 1-5, Examples 6-14, and Comparative Examples 15 and 16 which was measured with a wavelength of 1.54060 . The abscissa axis represents the reflection angle 2-Theta or 2 in 2theta, and the ordinate axis the measured intensity in the dimensionless unit counts.

[0144] FIGS. 2b, 3b, 4b, and 5b respectively display the .sup.27Al MAS NMR spectra obtained using the samples from Reference Examples 2-5. In the figures, the values in ppm are plotted along the abscissa, and the signal intensity in arbitrary units is plotted along the ordinate, respectively.

[0145] FIGS. 2c, 3c, 4c, 5c, 6b, 7b, 8b, 9b, 10b, 11 b, 12b, 13b, 14b, 15b, and 16b respectively display the .sup.29Si MAS NMR spectra obtained using the samples from Reference Examples 2-5, Examples 6-14, and Comparative Examples 15 and 16. In the figures, the values in ppm are plotted along the abscissa, and the signal intensity in arbitrary units is plotted along the ordinate, respectively.

[0146] FIGS. 11c, 11d, 13c, 14c, 15c, 16c respectively display the results from methanol-to-olefin (MTO) catalytic testing obtained using the samples from Reference Examples 11, 13, and 14, and Comparative Examples 15 and 16. In the figures, the time on stream in hours is plotted along the abscissa, and the conversion rate in % as well as the selectivities in % relative to specific compounds in the product stream including propene .square-solid. and butene .diamond-solid. are plotted along the ordinate.

EXPERIMENTAL SECTION

[0147] Powder XRD patterns were collected on a Rint-Ultima III (Rigaku) using a Cu K X-ray source (40 kV, 20 mA). Sample preparation for XRD was done by typical method using slide glass. First, sample was well grained using a mortar. Then it was put on slide glass, and it was pressed flat with a slide glass.

[0148] .sup.27Al MAS NMR: Solid-state .sup.27Al MAS NMR spectra of these samples were recorded on a JEOL ECA-600 spectrometer at a resonance frequency of 156.4 MHz using a 4 mm sample rotor with a spinning rate of 15.0 kHz. The spectra were recorded with single-pulse acquisition at ambient temperature using /2 pulse and a recycle delay of 0.5 s and accumulating 2000 scans. For .sup.27Al MAS NMR, Chemical shifts were referenced relative to an aqueous Al(NO.sub.3).sub.3 solution. To deconvolute the spectra and integrate the peak areas, Alice2 Ver. 6.1 (JEOL) was used.

[0149] .sup.29Si MAS NMR: Solid-state .sup.29Si MAS NMR spectra were measured on a JEOL ECA-400 spectrometer at a resonance frequency of 79.5 MHz using a 6 mm sample rotor with a spinning rate of 5.5 kHz. The spectra were recorded with single-pulse acquisition at ambient temperature using /2 pulse and a recycle delay of 60 s and accumulating 1000 scans. The calcined samples were allowed to be cooled to ambient temperature and then stored in glass vessel. The acid-treated samples were dried overnight and stored in the same way. These samples were not further treated prior to the measurement of NMR spectra. For .sup.29Si MAS NMR, Chemical shifts were referenced relative to tetramethylsilane. To deconvolute the spectra and integrate the peak areas, Alice2 Ver. 6.1 (JEOL) was used.

Reference Example 1: Organotemplate-Free Synthesis of Zeolite Beta

[0150] 335.1 g of NaAlO.sub.2 were dissolved in 7314 g of H.sub.2O while stirring, followed by addition of 74.5 g of zeolite Beta seeds (commercially obtained from Zeolyst International, product name: CP814C. Prior to the synthesis, the product was calcined at 500 C. for 5 h (heating ramp 1 C./min to obtain the H-Form)). The mixture was placed in a 20 L autoclave together with 7340 g sodium waterglass and 1436 g Ludox AS40, affording an aluminosilicate gel with a molar ratio of 1.00 SiO.sub.2:0.042 Al.sub.2O.sub.3:0.57 Na.sub.2O:17.5 H.sub.2O. Crystallization took place at 120 C. for 117 h. After the reaction mixture was cooled down to room temperature, the solid was separated by filtration, repeatedly washed with distilled water and then dried at 120 C. for 16 h affording 1337 g of a white crystalline product. Chemical analysis indicated an SiO.sub.2: Al.sub.2O.sub.3 molar ratio of 10.89 and 6.7 wt-% of Na.sub.2O on a calcined basis.

