A COMPOSITION COMPRISING A MIXED METAL OXIDE AND A MOLDING COMPRISING A ZEOLITIC MATERIAL HAVING FRAMEWORK TYPE CHA AND AN ALKALINE EARTH METAL

Abstract

The present invention relates to a composition comprising a) a molding comprising a zeolitic material having framework type CHA, wherein the zeolitic material comprises one or more alkaline earth metals M and b) a mixed metal oxide comprising chromium, zinc, and aluminium. It also relates to the use of the composition in a process for producing C2 to C4 olefins from syngas.

Claims

1.-15. (canceled)

16. A composition comprising a) a molding comprising a zeolitic material having framework type CHA, wherein the zeolitic material has a framework structure comprising a tetravalent element Y, a trivalent element X, and oxygen, wherein the zeolitic material further comprises one or more alkaline earth metals M; and b) a mixed metal oxide comprising chromium, zinc, and aluminum; wherein Y is one or more of Si, Ge, Sn, Ti, and Zr; wherein X is one or more of Al, B, Ga, and In.

17. The composition of claim 16, wherein Y is Si and X is Al.

18. The composition of claim 16, wherein in the framework structure of the zeolitic material, the molar ratio Y:X calculated as YO.sub.2:X.sub.2O.sub.3 is at least 5:1.

19. The composition of claim 16, wherein at least 95 weight-% of the framework structure of the zeolitic material consist of Y, X, O, and H.

20. The composition of claim 16, wherein the one or more alkaline earth metals M is one or more of Be, Mg, Ca, Sr and Ba.

21. The composition of claim 16, wherein the zeolitic material comprises the one or more alkaline earth metals M, calculated as elemental alkaline earth metal, in a total amount in the range of from 0.1 to 5 weight-%, based on the weight of the zeolitic material comprised in the molding.

22. The composition of claim 16, wherein the zeolitic material has an amount of medium acid sites, wherein the amount of medium acid sites is the amount of desorbed ammonia per mass of the calcined zeolitic material as measured according to the temperature programmed desorption of ammonia in the temperature range of from 100 to 350 C. determined according to the method as described in Reference Example 1.2, wherein the amount of medium acid sites is at least 0.7 mmol/g and wherein the zeolitic material has an amount of strong acid sites, wherein the amount of strong acid sites is the amount of desorbed ammonia per mass of the calcined zeolitic material as measured according to the temperature programmed desorption of ammonia in the temperature range of from 351 to 500 C. determined according to the method as described in Reference Example 12, wherein the amount of strong acid sites is less than 1.0 mmol/g.

23. The composition of claim 16, wherein the molding further comprises a binder material.

24. The composition of claim 23, wherein in the molding, the weight ratio of the zeolitic material relative to the binder material is in the range of from 1:1 to 20:1.

25. The composition of claim 16, wherein at least 98 weight-% of the mixed metal oxide consists of chromium, zinc, aluminum, and oxygen.

26. The composition of claim 25, wherein in the mixed metal oxide, the weight ratio of the zinc, calculated as element, relative to the chromium, calculated as element, is in the range of from 2.5:1 to 6.0:1, the weight ratio of the aluminum, calculated as element, relative to the chromium, calculated as element, is in the range of from 0.1:1 to 2:1 and the weight ratio of the mixed metal oxide relative to the zeolitic material is at least 0.2:1.

27. The composition of claim 16, wherein at least 95 weight-% of the composition consist of the molding and the mixed metal oxide.

28. A process for preparing the composition according to claim 16, the process comprising (i) providing a molding comprising a zeolitic material having framework type CHA, wherein the zeolitic material has a framework structure comprising a tetravalent element Y, a trivalent element X, and oxygen, wherein the zeolitic material further comprises one or more alkaline earth metals M, wherein Y is one or more of Si, Ge, Sn, Ti, and Zr, wherein X is one or more of Al, B, Ga, and In; (ii) providing a mixed metal oxide comprising chromium, zinc, and aluminum; (iii) mixing the molding provided according to (i) with the mixed metal oxide provided according to (ii), obtaining the composition.

29. A process for preparing C2 to C4 olefins from a synthesis gas comprising hydrogen and carbon monoxide, the process comprising (1) providing a gas stream which comprises a synthesis gas stream comprising hydrogen and carbon monoxide; (2) providing a catalyst comprising the composition according to claim 16; (3) bringing the gas stream provided in (1) in contact with the catalyst provided in (2), obtaining a reaction mixture stream comprising C2 to C4 olefins.

30. The process of claim 29, wherein the reaction mixture obtained according to (3) comprises ethene, propene, and butene, wherein in the reaction mixture obtained according to (3), the molar ratio of propene relative to ethene is greater than 1 and the molar ratio of ethene relative to butene is greater than 1.

