PROCESS FOR THE PRODUCTION OF THE CHA-AFT ZEOLITE INTERGROWTH COE-10 AND USE THEREOF IN HETEROGENEOUS CATALYSIS

Abstract

A process for the production of a zeolitic material comprising one or more zeolite intergrowth phases of one or more zeolites having a CHA-type framework structure comprising SiO.sub.2 and X.sub.2O.sub.3, and one or more zeolites having an AFT-type framework CT structure comprising SiO.sub.2 and X.sub.2O.sub.3, wherein X is a trivalent element, and wherein said process comprises: (1) preparing a mixture comprising one or more sources for SiO.sub.2, one or more sources for X.sub.2O.sub.3, and seed crystals comprising a zeolitic material, said zeolitic material comprising SiO.sub.2 and X.sub.2O.sub.3 in its framework structure and having a CHA-type framework structure; (2) heating the mixture prepared in (1) for obtaining a zeolitic material comprising one or more zeolite intergrowth phases; and (R) subjecting the zeolitic material obtained in (2) to a procedure for removing at least a portion of X from the framework structure of the zeolitic material.

Claims

1. A process for the production of a zeolitic material comprising one or more zeolite intergrowth phases of one or more zeolites having a CHA-type framework structure comprising SiO.sub.2 and X.sub.2O.sub.3, and one or more zeolites having an AFT-type framework structure comprising SiO.sub.2 and X.sub.2O.sub.3, wherein X is a trivalent element, and wherein the process comprises: (1) preparing a mixture comprising one or more sources for SiO.sub.2, one or more sources for X.sub.2O.sub.3, and seed crystals comprising a zeolitic material, wherein saidthe zeolitic material comprises SiO.sub.2 and X.sub.2O.sub.3 in its framework structure and has a CHA-type framework structure; (2) heating the mixture prepared in (1) for obtaining a zeolitic material comprising one or more zeolite intergrowth phases of one or more zeolites having a CHA framework structure and one or more zeolites having an AFT-type framework structure; and (3) subjecting the zeolitic material obtained in (2) to a procedure for removing at least a portion of X, from the framework structure of the zeolitic material.

2. The process of claim 1, wherein the zeolitic material obtained in (2) comprising one or more zeolite intergrowth phases of one or more zeolites having a CHA framework structure and one or more zeolites having an AFT-type framework structure, comprises COE 10.

3. The process of claim 1, wherein the zeolitic material comprised in the seed crystals in (1) is obtained by a process comprising: (A) preparing a mixture comprising one or more structure directing agents and a first zeolitic material comprising SiO.sub.2 and X.sub.2O.sub.3 in its framework structure, wherein the first zeolitic material has an FAU-, FER-, TON-, MTT-, BEA-, MFI-type or combination thereof framework structure; and (B) heating the mixture obtained in (A) for obtaining a second zeolitic material comprising SiO.sub.2 and X.sub.2O.sub.3 in its framework structure, wherein the second zeolitic material has a CHA-type framework structure.

4. The process of claim 3, wherein the first zeolitic material having an FAU-type framework structure comprises one or more zeolites having an FAU-type framework structure, wherein the one or more zeolites having an FAU-type framework structure are chosen from Li-LSX, zeolite X, zeolite Y, ECR-30, ZSM-20, LZ-210, SAPO-37, US-Y, CSZ-1, ZSM-3, Faujasite, and mixtures of two or more thereof.

5. The process of claim 1, wherein the mixture prepared in (1) and heated in (2) comprises substantially no organotemplate.

6. The process of claim 3, wherein the mixture prepared in (A) and heated in (B) comprises substantially no phosphorous and/or phosphorous containing compounds.

7. The process of claim 3, wherein the framework of the zeolitic material obtained in (B) comprises substantially no phosphorous.

8. The process of claim 1, wherein the mixture prepared in (1) and heated in (2) comprises substantially no phosphorous, phosphorous containing compounds, or both.