[0151] 1000 g sodium form of the crystalline product was added into 10,000 g of a 10 wt % solution of ammonium nitrate. The suspension was heated to 80 C. and kept at this temperature under continuous stirring for 2 h. The solid was filtered hot (without additional cooling) over a filter press. The filter cake then was then washed with distilled water (room temperature wash water) until the conductivity of the wash water was below 200 S cm.sup.1. The filter cake was dried for 16 h at 120 C. This procedure was repeated once, affording the ion-exchanged crystalline product in its ammonium form. Chemical analysis indicated an SiO.sub.2: Al.sub.2O.sub.3 molar ratio of 10.51 and 6.7 wt-% of Na.sub.2O on a calcined basis.

[0152] The following values obtained from the X-ray diffractogram (cf. FIG. 1) indicated that a BEA-type framework structure has been obtained.

TABLE-US-00007 Angle Intensity [2-Theta ] [%] 6.475 6 7.058 22.1 7.616 35.3 9.7 7.8 11.776 5 12.743 6.5 13.247 8.9 14.42 6.7 17.895 5.6 19.599 5 20.021 5.8 21.152 18.7 22.207 100 22.488 18.6 24.471 6.3 25.093 16.1 25.672 9 26.309 5.2 26.771 13.6 27.593 6.3 28.525 14.2 29.297 21.5 30.136 9.3 30.543 5.4 30.911 5 33.055 9.4

[0153] To convert the NH.sub.4-form into H-form, the sample was treated by a calcination step at 500 C. for 5 h (heat ramp 1 C./min). Chemical analysis indicated an Si/Al molar ratio of 5.0 and <0.1 wt-% of Na.sub.2O on a calcined basis.

[0154] .sup.27Al MAS NMR analysis revealed the following signal intensities in %: 50-60 ppm (Tetra-coordinated Al-sites) 100.0%, 15-45 ppm (Penta-coordinated Al-sites) 0.0%, 10-10 ppm (Hexa-coordinated Al-sites) 0.0%.

Reference Example 2: Calcination of Zeolite Beta at 800 C. for 24 h

[0155] For calcination, the NH.sub.4-form of zeolite beta obtained in Reference Example 1 was taken as starting material. The white powder was heated in a muffle furnace with 3K/min to 800 C. under air. The temperature was held constant for 24 h. Afterwards, the sample was cooled down to room temperature. Chemical analysis indicated an Si/Al molar ratio of 5.0 and <0.1 wt-% of Na.sub.2O on a calcined basis.

[0156] The X-ray diffraction pattern of the sample obtained is displayed in FIG. 2a. The BET surface area was measured by means of nitrogen sorption at 77K and afforded a value of 611 m.sup.2/g. .sup.27Al MAS NMR analysis (cf. FIG. 2b) revealed the following signal intensities in %: 50-60 ppm (Tetra-coordinated Al-sites) 45.3%, 15-45 ppm (Penta-coordinated Al-sites) 23.5%, 10-10 ppm (Hexa-coordinated Al-sites) 31.1%. The .sup.29Si MAS NMR of the sample obtained is displayed in FIG. 2c and revels the following signal intensities in %: 102 ppm (Q4 (1Al)+Q3) 26%, 15-108 ppm (Q4 (0Al, T3-T9)) 61%, 112 ppm (Q4 (0Al, T1-T2)) 9%.

Reference Example 3: Calcination of Zeolite Beta at 750 C. for 15 h

[0157] For calcination, the NH.sub.4-form of zeolite beta obtained in Reference Example 1 was taken as starting material. The white powder was heated in a muffle furnace with 3K/min to 750 C. under air. The temperature was held constant for 15 h. Afterwards, the sample was cooled down to room temperature. Chemical analysis indicated a Si/Al ratio of 5.0 and <0.1 wt-% of Na.sub.2O on a calcined basis. The BET surface area was measured by means of nitrogen sorption at 77K affording a value of 604 m.sup.2/g.

[0158] The X-ray diffraction pattern of the sample obtained is displayed in FIG. 3a, and displays the following reflections and corresponding intensities:

TABLE-US-00008 Angle Intensity [2-Theta ] [%] 3.39 12.2 6.603 12 7.134 34.3 7.694 50.8 9.817 11.7 11.782 8.7 13.346 13.4 13.57 7.4 14.508 10.5 18.202 8.1 20.154 9.5 21.345 22.1 21.703 14.3 22.4 100 22.641 27.1 24.435 9.2 24.762 9.4 25.297 16 25.966 10 26.948 14.4 27.93 8 28.643 13.6 29.297 34.7 29.536 14.2 30.413 8.1 30.83 6.9 32.465 6 33.358 8.2 36.124 5.6

[0159] .sup.27Al MAS NMR analysis (see FIG. 3b) revealed the following signal intensities in %: 50-60 ppm (Tetra-coordinated Al-sites) 50.7%, 15-45 ppm (Penta-coordinated Al-sites) 16.1%, 10-10 ppm (Hexa-coordinated Al-sites) 33.1%. The .sup.29Si MAS NMR of the sample obtained is displayed in FIG. 3c and revels the following signal intensities in %: 102 ppm (Q4 (1Al)+Q3) 26%, 15-108 ppm (Q4 (0Al, T3-T9)) 63%, 112 ppm (Q4 (0Al, T1-T2)) 8%.