Description

EXAMPLES

Reference Example 1: Analytical Methods

Reference Example 1.1: Determination of the BET Specific Surface Area

[0244] The BET specific surface area was determined via nitrogen physisorption at 77 K according to the method disclosed in DIN 66131.

Reference Example 1.2: Temperature Programmed Desorption of Ammonia (NH.SUB.3.-TPD)

[0245] The temperature-programmed desorption of ammonia (NH.sub.3-TPD) was conducted in an automated chemisorption analysis unit (Micromeritics AutoChem II 2920) having a thermal conductivity detector. Continuous analysis of the desorbed species was accomplished using an online mass spectrometer (OmniStar QMG200 from Pfeiffer Vacuum). The sample (0.1 g) was introduced into a quartz tube and analyzed using the program described below. The temperature was measured by means of a Ni/Cr/Ni thermocouple immediately above the sample in the quartz tube. For the analyses, He of purity 5.0 was used. Before any measurement, a blank sample was analyzed for calibration. [0246] 1. Preparation: Commencement of recording; one measurement per second. Wait for 10 minutes at 25 C. and a He flow rate of 30 cm.sup.3/min (room temperature (about 25 C.) and 1 atm); heat up to 600 C. at a heating rate of 20 K/min; hold for 10 minutes. Cool down under a He flow (30 cm.sup.3/min) to 100 C. at a cooling rate of 20 K/min (furnace ramp temperature); Cool down under a He flow (30 cm.sup.3/min) to 100 C. at a cooling rate of 3 K/min (sample ramp temperature). [0247] 2. Saturation with NH.sub.3: Commencement of recording; one measurement per second. Change the gas flow to a mixture of 10% NH.sub.3 in He (75 cm.sup.3/min; 100 C. and 1 atm) at 100 C.; hold for 30 minutes. [0248] 3. Removal of the excess: Commencement of recording; one measurement per second. Change the gas flow to a He flow of 75 cm.sup.3/min (100 C. and 1 atm) at 100 C.; hold for 60 min. [0249] 4. NH.sub.3-TPD: Commencement of recording; one measurement per second. Heat up under a He flow (flow rate: 30 cm.sup.3/min) to 600 C. at a heating rate of 10 K/min; hold for 30 minutes. [0250] 5. End of measurement.

[0251] Desorbed ammonia was measured by means of the online mass spectrometer, which demonstrates that the signal from the thermal conductivity detector was caused by desorbed ammonia. This involved utilizing the m/z=16 signal from ammonia in order to monitor the desorption of the ammonia. The amount of ammonia adsorbed (mmol/g of sample) was ascertained by means of the Micromeritics software through integration of the TPD signal with a horizontal baseline.

Reference Example 1.3: Determination of Selectivities and Yields

[0252] The selectivity of a given product compound, in %, referred to in the following as S.sub.N_SubstanceA, is a normalized selectivity S.sub.N and is calculated as follows:

S.sub.N_SubstanceA/%=S_SubstanceA/%*Fact_normS

[0253] wherein

[0254] S_SubstanceA/%=selectivity of substance A

[0255] Fact_normS=normalization factor, used to achieve a sum of the selectivities of 100%

[0256] a) S_SubstanceA

[0257] The selectivity of substance A, S_SubstanceA, is defined as

S_SubstanceA/%=(Y_SubstanceA/X_CO(IntStd))*100

[0258] wherein [0259] Y_SubstanceA=yield of substance A [0260] X_CO(IntStd)=conversion of CO calculated based on an internal standard, in the present case an inert liner (Argon)

[0261] a.1) Y_SubstanceA

[0262] The yield of substance A, Y_SubstanceA, is defined

Y_SubstanceA/%=(R(C)_SubstanceA/R(C)_CO_in)*100

[0263] wherein [0264] R(C)_SubstanceA=the rate of carbon of substance A, determined in g/h via gas chromatography [0265] R(C)_CO_in =the rate of carbon monoxide CO which is fed to the reactor, determined in (g carbon)/h

[0266] a.2) X_CO(IntStd)

[0267] The conversion of CO, X_CO(IntStd), is defined as

X_CO(IntStd)=(1(RA_CO/Arout)/(RA_CO/AroutRef))*100

[0268] wherein [0269] RA_CO/Arout=rate of CO determined via gas chromatography, divided by the rate of the inert liner Ar determined via GC [0270] RA_CO/AroutRef=rate of CO/reference determined via gas chromatography, divided by the rate of inert liner Ar/reference determined via gas chromatography (i.e. rate of CO at the inlet divided by rate of Ar at the inlet

[0271] b) Fact_normS

[0272] The normalization factor, Fact_normS, is defined as

Fact_normS=100/((Sum of all S)(S_starting material))