9. The process of claim 1. wherein the framework of the zeolitic material obtained in (2) comprises substantially no phosphorous.

10. The process of claim 3, wherein the mixture prepared according to (A) further comprises one or more solvents.

11. The process of claim, wherein the mixture prepared in (A) and heated in (B) further comprises at least one source for OH.sup.—.

12. The process of claim 3, wherein the second zeolitic material having a CHA-type framework structure comprises one or more zeolites having a CHA-type framework structure, wherein the one or more zeolites having a CHA-type framework structure are chosen from Willhendersonite, ZYT-6, SAPO-47, Na-Chabazite, Chabazite, LZ-218, Linde D, Linde R, SAPO-34, ZK-14, K-Chabazite, MeAPSO-47, Phi, DAF-5, UiO-21, |Li-Na| [Al—Si—O]—CHA, (Ni(deta)2)-UT-6, SSZ-13, SSZ-62, and mixtures of two or more thereof.

13. The process of claim 3, wherein the one or more structure directing agents comprises one or more tetraalkylammonium cation-containing compounds.

14. The process of claim 13, wherein the one or more tetraalkylammonium cation-containing compounds comprise one or more compounds of 1-adamantyltri(C.sub.1-C.sub.3)alkylammonium compounds, N,N,N-trimethyl-N-benzylammonium compounds, and mixtures of two or more thereof.

15. The process of claim 13, wherein the one or more tetraalkylammonium cation-containing compounds comprise one or more compounds of N,N,N-tri(C.sub.1-C.sub.2)alkyl-(C.sub.5-C.sub.6)cycloalkylammonium compounds, and mixtures of two or more thereof.

Description

DESCRIPTION OF THE FIGURES

[0262] FIG. 1 displays the reconstructed ADT data from Example 3.

[0263] FIG. 2 displays the comparison of the experimental and simulated electron diffraction patterns of zone [100] of Example 3. In the figure, experimental (black) and simulated (for p=0.25 in dark grey) intensity profiles 021, 031 and 041 taken along corresponding diffraction line marked by dark grey rectangles.

[0264] FIG. 3 displays the XRD patterns of the steam treated samples obtained from Example 4 compared to the H-form of the zeolitic material COE-10 from Example 3. In the respective diffractograms, the diffraction angle 2 theta in ° is shown along the abscissa and the intensities are plotted along the ordinate.

[0265] FIG. 4 displays the nitrogen adsorption-desorption measurements performed on the steam treated samples obtained from Example 4 compared to the H-form of the zeolitic material COE-10 from Example 3. In the respective isotherms, the relative pressure P/Po is shown along the abscissa and the absorbed volume in cm.sup.3/g is plotted along the ordinate.

[0266] FIG. 5 displays the NH.sub.3-TPD profiles obtained for the steam treated samples obtained from Example 4 compared to the H-form of the zeolitic material COE-10 from Example 3. In the respective TPD, the temperature in ° C. is shown along the abscissa and the TCD signal in arbitrary units is plotted along the ordinate.

[0267] FIG. 6 displays the CO FT-IR measurements obtained for the H-form of the zeolitic material COE-10 from Example 3. In the IR spectrum, the wavenumber in cm.sup.−1 is shown along the abscissa and the absorbance in arbitrary units is plotted along the ordinate.

[0268] FIG. 7 displays the CO FT-IR measurements obtained for the sample from Example 4 which was steam treated at 600° C. In the IR spectrum, the wavenumber in cm.sup.−1 is shown along the abscissa and the absorbance in arbitrary units is plotted along the ordinate.

[0269] FIG. 8 displays the results from MTO testing obtained in Example 5 for the H-form of the zeolitic material COE-10 from Example 3. In the graph, the time on stream in hours is shown along the abscissa and the conversion “0” as well as the selectivities towards ethene “.circle-solid.”, propene “.square-solid.”, butene “.box-tangle-solidup.”, C1-C4 alkane “”, compounds with more than 5 carbon atoms “”, and dimethylether “.star-solid.” in % are plotted along the ordinate.