Reference Example 4: Calcination of Zeolite Beta at 750 C. for 5 h

[0160] For calcination, the NH.sub.4-form of zeolite beta obtained in Reference Example 1 was taken as starting material. The white powder was heated in a muffle furnace with 3K/min to 750 C. under air. The temperature was held constant for 5 h. Afterwards, the sample was cooled down to room temperature. Chemical analysis indicated an Si/Al molar ratio of 5.0 and <0.1 wt-% of Na.sub.2O on a calcined basis. The BET surface area was measured by means of nitrogen sorption at 77K afforded a value of 644 m.sup.2/g.

[0161] The X-ray diffraction pattern of the sample obtained is displayed in FIG. 4a, and displays the following reflections and corresponding intensities:

TABLE-US-00009 Angle Intensity [2-Theta ] [%] 7.155 34.1 7.714 49.6 9.826 11.5 11.952 9.2 13.383 12.6 13.669 7.5 14.364 9.6 14.514 10.8 15.414 6 18.235 8.1 20.224 9 21.383 20.8 21.692 13.6 22.406 100 22.66 27.8 24.708 9.4 25.299 16.4 25.991 10 26.958 15.3 27.903 8.1 28.747 14.8 29.535 15.6 30.424 8.9 30.93 7.2 32.651 6.6 33.394 8.9 34.677 5.2 36.162 6.1

[0162] .sup.27Al MAS NMR analysis (see FIG. 4b) revealed the following signal intensities in %: 50-60 ppm (Tetra-coordinated Al-sites) 56.5%, 15-45 ppm (Penta-coordinated Al-sites) 9.9%, 10 10 ppm (Hexa-coordinated Al-sites) 33.5%. The .sup.29Si MAS NMR of the sample obtained is displayed in FIG. 4c and revels the following signal intensities in %: 102 ppm (Q4 (1Al)+Q3) 26%, 15-108 ppm (Q4 (0Al, T3-T9)) 56%, 112 ppm (Q4 (0Al, T1-T2)) 7%.

Reference Example 5: Calcination of Zeolite Beta at 700 C. for 5 h

[0163] For calcination, the NH.sub.4-form of zeolite beta obtained in Reference Example 1 was taken as starting material. The white powder was heated in a muffle furnace with 3K/min to 700 C. under air. The temperature was held constant for 5 h. Afterwards, the sample was cooled down to room temperature. Chemical analysis indicated an Si/Al molar ratio of 5.0 and <0.1 wt-% of Na.sub.2O on a calcined basis. The BET surface area was measured by means of nitrogen sorption at 77K and afforded a value of 660 m.sup.2/g.

[0164] The X-ray diffraction pattern of the sample obtained is displayed in FIG. 5a, and displays the following reflections and corresponding intensities:

TABLE-US-00010 Angle Intensity [2-Theta ] [%] 7.065 26.4 7.65 38.7 9.745 9 11.856 7.7 13.302 10.8 13.562 6.3 14.487 9.4 18.077 7.5 20.172 8.7 21.293 20.2 22.346 100 22.592 26.7 24.451 9.2 25.198 16.2 25.853 10.7 26.848 15.9 27.774 8.5 28.689 15.6 29.405 16.2 30.35 9.3 30.777 7.8 32.439 7.1 33.277 9.6 34.542 5.4 36.082 6.3 37.317 5.4

[0165] .sup.27Al MAS NMR analysis (see FIG. 5b) revealed the following signal intensities in %: 50-60 ppm (Tetra-coordinated Al-sites) 71.9%, 15-45 ppm (Penta-coordinated Al-sites) 1.2%, 10 10 ppm (Hexa-coordinated Al-sites) 26.9%. The .sup.29Si MAS NMR of the sample obtained is displayed in FIG. 5c and revels the following signal intensities in %: 102 ppm (Q4 (1Al)+Q3) 36%, 15-108 ppm (Q4 (0Al, T3-T9)) 49%, 112 ppm (Q4 (0Al, T1-T2)) 7%.

Example 6: Acid Treatment (1M) of Calcined Zeolite Beta (700 C./5 h) for 24 h at Ambient Temperature

[0166] The calcined sample obtained from Reference Example 5 was taken as starting material. 1 g of the white powder was dispersed in 50 ml 1 M nitric acid solution in H.sub.2O and stirred in a round bottom flask at 25 C. for 24 hours. Afterwards the solid was extracted by vacuum filtration and subsequent washing with deionized H.sub.2O until a pH of 7 was reached. Finally the obtained white powder was dried for 12 hours at 100 C. under air in a muffle furnace. Chemical analysis indicated an Si/Al molar ratio of 75 and <0.1 wt-% of Na.sub.2O on a calcined basis. The BET surface area was measured by means of nitrogen sorption at 77K afforded a value of 386 m.sup.2/g.