[0273] wherein [0274] Sum of all S=sum of all selectivities measured at the outlet of the reactor (which would include the selectivities of starting material at the out let of the conversion is not 100%) [0275] S_starting material=selectivites of the starting materials (if conversion is 100%, the value would be 0%)

Reference Example 1.4: Determination of XRD Patterns

[0276] The crystallinity of the zeolitic materials was determined by XRD analysis. The data were collected using a standard Bragg-Brentano diffractometer with a CuX-ray source and an energy dispersive point detector. The angular range of 2 to 70 (2 theta) was scanned with a step size of 0.02, while the variable divergence slit was set to a constant opening angle of 0.3. The data were then analyzed using TOPAS V5 software, wherein the sharp diffraction peaks were modeled using PONKCS phases for AEI and FAU and the crystal structure for CHA. The model was prepared according to Madsen I C, Scarlett NVY (2008) Quantitative phase analysis. In: Dinnebier R E, Billinge S J L (eds) Powder diffraction: theory and practice. The Royal Society of Chemistry, Cambridge, pp. 298-331. This was refined to fit the data. An independent peak was inserted at the angular position 28. This was used to describe the amorphous content. The crystalline content describes the intensity of the crystalline signal to the total scattered intensity. Included in the model were also a linear background, Lorentz and polarization corrections, lattice parameters, space group and crystallite size.

Reference Example 2: Preparation of a Molding Comprising a Zeolitic Material SAPO-34

[0277] a) Providing a SAPO-34 Zeolitic Material

[0278] The SAPO-34 zeolitic material was purchased from the company Zeochem.

[0279] b) Preparing an Extrudate of the SAPO-34 Zeolitic Material

[0280] Materials Used:

TABLE-US-00001 SAPO-34 zeolitic material, according to a) above: 72 g De-ionized water: 25 ml LudoxAS40 (Grace; colloidal silica; 45 g aqueous solution, 40 weight-%): Walocel 5 % 90.0 g

[0281] The zeolitic material, the Ludox and the PEO were kneaded for 1 h with gradual addition of the deionized water. The paste obtained was extruded and strands of a diameter of 1 mm diameter were formed. The strands were dried at 120 C. and then calcined for 5 hours at 500 C. 60 g of product were obtained.

Reference Example 2.1: Preparation of a Molding Comprising a 0.5 Weight-% Mg-SAPO-A Zeolitic Material

[0282] a) Providing a SAPO-34 zeolitic material.

[0283] The SAPO-34 zeolitic material was purchased from the company Zeochem according to Reference Example 2a) above.

[0284] b) Providing a Mg-SAPO-34 Zeolitic Material

TABLE-US-00002 SAPO-34 zeolitic material of a) 80 g Mg(NO.sub.3).sub.2 H.sub.2O 4.1 g Deionized water 55 g

[0285] Mg(NO.sub.3).sub.2H.sub.2O was dissolved in water and homogenized. The solution was added dropwise to the zeolitic material comprised in a beaker. The impregnated zeolite was transferred in a porcelain bowl. The material was dried at 120 C. and then calcined for 5 hours at 500 C. 80 g of product were obtained. Elemental analysis of the zeolitic material showed a Mg content of 0.5 weight-%. The NH3-TPD analysis performed according to Reference Example 1.2 showed the following peaks (see Table 1 below).

TABLE-US-00003 TABLE 1 Results of the NH3-TPD analysis Temperature Peak Peak at maximum/ Quantity/ concentration/ number C. mmol/g % 1 189.3 0.123 0.91 2 341.8 0.144 0.81 3 544.6 0.039 0.67

[0286] The plot of the NH3-TPD analysis is shown in FIG. 1.

[0287] c) Preparing a Molding Comprising the 0.5 Weight-% Mg-SAPO-34 Zeolitic Material

[0288] Materials Used:

TABLE-US-00004 0.5 % Mg-SAPO-34 zeolitic material, according to a) above: 75 g Ludox AS40 (Grace; colloidal silica; aqueous solution, 46.9 g 40 weight-%): Walocel 5% 93.8 g

[0289] The zeolitic material, the Ludox and the Walocel were kneaded for 1 h (with no addition of water). The material obtained was extruded and strands of a diameter of 1 mm diameter were formed. The strands were dried hours at 120 C. and then calcined for 5 hours at 500 C. 60 g of product were obtained.

Reference Example 2.2: Preparation of a Molding Comprising a 1.1 Weight-% Mg-SAPO-34 Zeolitic Material

[0290] a) Providing a SAPO-34 Zeolitic Material.

[0291] The SAPO-34 zeolitic material was purchased from the company Zeochem according to Reference Example 2a) above.