[0270] FIG. 9 displays the results from MTO testing obtained in Example 5 for the sample from Example 4 which was steam treated at 500° C. In the graph, the time on stream in hours is shown along the abscissa and the conversion “∘” as well as the selectivities towards ethene “.circle-solid.”, propene “.square-solid.”, butene “.box-tangle-solidup.”, C1-C4 alkane “”, compounds with more than 5 carbon atoms “”, and dimethylether “.star-solid.” in % are plotted along the ordinate.

[0271] FIG. 10 displays the results from MTO testing obtained in Example 5 for the sample from Example 4 which was steam treated at 600° C. In the graph, the time on stream in hours is shown along the abscissa and the conversion “0” as well as the selectivities towards ethene “.circle-solid.”, propene “.square-solid.”, butene “.box-tangle-solidup.”, C1-C4 alkane “”, compounds with more than 5 carbon atoms “”, and dimethylether “.star-solid.” in % are plotted along the ordinate.

[0272] FIG. 11 displays the results from MTO testing obtained in Example 5 for the sample from Example 4 which was steam treated at 700° C. In the graph, the time on stream in hours is shown along the abscissa and the conversion “0” as well as the selectivities towards ethene “.circle-solid.”, propene “.square-solid.”, butene “.box-tangle-solidup.”, C1-C4 alkane “”, compounds with more than 5 carbon atoms “”, and dimethylether “.star-solid.” in % are plotted along the ordinate.

EXAMPLES

[0273] The present invention is further illustrated by the following examples and reference examples.

[0274] X-ray diffraction measurements

[0275] The powder X-ray diffraction (XRD) patterns were collected on a Rigaku Ultima III diffractometer using CuKa radiation (40 kV, 40 mA).

[0276] Nitrogen adsorption-desorption measurements

[0277] The nitrogen adsorption-desorption measurements were performed on a BEL-mini analyzer, BEL Japan. Prior to the measurements, all samples were degassed at 350° C. for 3 h.

[0278] NH.sub.3-TPD measurements

[0279] Temperature-programmed desorption of ammonia (NH.sub.3-TPD) profiles were recorded on a Multi-track TPD equipment (Japan BEL). Typically, 25 mg catalyst were pretreated at 873 K in a He flow (50 mL/min) for 1 h and then cooled to 373 K. Prior to the adsorption of NH.sub.3, the sample was evacuated at 373 K for 1 h. Approximately 2500 Pa of NH.sub.3 were allowed to make contact with the sample at 373 K for 30 min. Subsequently, the sample was evacuated to remove weakly adsorbed NH.sub.3 at the same temperature for 30 min. Finally, the sample was heated from 373 to 873 K at a ramping rate of 10 K/min in a He flow (50 mL/min). A thermal conductivity detector (TCD) was used to monitor desorbed NH.sub.3.

[0280] CO FT-IR measurements

[0281] FTIR spectra were obtained at a resolution of 4 cm.sup.−1 using a Jasco FTIR 4100 spectrometer equipped with a TGS detector. The powdered samples (-30 mg) were pelletized into a self-supporting disk of 1 cm in diameter, which was held in a glass cell. After evacuation at 500° C. for 1 h, the sample was cooled back to -120° C. prior to background spectra acquisition. Then CO was introduced into the cell in a pulse mode fashion (approx. 5 Pa for the first pulse, until total pressure in the IR cell reached approx. 1000 Pa). After equilibrium NO pressure was reached after each pulse of CO, an IR spectrum was acquired.