[0167] The X-ray diffraction pattern of the sample obtained is displayed in FIG. 6a, and displays the following reflections and corresponding intensities:

TABLE-US-00011 Angle Intensity [2-Theta ] [%] 7.065 26.4 7.65 38.7 9.745 9 11.856 7.7 13.302 10.8 13.562 6.3 14.487 9.4 18.077 7.5 20.172 8.7 21.293 20.2 22.346 100 22.592 26.7 24.451 9.2 25.198 16.2 25.853 10.7 26.848 15.9 27.774 8.5 28.689 15.6 29.405 16.2 30.35 9.3 30.777 7.8 32.439 7.1 33.277 9.6 34.542 5.4 36.082 6.3 37.317 5.4

[0168] The .sup.29Si MAS NMR of the sample obtained is displayed in FIG. 6b and revels the following signal intensities in %: 102 ppm (Q4 (1Al)+Q3) 44%, 15-108 ppm (Q4 (0Al, T3-T9)) 38%, 112 ppm (Q4 (0Al, T1-T2)) 13%.

Example 7: Acid Treatment (1 M) of Calcined Zeolite Beta (750 C./15 h) for 2 h Under Reflux

[0169] The calcined sample obtained from Reference Example 3 was taken as starting material. 1 g of the white powder was dispersed in 50 ml 1 M nitric acid solution in H.sub.2O and stirred in a round bottom flask at 100 C. under reflux for 2 hours. Afterwards the solid was extracted by vacuum filtration and subsequent washing with DI H.sub.2O until a pH of 7 was reached. Finally the obtained white powder was dried for 12 hours at 100 C. under air in a muffle furnace. Chemical analysis indicated a Si/Al ratio of 98 and <0.1 wt-% of Na.sub.2O on a calcined basis. The BET surface area was measured by means of nitrogen sorption at 77K of 571 m.sup.2/g.

[0170] The X-ray diffraction pattern of the sample obtained is displayed in FIG. 7a, and displays the following reflections and corresponding intensities:

TABLE-US-00012 Angle Intensity [2-Theta ] [%] 3.613 30.1 7.311 42.1 7.9 56.7 9.757 25.1 13.601 23.9 14.965 30.2 18.624 24.9 19.791 27.2 22 44.9 23.05 100 25.951 37.7 26.545 27.5 27.332 26.5 27.492 28.2 29.5 20.8 30.271 20 31.234 17.7 34.301 13.8

[0171] The .sup.29Si MAS NMR of the sample obtained is displayed in FIG. 7b and revels the following signal intensities in %: 102 ppm (Q4 (1Al)+Q3) 36%, 15-108 ppm (Q4 (0Al, T3-T9)) 42%, 112 ppm (Q4 (0Al, T1-T2)) 19%.

Example 8: Acid Treatment (6M) of Zeolite Beta (750 C./5 h) for 24 h Under Reflux

[0172] The calcined sample obtained from Reference Example 4 was taken as starting material. 1 g of the white powder was dispersed in 50 ml 6 M nitric acid solution in H.sub.2O and stirred in a round bottom flask at 100 C. under reflux for 24 hours. Afterwards the solid was extracted by vacuum filtration and subsequent washing with deionized H.sub.2O until a pH of 7 was reached. Finally the obtained white powder was dried for 12 hours at 100 C. under air in a muffle furnace. Chemical analysis indicated an Si/Al molar ratio of 227 and <0.1 wt-% of Na.sub.2O on a calcined basis. The BET surface area was measured by means of nitrogen sorption at 77K afforded a value of 495 m.sup.2/g.

[0173] The X-ray diffraction pattern of the sample obtained is displayed in FIG. 8a, and displays the following reflections and corresponding intensities:

TABLE-US-00013 Angle Intensity [2-Theta ] [%] 6.542 17.8 7.205 37.6 7.771 50.4 8.676 22.2 9.746 19.2 11.992 12.5 13.499 18.4 14.377 14.3 14.675 20.9 15.256 12.8 18.072 14.7 19.74 15.6 21.573 28.1 22.601 100 22.66 45.6 25.551 21.8 26.534 13.5 27.16 18.7 27.8 12.8 28.948 14.2 29.812 14.5 30.72 10.3 31.123 9.6 33.655 8.5 34.952 6.6 36.501 6.8 37.708 5.7

[0174] The .sup.29Si MAS NMR of the sample obtained is displayed in FIG. 8b and revels the following signal intensities in %: 102 ppm (Q4 (1Al)+Q3) 24%, 15-108 ppm (Q4 (0Al, T3-T9)) 52%, 112 ppm (Q4 (0Al, T1-T2)) 21%.