[0292] b) Providing a Mg-SAPO-34 Zeolitic Material

TABLE-US-00005 SAPO-34 zeolitic material of a) 80 g Mg(NO.sub.3).sub.2 H.sub.2O 8.8 g Deionized water 55 g

[0293] Mg(NO.sub.3).sub.2H.sub.2O was dissolved in water and homogenized. The solution was added dropwise to the zeolitic material comprised in a beaker. The impregnated zeolite was transferred in a porcelain bowl. The material was dried at 120 C. and then calcined for 5 hours at 500 C. 80 g of product were obtained. Elemental analysis of the zeolitic material showed a Mg content of 1.1 weight-%. The NH3-TPD analysis performed according to Reference Example 1.2 shows the following peaks (see Table 2 below).

TABLE-US-00006 TABLE 2 Results of the NH3-TPD analysis Temperature at maximum Quantity/ Peak concentration/ Peak number ( C. mmol/g % 1 178.3 0.030 0.70 2 314.7 0.031 0.68

[0294] The plot of the NH3-TPD analysis is shown in FIG. 2.

[0295] c) Preparing an Extrudate Comprising the 1.1 Weight-% Mg-SAPO-34 Zeolitic Material

[0296] Materials Used:

TABLE-US-00007 1.1% Mg-SAPO-34 zeolitic material, according to a) above: 75 g Ludox AS40 (Grace; colloidal silica; aqueous solution, 46.9 g 40 weight-%): Walocel 5% 93.8 g

[0297] The zeolitic material, the Ludox and the Walocel were kneaded for 1 h (with no addition of water). The material obtained was extruded and strands of 1 mm diameter were formed. The strands obtained were dried hours at 120 C. and then calcined for 5 hours at 500 C. 60 g of product were obtained.

Reference Example 2.3: Preparation of a Molding Comprising a 2 Weight-% Mg-SAPO-34 Zeolitic Material

[0298] a) Providing a SAPO-34 Zeolitic Material.

[0299] The SAPO-34 zeolitic material was purchased from the company Zeochem according to Reference Example 2a) above.

[0300] b) Providing a Mg-SAPO-34 Zeolitic Material

TABLE-US-00008 SAPO-34 zeolitic material of a) 80 g Mg(NO.sub.3).sub.2 H.sub.2O 16.8 g Deionized water 55 g

[0301] Mg(NO.sub.3).sub.2H.sub.2O was dissolved in water and homogenized. The solution was added dropwise to the zeolitic material comprised in a beaker. The impregnated zeolite was transferred in a porcelain bowl. The material was dried at 120 C. and then calcined for 5 hours at 500 C. 80 g of product were obtained. Elemental analysis of the zeolitic material showed a Mg content of 2 weight-%. The NH3-TPD analysis performed as disclosed in Reference Example 1.2 showed the following peaks (see Table 3 below).

TABLE-US-00009 TABLE 3 Results of the NH3-TPD analysis Peak Temperature at Quantity/ Peak concentration/ number maximum/ C. mmol/g % 1 178.8 0.031 0.71 2 301.2 0.041 0.69

[0302] The plot of the NH3TPD analysis is shown in FIG. 3.

[0303] c) Preparing an Extrudate Comprising the 2 Weight-% Mg-SAPO-34 Zeolitic Material

[0304] Materials Used:

TABLE-US-00010 2% Mg-SAPO-34 zeolitic material, according to a) above: 75 g Ludox AS40 (Grace; colloidal silica; aqueous solution, 46.9 g 40 weight-%): Walocel 5% 93.8 g

[0305] The zeolitic material, the Ludox and the Walocel were kneaded for 1 h (with no addition of water). The material obtained was extruded and strands of 1 mm diameter were formed. The strands obtained were dried hours at 120 C. and then calcined for 5 hours at 500 C. 60 g of product were obtained.

Reference Example 3: Preparation of a Molding Comprising a Zeolitic Material SAPO-34

[0306] a) Preparing a SAPO-34 Zeolitic Material

[0307] Materials Used:

TABLE-US-00011 Al.sub.2O.sub.3 (Pural SB) 7.97 g De-ionized water 88.11 g 85% H.sub.3PO.sub.4 20.19 g Ludox AS30 10.53 g Triethanolamine (TEA) 33.20 g

[0308] The water was provided in a beaker provided with a blade stirrer. The 85% H.sub.3PO.sub.4 and the TEA were slowly added. Al.sub.2O.sub.3 was added under stirring. The mixture was heated at 50 C. and then stirred for 1 h. Then, thereto Ludox AS30 was added and the mixture was subjected to stirring for 30 min. The resulting mixture was heated to a temperature of 190 C. hours in an autoclave. The product was then crystallized at 190 C. for 24 h without stirring. The product was subjected to centrifugal separation and washing with water (pH=7) and then dried at 120 C. The product was calcined at 500 C. for 5 h in air to obtain 59 g of the zeolitic material.