Reference Example 1

Synthesis of CHA Seeds

[0282] 2.31 g of Y zeolite (CBV712 from Zeolyst, having an SO.sub.2:Al.sub.2O.sub.3 molar ratio of 12) were added to an aqueous solution containing 0.28 g of NaOH (97%; from Wako Chemicals) and 7.28 g of a 20 wt-% aqueous trimethyladamantylammonium hydroxide (TMAdaOH) solution (corresponding to 1.42 g of trimethyladamantylammonium hydroxide in solution), after which the mixture was stirred for 1 h. The molar composition of the resultant gel was 1 SiO.sub.2:0.083 Al.sub.2O.sub.3:0.1 NaOH : 0.2 TMAdaOH:10 H.sub.2O. The thus prepared mother gel was crystallized in an autoclave at 150 ° C. for 2 days under tumbling conditions (40 rpm.). The crystalline solid product, a zeolitic material having framework type CHA, was recovered by filtration, washed with distilled water, dried overnight at 100° C., and calcined at 600° C. for 6 h under air.

Example 2

Synthesis of COE-10 having a CHA-AFT Intergrowth Phase

[0283] 0.817 g aluminum triisopropylate (Al(OiPr).sub.3 (>99.9%; from Kanto Chemical) were added to an aqueous solution containing 72 g of distilled water, 0.96 g NaOH (>99%; from Wako Chemicals), and 0.224 g KOH (>85%, from Wako Chemicals), after which the solution was stirred for 1 h. Then, 2.4 g fumed silica (Cab-O-Sil® M5, from Cabot) were added to the mixture, which was then stirred for 1 h. The molar composition of the resultant gel was 1 SO.sub.2:0.1 Al(0iPr).sub.3 : 0.6 NaOH : 0.1 KOH : 100 H.sub.2O. Then, 0.48 g (20 weight-% based on silica) of the calcined CHA seeds from Reference Example 1 were added to the mixture. The thus prepared mother gel was crystallized in an autoclave at 170° C. for 2 days under tumbling condition (20 rpm). The solid crystalline product was recovered by filtration, washed with distilled water, and dried overnight at 100° C. in air.

[0284] 1 g of the zeolitic material obtained from crystllization was treated with 100 mL aqueous 2.5 M NH.sub.4NO.sub.3 at 80° C. for 3 h. The procedure was then repeated to obtain the ammonium form of the zeolitic material. Said product is referred to herein as NH4-COE-10.

[0285] The zeolitic material NH4-COE-10 was then calcined at 500° C. for 5 h under air to obtain the H-form of the zeolitic material, which is referred to herein as H-COE-10.

[0286] Elemental analysis of the product was performed on an inductively coupled plasma-atomic emission spectrometer (ICP-AES, Shimadzu ICPE-9000). The weight contents of Si and Al in the H-form of the zeolite COE-10 are 36.9 and 9.6%, respectively, based on the ICP results.