Example 9: Acid Treatment (6M) of Zeolite Beta (700 C./5 h) for 24 h Under Reflux

[0175] The calcined sample obtained from Reference Example 5 was taken as starting material. 1 g of the white powder was dispersed in 50 ml 6 M nitric acid solution in H.sub.2O and stirred in a round bottom flask at 100 C. under reflux for 24 hours. Afterwards the solid was extracted by vacuum filtration and subsequent washing with deionized H.sub.2O until a pH of 7 was reached. Finally the obtained white powder was dried for 12 hours at 100 C. under air in a muffle furnace. Chemical analysis indicated a Si/Al ratio of 316 and <0.1 wt-% of Na.sub.2O on a calcined basis. The BET surface area was measured by means of nitrogen sorption at 77K afforded a value of 362 m.sup.2/g.

[0176] The X-ray diffraction pattern of the sample obtained is displayed in FIG. 9a, and displays the following reflections and corresponding intensities:

TABLE-US-00014 Angle Intensity [2-Theta ] [%] 6.502 26.8 7.27 42.2 7.807 53.3 8.648 31.6 9.711 31.4 13.499 25.6 14.793 29.2 15.308 21.7 18.033 25.6 19.654 30.7 20.59 31 21.768 44.9 22.762 100 25.765 37.1 26.44 28.1 27.248 29.4 27.705 26.3 27.945 24.3 29.088 22.3 29.866 21 31.025 18.6 33.845 14.9 36.798 12.3

[0177] The .sup.29Si MAS NMR of the sample obtained is displayed in FIG. 9b and revels the following signal intensities in %: 102 ppm (Q4 (1Al)+Q3) 26%, 15-108 ppm (Q4 (0Al, T3-T9)) 46%, 112 ppm (Q4 (0Al, T1-T2)) 27%.

Example 10: Acid Treatment (6M) of Zeolite Beta (800 C./24 h) for 24 h Under Reflux

[0178] The calcined sample obtained from Reference Example 2 was taken as starting material. 1 g of the white powder was dispersed in 50 ml 6 M nitric acid solution in H.sub.2O and stirred in a round bottom flask at 100 C. under reflux for 24 hours. Afterwards the solid was extracted by vacuum filtration and subsequent washing with deionized H.sub.2O until a pH of 7 was reached. Finally the obtained white powder was dried for 12 hours at 100 C. under air in a muffle furnace. Chemical analysis indicated an Si/Al molar ratio of 204 and <0.1 wt-% of Na.sub.2O on a calcined basis. The BET surface area was measured by means of nitrogen sorption at 77K afforded a value of 560 m.sup.2/g.

[0179] The X-ray diffraction pattern of the sample obtained is displayed in FIG. 10a, and displays the following reflections and corresponding intensities:

TABLE-US-00015 Angle Intensity [2-Theta ] [%] 3.032 13.5 7.166 34.2 7.734 49.7 9.788 11.8 12.071 9.2 13.447 13.4 14.616 17.4 18.385 9.5 20.318 10.3 21.498 22 22.544 100 22.918 21.1 25.442 18.2 27.151 15.1 27.875 7.7 28.902 11.3 29.723 12.2 30.604 7 31.098 6.5 33.541 7.4 36.318 5.5

[0180] The .sup.29Si MAS NMR of the sample obtained is displayed in FIG. 10b and revels the following signal intensities in %: 102 ppm (Q4 (1Al)+Q3) 19%, 15-108 ppm (Q4 (0Al, T3-T9)) 60%, 112 ppm (Q4 (0Al, T1-T2)) 21%.

Example 11: Acid Treatment (6M) of Zeolite Beta (800 C./24 h) for 2 h Under Reflux

[0181] The calcined sample obtained from Reference Example 2 was taken as starting material. 1 g of the white powder was dispersed in 50 ml 6 M nitric acid solution in H.sub.2O and stirred in a round bottom flask at 100 C. under reflux for 2 hours. Afterwards the solid was extracted by vacuum filtration and subsequent washing with deionized H.sub.2O until a pH of 7 was reached. Finally the obtained white powder was dried for 12 hours at 100 C. under air in a muffle furnace. Chemical analysis indicated an Si/Al molar ratio of 112 and <0.1 wt-% of Na.sub.2O on a calcined basis. The BET surface area was measured by means of nitrogen sorption at 77K afforded a value of 605 m.sup.2/g.