[0309] b) Preparing an Extrudate of the SAPO-34 Zeolitic Material

[0310] Materials Used:

TABLE-US-00012 SAPO-34 zeolitic material, according to a) above: 59 g De-ionized water: 30 ml Ludox AS40 (Grace; colloidal silica; 37 g aqueous solution, 40 weight-%): Walocel 5% 73.8 g

[0311] The zeolitic material, the Ludox and the Walocel were kneaded for 1 h with gradual addition of the deionized water. The paste obtained was extruded and strands of a diameter of 1 mm were formed. The strands were dried at 120 C. and then calcined for 5 hours at 500 C.

[0312] The NH3-TPD analysis performed according to Reference Example 1.2 showed the following peaks (Table 4).

TABLE-US-00013 TABLE 4 Results of the NH3-TPD analysis Temperature at Peak maximum/ Quantity/ concentration/ Peak number C. mmol/g % 1 201.4 0.286 1.35 2 424.5 0.224 1.11 3 334.9 0.297 0.99

[0313] The plot of the NH3-TPD analysis is shown in FIG. 4

Reference Example 4: Preparation of a Molding Comprising a Zeolitic Material Having Framework Type CHA

[0314] a) Providing a CHA Zeolitic Material

[0315] A zeolitic material having framework type CHA was prepared as follows:

[0316] 2,040 kg of water were placed in a stirring vessel and 3,924 kg of a solution of 1-adamantyltrimethyl ammoniumhydroxide (20 weight-% aqueous solution) were added thereto under stirring. 415.6 kg of a solution of sodium hydroxide (20 weight-% aqueous solution) were then added, followed by 679 kg of aluminum triisopropylate (Dorox D 10, Ineos), after which the resulting mixture was stirred for 5 min. 7800.5 kg of a solution of colloidal silica (40 weight-% aqueous solution; Ludox AS 40, Sigma Aldrich) were then added and the resulting mixture stirred for 15 min before being transferred to an autoclave. 1,000 kg of distilled water used for washing out the stirring vessel were added to the mixture in the autoclave, and the final mixture was then heated under stirring for 19 h at 170 C. The solid product was then filtered off and the filter cake washed with distilled water. The resulting filter cake was then dispersed in distilled water in a spray dryer mix tank to obtain a slurry with a solids concentration of approximately 24 weight-% and then spray dried, wherein the inlet temperature was set to 477-482 C. and the outlet temperature was measured to be 127-129 C., thus affording a spray dried powder of a zeolite having the CHA framework structure. The resulting material had a particle size distribution affording a Dv10 value of 1.4 micrometer, a Dv50 value of 5.0 micrometer, and a Dv90 value of 16.2 micrometer. The material displayed a BET specific surface area of 558 m.sup.2/g, a silica to alumina ratio of 34, a crystallinity of 105% as determined by powder X-ray diffraction. The sodium content of the product was determined to be 0.75 weight-% calculated as Na.sub.2O.

[0317] b) Preparing an Extrudate of the CHA Zeolitic Material

[0318] Materials Used:

TABLE-US-00014 CHA zeolitic material, according to a) above: 75 g De-ionized water: 65 ml Ludox AS40 (Grace; colloidal silica; aqueous 46.7 g solution, 40 weight-%): Walocel 5% 93.8 g

[0319] The zeolitic material, the Ludox and the Walocel were kneaded for 1 h with gradual addition of the deionized water. The paste obtained was extruded and strands of a diameter of 1 mm were formed. The strands were dried at 120 C. and then calcined for 5 hours at 500 C. 65 g of product were obtained.

Reference Example 5: Preparation of a Mixed Oxide of Cr, Zn, and Al

Reference Example 5.1: Preparation at 400 C.

[0320] The mixed oxide was prepared by co-precipitation. 43.68 g of Zn(NO.sub.3).sub.26H.sub.2O (Sigma-Aldrich, purity 99%), 16.8 g Cr(NO.sub.3).sub.39H.sub.2O (Sigma-Aldrich, purity 99%) and 15.75 g Al(NO.sub.3).sub.39H.sub.2O (Fluka, purity 98%) were dissolved in 500 ml distilled water at 70 C. under stirring. A 20% aqueous solution of (NH.sub.4).sub.2CO.sub.3 was used as precipitation agent. The precipitation agent was added dropwise to the metal solution within 60 min so that the final pH of the solution was 7. After addition of the precipitation agent the mixture was stirred for 180 min at 70 C. The resulting precipitate was filtered and washed with distilled water until the nitrate-test strip indicated that the washing water was free of nitrate ions. The sample was then dried at 110 C. for 15 h under static air, and subsequently calcined at 400 C. for 1 h under static air. The calcined sample was then sieved to obtain the particle fraction needed for testing. The resulting chemical composition of the calcined sample, determined by elemental analysis, was 6.9 weight-% Al, 12.6 weight-% Cr and 51 weight-% Zn. The N.sub.2-BET surface area of the calcined powder determined according to Reference Example 1.1 was 107 m.sup.2/g. The XRD pattern of the calcined powder determined according to Reference Example 1.4 showed broad reflections which were assigned to zyncite-like phase ZnO and gahnite-like phase Zn(Al.sub.1.06Cr.sub.0.94)O.sub.4. The XRD pattern is shown in FIG. 8.