Example 3

Characterization of the CHA-AFT Intergrowth Phase COE-10

[0287] A powdered sample of the H-form of the zeolitic material obtained from Example 2 was dispersed in ethanol using an ultrasonic bath and sprayed onto a carbon-coated copper grid using a sonifier adapted for transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), electron dispersive X-ray spectroscopy (EDXS) and automated electron diffraction tomography (ADT) investigations. The sonifier used is described in E. Mugnaioli et al., Ultramicroscopy, 109 (2009) 758-765. TEM, EDX and ADT measurements were carried out with an FEI TECNAI F30 S-TWIN transmission electron microscope equipped with a field emission gun and working at 300 kV. TEM images and nano electron diffraction (NED) patterns were taken with a CCD camera (16-bit 4,096×4,096 pixel GATAN ULTRASCAN4000) and acquired by Gatan Digital Micrograph software. Scanning transmission electron microscopy (STEM) images were collected by a FISCHIONE high-angular annular dark field (HAADF) detector and acquired by Emispec ES Vision software. Three-dimensional electron diffraction data were collected using an automated acquisition module developed for FEI microscopes according to the procedure described in U. Kolb et al., Ultramicroscopy, 107 (2007) 507-513. For high tilt experiments, all acquisitions were performed with a FISCHIONE tomography holder. A condenser aperture of 10 pm and mild illumination settings (gun lens 8, spot size 6) were used in order to produce a semi-parallel beam of 200 nm in diameter on the sample (104 elnm.sup.2s). Crystal position tracking was performed in microprobe STEM mode and NED patterns were acquired sequentially in steps of 1°. Tilt series were collected within a total tilt range up to 90°, occasionally limited by overlapping of surrounding crystals or grid edges. ADT data were collected with electron beam precession (precession electron diffraction, PED) according to the procedure described in R. Vincent et al., Ultramicroscopy, 53 (1994) 271-282. PED was used in order to improve reflection intensity integration quality as described in E. Mugnaioli et al., Ultramicroscopy, 109 (2009) 758-765. PED was performed using a Digistar unit developed by NanoMEGAS SPRL. The precession angle was kept at 1.0°. The eADT software package was used for three-dimensional electron diffraction data processing as described in U. Kolb et al., Cryst. Res. Technol., 46 (2011) 542-554. Ab initio structure solution was performed assuming the kinematic approximation I≈|F.sub.hkl|.sup.2 by direct methods implemented in the program SIR2014 as described in M.C. Burla et al., Journal of Applied Crystallography, 48 (2015) 306-309. Difference Fourier mapping and least-squares refinement were also performed with the software SIR2014 as described in M. C. Burla et al., Journal of Applied Crystallography, 48 (2015) 306-309. Scattering factors for electrons were taken from Doyle and Turner as described in P.A. Doyle et al., Acta Crystallographica Section A, 24 (1968) 390-397.

[0288] An ADT dataset was collected from an isolated lying particle and reconstructed in three-dimensional diffraction volume. For each measured particle, the diffraction volumes showed the same primitive lattice with diffuse scattering along the shortest reciprocal direction. For instance, the diffraction volume shown in FIG. 1, delivered a primitive lattice with the parameters a=14.26 Å, b=14.23 Å, c=15.80 Å, α=90.0°, β=90.1° and γ=119.6°. Under consideration of the scale factor based on the effective camera length, the lattice determined by ADT (14.245/15.80=0.9016) agrees the lattice parameters of loc-512_dehyd (13.4791/14.8954=0.9049). It should be noted, that the extinctions inferred from rhombohedral centering are violated. The data was indexed in rhombohedral setting with hexagonal lattice (R.sub.sym=0.132, Laue class-3m) and the structure solved in space group R-3m (details listed in Table 1). Ab initio structure solution converged to a final residual R.sub.F of 0.0981. The five strongest maxima of the electron density map (from 1.13 to 0.56 e|.sup.−3) correspond to one silicon atom and four oxygen atoms. The following 12 weakest maxima (from 0.38 to 0.03 eÅ.sup.−3) were not taken into account.

TABLE-US-00001 TABLE 1 Crystallographic information about ADT measurements and structure solution of CHA. System CHA Tilt range/° −45/+45 No. of sampled reflections 10704 No. of independent reflections 233 Resolution/Å 1.0 Indep. refl. coverage/% 68 R.sub.sym 0.104 Overall U/Å.sup.2 0.046 Residual R(F) (SIR2014) 0.098 Reflections/parameter ratio 5.9 No. of indep. Si and O atoms 5 Space group R-3 m a/Å 13.4791 b/Å 13.4791 c/Å 14.8954 α/° 90.0 β/° 90.0 γ/° 120.0 V/Å.sup.3 2343.70

[0289] Disorder Modelling and Diffraction Simulations

[0290] The stacked sequence of 6-rings in CHA (AABBCC . . . ) is partly disordered, indicated by the diffuse scattering along the direction c* obtained in the reconstructed diffraction data (see FIG. 1). The probability p, described as in the correlation matrix in Table 2, correlates with the volume fraction for an usual obverse-reverse twinning (a twinning via a two fold axis) in rhombohedrat crystal structures.