[0182] The X-ray diffraction pattern of the sample obtained is displayed in FIG. 11a, and displays the following reflections and corresponding intensities:

TABLE-US-00016 Angle Intensity [2-Theta ] [%] 3.153 15.4 7.153 29.6 7.741 42.1 9.777 11.5 12.061 9.3 13.472 12.9 14.659 17.4 18.363 9.8 20.373 10.9 21.548 23.6 22.598 100 22.841 28.1 25.498 19.9 27.191 16.7 29.013 13 29.801 13 30.659 8.7 31.188 7.8 33.657 7.8 34.997 5.5 36.466 6.3

[0183] The .sup.29Si MAS NMR of the sample obtained is displayed in FIG. 11b and revels the following signal intensities in %: 102 ppm (Q4 (1Al)+Q3) 24%, 15-108 ppm (Q4 (0Al, T3-T9)) 54%, 112 ppm (Q4 (0Al, T1-T2)) 21%.

[0184] The catalyst sample was tested in the conversion of methanol to olefins. The testing conditions were as follows: P.sub.MeOH=50 kPa, Catalyst, 0.05 g; Catalyst bed height 1-1.5 cm, MeOH liquid, 6.75 l/min; He gas, 4.1 ml/min; Temperature, 500 C. The product stream was analyzed with a GC-FID detector from Shimazu GC-2014 applying a Divinylbenzene-styrene Copolymer column (J&W, HP-PLOT Q). The test was run at a load of W/F=5 g.Math.h/mol, the results of which are displayed in FIG. 11 c, as well as at a load of W/F=10 g.Math.h/mol, the results of which are displayed in FIG. 11d.

[0185] Thus, as may be taken from the results from testing in the conversion of methanol to olefins obtained for the present inventive example, not only may a conversion rate be achieved at high selectivities for the conversion of methanol to propene and butene, respectively, but said high conversion and selectivities may quite unexpectedly be maintained for a long period of time on stream without the slightest decrease. In particular, as compared to the results achieved for the comparative examples (cf. FIGS. 15c and 16c for Comparative Examples 15 and 16, respectively), far higher yields of propene and butene may be obtained at far higher overall selectivities due to the extremely constant conversion rate and selectivies leading to unprecedented times on stream prior to the regeneration of the catalyst. Accordingly, as demonstrated by the present results from comparative testing, a highly efficient catalyst is provided by the present invention compared to the commercial catalysts exemplified by Comparative Examples 15 and 16 below.

Example 12: Acid Treatment (3M) of Zeolite Beta (800 C./24 h) for 2 h Under Reflux

[0186] The calcined sample obtained from Reference Example 2 was taken as starting material. 1 g of the white powder was dispersed in 50 ml 3 M nitric acid solution in H.sub.2O and stirred in a round bottom flask at 100 C. under reflux for 2 hours. Afterwards the solid was extracted by vacuum filtration and subsequent washing with deionized H.sub.2O until a pH of 7 was reached. Finally the obtained white powder was dried for 12 hours at 100 C. under air in a muffle furnace. Chemical analysis indicated a Si/Al ratio of 92 and <0.1 wt-% of Na.sub.2O on a calcined basis. The BET surface area was measured by means of nitrogen sorption at 77K afforded a value of 621 m.sup.2/g.

[0187] The X-ray diffraction pattern of the sample obtained is displayed in FIG. 12a, and displays the following reflections and corresponding intensities:

TABLE-US-00017 Angle Intensity [2-Theta ] [%] 3.242 33.8 7.205 48.3 7.781 66.6 9.821 17.7 12.102 14 13.527 19.2 14.75 28.4 18.353 14.7 20.511 15.9 21.667 28.8 22.755 100 23.086 28.9 25.651 23.2 27.292 18.4 28.192 11.9 29.159 13.6 29.944 13.6 30.943 9.5 31.443 8.9 33.857 8.5 36.687 6.9

[0188] The .sup.29Si MAS NMR of the sample obtained is displayed in FIG. 12b and revels the following signal intensities in %: 102 ppm (Q4 (1Al)+Q3) 30%, 15-108 ppm (Q4 (0Al, T3-T9)) 49%, 112 ppm (Q4 (0Al, T1-T2)) 18%.

Example 13: Acid Treatment (1 M) of Zeolite Beta (800 C./24 h) for 2 h Under Reflux

[0189] The calcined sample obtained from Reference Example 2 was taken as starting material. 1 g of the white powder was dispersed in 50 ml 1 M nitric acid solution in H.sub.2O and stirred in a round bottom flask at 100 C. under reflux for 2 hours. Afterwards the solid was extracted by vacuum filtration and subsequent washing with deionized H.sub.2O until a pH of 7 was reached. Finally the obtained white powder was dried for 12 hours at 100 C. under air in a muffle furnace. Chemical analysis indicated a Si/Al ratio of 80 and <0.1 wt-% of Na.sub.2O on a calcined basis. The BET surface area was measured by means of nitrogen sorption at 77K affording a value of 569 m.sup.2/g.