Reference Example 5.2: Preparation at 500 C.

[0321] The mixed oxide was prepared by co-precipitation. 8.2 g of Zn(NO.sub.3).sub.26H.sub.2O (Sigma-Aldrich, purity 99%), 22.4 g Cr(NO.sub.3).sub.39H.sub.2O (Sigma-Aldrich, purity 99%) and 21.0 g Al(NO.sub.3).sub.39H.sub.2O (Fluka, purity 98%) were dissolved in 500 ml distilled water at 70 C. under stirring. A 20 wt % aqueous solution of (NH.sub.4).sub.2CO.sub.3 was used as precipitation agent. The precipitation agent was added dropwise to the metal solution in-between 63 min so that the final pH of the solution was 7. After addition of the precipitation agent the mixture was stirred for 180 min at 70 C. The resulting precipitate was filtered and washed with distilled water until the nitrate-test strip indicated that the washing water was free of nitrate ions. The sample was then dried at 110 C. for 15 h under static air, and subsequently calcined at 500 C. for 1 h under static air. The calcined sample was then sieved to obtain the particle fraction needed for testing. The resulting chemical composition of the calcined catalyst, determined by elemental analyses, was 6.9 weight-% Al, 12.5 weight-% Cr and 53 weight-% Zn. The N.sub.2-BET surface area of the calcined powder determined according to Reference Example 1.1 was 79 m.sup.2/g. The XRD pattern of the calcined powder determined according to Reference Example 1.4 showed broad reflections which were assigned to zyncite-like phase ZnO and gahnite-like phase Zn(Al.sub.1.06Cr.sub.0.94)O.sub.4. The XRD pattern is shown in FIG. 9.

Reference Example 5.3: Preparation at 750 C.

[0322] The mixed oxide was prepared by co-precipitation. 58.2 g of Zn(NO.sub.3).sub.26H.sub.2O (Sigma-Aldrich, purity 99%), 22.4 g Cr(NO.sub.3).sub.39H.sub.2O (Sigma-Aldrich, purity 99%) and 21.0 g Al(NO.sub.3).sub.39H.sub.2O (Fluka, purity 98%) were dissolved in 500 ml distilled water at 70 C. under stirring. A 20 wt % aqueous solution of (NH.sub.4).sub.2CO.sub.3 was used as precipitation agent. The precipitation agent was added dropwise to the metal solution in-between 63 min so that the final pH of the solution was 7. After addition of the precipitation agent the mixture was stirred for 180 min at 70 C. The resulting precipitate was filtered and washed with distilled water until the nitrate-test strip indicated that the washing water was free of nitrate ions. The sample was then dried at 110 C. for 15 h under static air, and subsequently calcined at 750 C. for 1 h under static air. The calcined sample was then sieved to obtain the particle fraction needed for testing. The resulting chemical composition of the calcined catalyst, determined by elemental analyses, was 7.4 weight-% Al, 13.1 weight-% Cr and 54 weight-% Zn. The N.sub.2-BET surface area of the calcined powder determined according to Reference Example 1.1 was 21 m.sup.2/g. The XRD pattern of the calcined powder determined according to Reference Example 1.4 showed broad reflections which were assigned to zyncite-like phase ZnO and gahnite-like phase Zn(Al.sub.1.06Cr.sub.0.94)O.sub.4. The XRD pattern is shown in FIG. 10.

Comparative Example 1: Preparation of Comparative Catalysts

[0323] The comparative catalysts were prepared by physically mixing (shaking) the mixed metal oxides of Reference Examples 5 and the zeolite material of Reference Examples 2 to 4 in a beaker. The compositions of the catalysts are shown in Table 5 below:

TABLE-US-00015 TABLE 5 Composition of the catalysts Ref- Vol- Vol- Ratio erence Zeolitic Metal ume ume MO/ Example material (Zeo) Oxide (MO) Zeo/ml MO/ml Zeo/g/g RE 6.1 SAPO-A (RE 2) Cr.sub.2/ZnO (500 C.) 1.028 0.172 0.33 RE 6.2 SAPO-A (RE 2) Cr.sub.2/ZnO (500 C.) 0.681 0.519 1.5 RE 6.3 SAPO-B (RE 3) Cr.sub.2/ZnO (400 C.) 0.884 0.316 0.33 RE 6.4 SAPO-B (RE 3) Cr.sub.2/ZnO (500 C.) 1.063 0.137 0.33 RE 6.5 SAPO-B (RE-3) Cr.sub.2/ZnO (750 C.) 1.067 0.133 0.33 RE 6.6 CHA (RE 4) Cr.sub.2/ZnO (500 C.) 1.081 0.119 0.33 RE 6.7 CHA (RE 4) Cr/ZnO.sub.2 (500 C.) 0.800 0.400 1.5 RE 6.8 0.5% Cr.sub.2/ZnO (500 C.) 1.028 0.172 0.33 Mg-SAPO-A (RE 2.1) RE 6.9 1.1% Cr.sub.2/ZnO (500 C.) 1.029 0.171 0.33 Mg-SAPO-A (RE 2.2) RE 6.10 2% Cr.sub.2/ZnO (500 C.) 1.026 0.174 0.33 Mg-SAPO-A (RE 2.3)

Example 1: Preparation of a Molding Comprising a 0.48 Weight-% Mg-CHA Zeolitic Material

[0324] a) Providing a Mg-CHA Zeolitic Material

TABLE-US-00016 CHA zeolitic material of Reference Example 4a) 80 g Mg(NO.sub.3).sub.2 H.sub.2O 4.1 g De-ionized water 120 g

[0325] Mg(NO.sub.3).sub.2H.sub.2O was dissolved in water and homogenized. The solution was added dropwise to the zeolitic material comprised in a beaker. The impregnated zeolite was transferred in a porcelain bowl. The material was dried at 120 C. and then calcined for 5 hours at 500 C. 82 g of product were obtained. Elemental analysis of the zeolitic material releveled a Mg content of 0.48 weight-%. The NH3-TPD analysis performed as disclosed in Reference Example 1.2 showed the following peaks (see Table 6 below).

TABLE-US-00017 TABLE 6 Results of the TPD-NH3 analysis Peak Temperature at Quantity/ Peak number maximum/ C. mmol/g concentration/% 1 219 0.719 1.77 2 475.6 0.227 0.93 3 573.8 0.074 0.80

[0326] The plot of the NH3-TPD analysis is disclosed in FIG. 5.

[0327] b) Preparing an Extrudate of the 0.48 Weight-% Mg-CHA Zeolitic Material

[0328] Materials Used:

TABLE-US-00018 0.48% Mg-CHA zeolitic material, according 75 g to a) above: Ludox AS40 (Grace; colloidal silica; aqueous 46.9 g solution, 40 weight-%): Walocel 5% 93.8 g

[0329] The zeolitic material, the Ludox and the Walocel were kneaded for 1 h (with no addition of water). The material obtained was extruded and strands of 1 mm diameter were formed. The strands obtained were dried hours at 120 C. and then calcined for 5 hours at 500 C. 70 g of product were obtained.

Example 2: Preparation of a Molding of a 1.2 Weight-% Mg-CHA Zeolitic Material

[0330] a) Providing a Mg-CHA Zeolitic Material

[0331] Materials used

TABLE-US-00019 CHA zeolitic material of Reference Example 4a) 80 g Mg(NO.sub.3).sub.2 H.sub.2O 8.8 g De-ionized water 120 g

[0332] Mg(NO.sub.3).sub.2H.sub.2O was dissolved in water and homogenized. The solution was added dropwise to the zeolitic material comprised in a beaker. The impregnated zeolite was transferred in a porcelain bowl. The material was dried at 120 C. and then calcined for 5 hours at 500 C. 82 g of product were obtained. Elemental analysis of the zeolitic material showed a Mg content of 1.2 weight-%. The NH3-TPD analysis performed according to Reference Example 1.2 showed the following peaks (see Table 7 below).

TABLE-US-00020 TABLE 7 Results of the TPD-NH3 analysis Peak Temperature at Quantity/ Peak number maximum/ C. mmol/g concentration/% 1 220.6 0.772 1.59 2 487.5 0.275 0.92 3 591.7 0.027 0.77

[0333] The plot of the NH3-TPD analysis is shown in FIG. 6.

[0334] b) Preparing an Extrudate of the 1.2 Weight-% Mg-CHA Zeolitic Material

[0335] Materials Used:

TABLE-US-00021 1.2% Mg-CHA zeolitic material, according to a) above: 75 g Ludox AS40 (Grace; colloidal silica; aqueous 46.9 g solution, 40 weight-%): Walocel 5% 93.8 g

[0336] The zeolitic material, the Ludox and the Walocel were kneaded for 1 h (with no addition of water). The material obtained was extruded and strands of 1 mm diameter were formed. The strands obtained were dried hours at 120 C. and then calcined for 5 hours at 500 C. 58 g of product were obtained.