TABLE-US-00002 TABLE 2 Elements of the correlation matrix describe the probability for all possible stacking events Layer α β α 1-p p β 1-p p

[0291] In order to cause diffuse scattering it must be assumed that within a scattering domain several twin surfaces occur, by change of the growth direction in an aperiodic crystal growth, as it is customary for polysynthetic twinning. A change in the growth direction results in a twinning plane containing a composite building unit aft, like in the framework type AFT [7] with an AABBCCAACCBB . . . sequence of 6-rings. This type of intergrowth leads to diffuse scattering in the reciprocal stacking direction c*.

[0292] Diffuse scattering between the Bragg reflections measured by ADT were compared with diffuse scattering calculated from simulated disordered crystals. The DISCUS program was used to model disordered CHA superstructures based on layer building units and to compare the simulated to experimental electron diffraction pattern as described in Y. Krysiak et al., Acta Crystallographica Section A Foundations and Advances, 74 (2018) 93-101. For the stacking module of DISCUS the correlation matrix that defines the specific sequence of layer types as function of the stacking probability, p, listed in Fehler! Verweisquelle konnte nicht gefunden werden. above, was used. It describes the probability of layer β (AACCBB) versus layer α (AABBCC).

[0293] An example of an integrated [100]-zone image based on ADT data of Cu_Cry1 is provided in FIG. 2. The corresponding simulated two-dimensional electron diffraction pattern was calculated for p=0.0 to 0.5 in 0.05 steps. Qualitatively, the experimental and simulated patterns of diffuse scattering on the crystallographic zones are comparable (FIG. 2). The strongest diffuse streaks of zone [100] are observable for 02/and 04/reflections. These diffuse streaks were taken into account for a quantitative disorder analysis dependent on the stacking probability of layer β. Therefor the extracted experimental diffuse streaks were compared with the diffuse lines calculated in DISCUS by diffuse_compare. The best agreement between the experimental and the simulated diffuse lines was achieved for p=0.25(5), corresponding to a portion of 62.5% of the total number of crystallographic layers consisting of αα and ββ stacking and 37.5% of mixed crystallographic stacking sequences αβ and βα a along the crystallographic c-axis. The later resembles the framework structure of the intergrowth phase consisting of AABBCCAAC-CBB crystallographic stacking sequences with 3 AFT and 3 CHA cages in the unit cell with double volume compared to the CHA crystal structure. Taking this into account the ratio of CHA/AFT cages can be estimated as 4.33 by (62.5+37.5/2)/37.5/2.

[0294] Conclusion

[0295] The correlation matrix shown in Fehler! Verweisquelle konnte nicht gefunden werden. with p=0.25 results in a stacking sequence in which statistically every fourth layer a is turned by 180° and shifted by the vector [−⅓, ⅓, 0] (layer β). With a probability of 75% layer a is stacked vice versa. Every stacking sequence αβ or αβ leads to a natural tiling t-aft, which is not part of the ordered CHA-structure. The twin volume fractions differ from particle to particle ranging from a probability of p=0.25 to 0.5.

Example 4

Steam Treatment of COE-10 having a CHA-AFT Intergrowth Phase

[0296] 0.5 g samples of the NH.sub.4-form of COE-10 from Example 2 (“NH4-COE-10”) were loaded in the middle of a quartz tube in a tube furnance. The samples were heated to the desired temperature (ranging from 500 to 700° C.) at 5° C/min ramp and held there for 1 h under 50% H.sub.2O/N.sub.2. The steaming treatment was performed during the entire heating process, including ramping up and cooling-down. Thus obtained products were denoted as “H-COE-10-xST”, where x means the steaming treatment temperature. As may be taken from the XRD and N.sub.2 adsorption results displayed in FIGS. 3 and 4, the CHA structure remained almost intact for steamtreated H-COE-10, regardless of the steaming temperature. As may be taken from Table 3 below, the micropore volume of the steamtreated samples varied from 0.18 to 0.22 cm.sup.3/g.