[0190] The X-ray diffraction pattern of the sample obtained is displayed in FIG. 13a, and displays the following reflections and corresponding intensities:

TABLE-US-00018 Angle Intensity [2-Theta ] [%] 3.214 27.3 6.538 17.8 7.197 37.6 7.802 52.9 9.812 15.9 12.121 12 13.497 16.5 14.729 22.6 18.31 13.5 20.512 15.3 21.708 28.5 22.745 100 23.104 27.7 25.649 22.6 27.254 18.3 27.972 12 29.156 13.9 29.949 13.7 30.862 9.7 31.35 8.9 33.855 8.5 36.695 6.9

[0191] The .sup.29Si MAS NMR of the sample obtained is displayed in FIG. 13b and revels the following signal intensities in %: 102 ppm (Q4 (1Al)+Q3) 27%, 15-108 ppm (Q4 (0Al, T3-T9)) 53%, 112 ppm (Q4 (0Al, T1-T2)) 19%.

[0192] The catalyst sample was tested in the conversion of methanol to olefins. The testing conditions were as follows: W/F=5 g.Math.h/mol, P.sub.MeOH=50 kPa, Catalyst, 0.05 g; Catalyst bed height 1-1.5 cm, MeOH liquid, 6.75 l/min; He gas, 4.1 ml/min; P.sub.MeOH=50 kPa; Temperature, 500 C. The product stream was analyzed with a GC-FID detector from Shimazu GC-2014 applying a Divinylbenzene-styrene Copolymer column (J&W, HP-PLOT Q), the results of which are displayed in FIG. 13c.

Example 14: Acid Treatment (1 M) of Zeolite Beta (800 C./24 h) for 24 h at Ambient Temperature

[0193] The calcined sample obtained from Reference Example 2 was taken as starting material. 1 g of the white powder was dispersed in 50 ml 1 M nitric acid solution in H.sub.2O and stirred in a round bottom flask at 25 C. for 24 hours. Afterwards the solid was extracted by vacuum filtration and subsequent washing with deionized H.sub.2O until a pH of 7 was reached. Finally the obtained white powder was dried for 12 hours at 100 C. under air in a muffle furnace. Chemical analysis indicated a Si/Al ratio of 50 and <0.1 wt-% of Na.sub.2O on a calcined basis. The BET surface area was measured by means of nitrogen sorption at 77K affording a value of 572 m.sup.2/g.

[0194] The X-ray diffraction pattern of the sample obtained is displayed in FIG. 14a, and displays the following reflections and corresponding intensities:

TABLE-US-00019 Angle Intensity [2-Theta ] [%] 3.361 28.2 7.252 49.6 7.812 76.2 9.817 18.6 12.113 14.6 13.592 20.2 14.789 24.6 18.31 14.1 20.634 15.7 21.747 28.3 22.806 100 23.156 29.5 25.747 21.6 27.405 17.6 29.244 14.1 30.034 13 31.018 9.8 31.484 9.1 33.932 8.6 36.781 6.5

[0195] The .sup.29Si MAS NMR of the sample obtained is displayed in FIG. 14b and revels the following signal intensities in %: 102 ppm (Q4 (1Al)+Q3) 30%, 15-108 ppm (Q4 (0Al, T3-T9)) 51%, 112 ppm (Q4 (0Al, T1-T2)) 18%.

[0196] The catalyst sample was tested in the conversion of methanol to olefins. The testing conditions were as follows: W/F=5 g.Math.h/mol, P.sub.MeOH=50 kPa, Catalyst, 0.05 g; Catalyst bed height 1-1.5 cm, MeOH liquid, 6.75 l/min; He gas, 4.1 ml/min; P.sub.MeOH=50 kPa; Temperature, 500 C. The product stream was analyzed with a GC-FID detector from Shimazu GC-2014 applying a Divinylbenzene-styrene Copolymer column (J&W, HP-PLOT Q), the results of which are displayed in FIG. 14c.

Comparative Example 15: Zeolite Beta from Templated Synthesis (Si/Al=150)

[0197] As a comparative Example, a commercial sample of zeolite beta as obtained from template synthesis (product name: CP811C-300; Zeolyst International) was employed. Chemical analysis indicated an Si/Al molar ratio of 150 and <0.1 wt-% of Na.sub.2O on a calcined basis. The BET surface area was measured by means of nitrogen sorption at 77K afforded a value of 585 m.sup.2/g.

[0198] The X-ray diffraction pattern of the sample obtained is displayed in FIG. 15a, and displays the following reflections and corresponding intensities:

TABLE-US-00020 Angle Intensity [2-Theta ] [%] 7.732 100 11.441 16.5 12.003 16.2 13.511 22.1 14.664 19.3 18.241 15.4 21.552 30.1 22.557 75 24.952 19 25.454 20.5 27.199 20.6 28.825 17.3 29.653 15.7 30.687 12.9 33.407 11.2 36.334 8.1 37.546 8.1

[0199] The .sup.29Si MAS NMR of the sample obtained is displayed in FIG. 15b and revels the following signal intensities in %: 102 ppm (Q4 (1Al)+Q3) 18%, 15-108 ppm (Q4 (0Al, T3-T9)) 62%, 112 ppm (Q4 (0Al, T1-T2)) 19%.

[0200] The catalyst sample was tested in the conversion of methanol to olefins. The testing conditions were as follows: W/F=10 g.Math.h/mol, P.sub.MeOH=50 kPa, Catalyst, 0.05 g; Catalyst bed height 1-1.5 cm, MeOH liquid, 6.75 l/min; He gas, 4.1 ml/min; Temperature, 500 C. The product stream was analyzed with a GC-FID detector from Shimazu GC-2014 applying a Divinylbenzene-styrene Copolymer column (J&W, HP-PLOT Q), the results of which are displayed in FIG. 15c.

[0201] Thus, as may be taken from the results from testing in the conversion of methanol to olefins, compared to the results obtained for inventive Example 11 under the same testing conditions (cf. catalytic testing results in FIG. 11d), both the conversion rate and the propene selectivity already begin to decline after a few hours on stream and increasing drop when the reaction is further conducted whereas quite surprisingly both the conversion rate and the propene selectivity achieved for the inventive example remains practically constant even after 30 hours on stream. Same applies with respect to the selectivity of the reaction towards butene which, again, remains constant for the inventive example even after 30 hours on stream, whereas in the present comparative example the selectivity begins to rapidly drop after 20 hours on stream.

Comparative Example 16: Zeolite Beta from Templated Synthesis (Si/Al=250)

[0202] As a comparative Example, a commercial sample of zeolite beta as obtained from template synthesis (product name: HSZ-980HOA; Tosoh Corp.) was employed. Chemical analysis indicated a Si/Al ratio of 250 and <0.1 wt-% of Na.sub.2O on a calcined basis. The BET surface area was measured by means of nitrogen sorption at 77K of 590 m.sup.2/g.

[0203] The X-ray diffraction pattern of the sample obtained is displayed in FIG. 16a, and displays the following reflections and corresponding intensities:

TABLE-US-00021 Angle Intensity [2-Theta ] [%] 7.133 40.7 7.768 66.2 12.084 11.8 13.463 16.8 14.613 17 18.284 10.9 20.408 11.7 21.464 24.1 22.52 100 24.605 12.2 25.415 19.5 26.053 10.7 27.152 20.9 28.833 14.2 29.697 14.6 30.543 9.3 30.933 8.6 32.691 7.3 33.518 9.3 34.862 6.1 36.253 7 37.494 5.9

[0204] The .sup.29Si MAS NMR of the sample obtained is displayed in FIG. 16b and revels the following signal intensities in %: 102 ppm (Q4 (1Al)+Q3) 16%, 15-108 ppm (Q4 (0Al, T3-T9)) 63%, 112 ppm (Q4 (0Al, T1-T2)) 21%.

[0205] The catalyst sample was tested in the conversion of methanol to olefins. The testing conditions were as follows: W/F=10 g.Math.h/mol, P.sub.MeOH=50 kPa, Catalyst, 0.05 g; Catalyst bed height 1-1.5 cm, MeOH liquid, 6.75 l/min; He gas, 4.1 ml/min; Temperature, 500 C. The product stream was analyzed with a GC-FID detector from Shimazu GC-2014 applying a Divinylbenzene-styrene Copolymer column (J&W, HP-PLOT Q), the results of which are displayed in FIG. 16c.

[0206] As for Comparative Example 15, as may be taken from the results from testing in the conversion of methanol to olefins, compared to the results obtained for inventive Example 11 under the same testing conditions (cf. catalytic testing results in FIG. 11d), both the conversion rate and the propene selectivity already begin to decline after a few hours on stream and constantly drop when the reaction is further conducted whereas quite surprisingly both the conversion rate and the propene selectivity achieved for the inventive example remains practically constant even after 30 hours on stream. In particular, although both the conversion rate and the propene selectivity are initially higher in the present comparative example, this is quickly compensated by the constant conversion rate and propene selectivity observed for inventive Example 11, such that unexpectedly higher yields may be obtained when employing the inventive catalaysts, not only due to the greater overal conversion and selectivity, but in particular in view of the far longer time on stream which is possible prior to the regeneration of the catalyst. As a result, an extremely efficient catalyst for the conversion of methanol to olefins is provided by the present invention.