TABLE-US-00003 TABLE 3 Results from BET surface area and micropore volume measurements obtained from the nitrogen adsorption-desorption measurements performed on the steam treated samples obtained from Example 4 compared to the H-form of the zeolitic material (“H-COE-10”) from Example 2. Sample S.sub.BET/m.sup.2g.sup.−1 V.sub.micro/cm.sup.3g.sup.−1 V.sub.total/cm.sup.3g.sup.−1 V.sub.meso/cm.sup.3g.sup.−1 H-COE-10 704 0.22 0.45 0.23 H-COE-10-500ST 530 0.18 0.58 0.40 H-COE-10-600ST 652 0.22 0.53 0.31 H-COE-10-700ST 579 0.20 0.52 0.32

[0297] Although the bulk Si/AI ratio of the samples remained at ca. 3.7 after steaming, the framework Si/AI ratio was increased, as was calculated from the .sup.29Si MAS NMR results. For example, the framework Si/AI ratios for H-COE-10 and H-COE-10-600ST were 4.3 and 6.4, respectively. These results indicate that more Al atoms were removed from the framework after the steaming treatment. From the NH.sub.3-TPD results displayed in FIG. 5, the acid amount gradually decreased with increasing the steaming temperature. The values obtained from the deconvolution of the results displayed in FIG. 5 are shown in Table 4 below. Moreover, the strong acid sites were preferentially removed after steaming treatment, as demonstrated by the CO adsorption FTIR results displayed in FIGS. 6 (for H-COE-10) and 7 (for H-COE-10-600ST).

TABLE-US-00004 TABLE 4 Deconvolution results from NH.sub.3-TPD profiles displayed in Figure 5 for the steam treated samples obtained from Example 4 compared to the H-form of the zeolitic material (“H-COE-10”) from Example 3. peak I/ peak II/ peak III/ peak IV/ Sample mmol/g (° C.) mmol/g (° C.) mmol/g (° C.) mmol/g (° C.) H-COE-10 0.835 0.437 0.520 0.448 (169) (203) (329) (472) H-COE-10-500ST 0.346 0.433 0.398 0.411 (167) (200) (281) (461) H-COE-10-600ST 0.218 0.394 0.500 0.300 (162) (196) (266) (422) H-COE-10-700ST 0.111 0.158 0.217 0.298 (157) (188) (239) (343)

Example 5

MTO Testing

[0298] The MTO reaction was carried out in a fix-bed reactor under atmospheric pressure. The pressure of methanol was set at 5 kPa. Helium was used as a carrier gas. W/F for methanol was set at 33.7 g-cat h mol-1. The catalyst was activated in flowing He at 500° C. for 1 h prior to the reaction and then cooled to the reaction temperature of 350° C. The reaction products were analyzed by an online gas chromatograph (GC-2014, Shimadzu) equipped with HP-PLOT/Q capillary column and an FID detector. The selectivities of the products were calculated on the basis of the carbon number. The methanol (MeOH) conversion was calculated based on the peak area in the GC spectra before and after reaction, i.e. Com %=[Peak Area (MeOH.sub.initial)−Peak Area (MeOH.sub.unreacted)]/Peak Area (MeOH.sub.initial). The product selectivity was determined by initial.sub.i the peak area in the GC spectra divided to the sum of all products, i.e. Sel. %=Peak Area (each product)/Peak Area (total products). It is noted that the relative correction factors were used for the oxygen-containing product (i.e., dimethyl ether (DME)) and MeOH.

[0299] The results from MTO testing as performed on the H-form of the zeolitic material (“H-COE-10”) from Example 3 as well as on the steam treated samples obtained from Example 4 are displayed in FIGS. 8-11, respectively. Thus, as may be taken from the results, it has quite surprisingly been found that the time on stream of the H-form of the zeolitic material (“H-COE-10”) from Example 3 in MTO may be increased by up to 8 times as long when steam treated. Furthermore, it has unexpectedly been found that the selectivity towards ethane and propene is reversed by the steam treatment of the catalyst, such that the higher selectivity towards propene observed for the non-steamed sample is transformed to a higher selectivity towards ethene in the experiments conducted with the steamed samples.

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