Example 3: Preparation of the Extrudate of a 1.6% Mg-CHA Zeolitic Material

[0337] a) Providing a Mg-CHA Zeolitic Material

TABLE-US-00022 CHA zeolitic material of Reference Example 4a) 80 g Mg(NO.sub.3).sub.2 H.sub.2O 16.8 g De-ionized water 120 g

[0338] Mg(NO.sub.3).sub.2H.sub.2O was dissolved in water and homogenized. The solution was added dropwise to the zeolitic material comprised in a beaker. The impregnated zeolite was transferred in a porcelain bowl. The material was dried at 120 C. and then calcined for 5 hours at 500 C. 85 g of product were obtained. Elemental analysis of the zeolitic material revealed a Mg content of 1.6 weight-%. The NH3-TPD analysis performed according to Reference Example 1.2 showed the following peaks (see Table 8 below).

TABLE-US-00023 TABLE 8 Results of the NH3-TPD analysis Peak Temperature at Quantity/ Peak number maximum/ C. mmol/g concentration/% 1 216.5 0.978 1.40 2 463.3 0.127 0.79 3 575.9 0.086 0.788

[0339] The plot of the NH3-TPD analysis is disclosed in FIG. 7.

[0340] b) Preparing an Extrudate of the 1.6% Mg-CHA Zeolitic Material

[0341] Materials Used:

TABLE-US-00024 1.6% Mg-CHA zeolitic material, according to a) above: 75 g Ludox AS40 (Grace; colloidal silica; aqueous 46.9 g solution, 40 weight-%): Walocel 5% 93.8 g

[0342] The zeolitic material, the Ludox and the Walocel were kneaded for 1 h (with no addition of water). The material obtained was extruded and strands of 1 mm diameter were formed. The strands obtained were dried hours at 120 C. and then calcined for 5 hours at 500 C. 56 g of product were obtained.

Example 4: Preparation of Catalysts According to the Invention

[0343] The catalysts were prepared by physically mixing (shaking) the mixed metal oxides and the moldings comprising the zeolite material in a beaker. The compositions of the catalysts are shown in Table 9 below.

TABLE-US-00025 TABLE 9 Compositions of the catalysts Zeolitic Metal Oxide Volume Volume Ratio MO/ Example material (Zeo) (MO) Zeo/ml MO/ml Zeo/g/g E4.1 0.5% Mg-CHA Cr.sub.2/ZnO 1.024 0.176 0.33 (E1) (500 C.) E4.2 1.2% Mg-CHA Cr.sub.2/ZnO 1.024 0.176 0.33 (E2) (500 C.) E4.3 1.6% Mg-CHA Cr.sub.2/ZnO 1.024 0.176 0.33 (E3) (500 C.) E4.4 1.6% Mg-CHA Cr.sub.2/ZnO 0.784 0.416 1.5 (E3) (500 C.)

Example 5: Process for Preparing C2 to C4 Olefins from a Synthesis Gas Stream Comprising H.SUB.2 .and CO

[0344] The catalysts prepared in Examples 4 and in Reference Example 5 (in each case 1.2 ml) were installed in a continuously operated, electrically heated tubular reactor. The catalysts were activated using a gas stream of 10% H.sub.2 in N.sub.2 (10/90 vol %/vol %) at a gas hourly space velocity (GHSV) of 6000 h.sup.1, heating to a temperature of 310 C. (heating rate 1 K/min) for 2 h, cooling to a temperature of 240 C., and washing with a gas stream of H.sub.2/CO (1.5:1). The pressure was slowly brought to 20 bar(abs). The synthesis gas stream to be converted was fed directly into the reactor for conversion into C2 to C4 olefins at a GSHV of 2208 h.sup.1 The pressure was maintained at 20 bar(abs). The reaction parameters were maintained over the entire run time. Downstream of the tubular reactor, the gaseous product mixture was analysed by on-line chromatography. The process varied in the H.sub.2/CO ratio and in the temperature according to following Table 10.

TABLE-US-00026 TABLE 10 Process parameters H.sub.2/CO volume Temperature Time on ratio of synthesis during Pressure/ Stage stream/h gas stream conversion/ C. bar(abs) 1 0-70 0.5:1 350 20 2 71-96 1.5:1 350 20 3 97-120 0.5:1 400 20 4 120-142 1.5:1 400 20

[0345] The results achieved in the tubular reactor for the catalysts according to Example 4 and Reference Example 5 and with respect to the selectivities are shown in Tables 11 to 14 for each stage. These are the average selectivities during the run time of the catalyst in which the conversion of CO is as indicated in the respective Tables 11 to 14.

TABLE-US-00027 TABLE 11 Stage 1 Select. Select. Conv. Select. Select. C2-C4 C2-C4 Select. Select. Select. CO/ MeOH/ CH4 paraf./ olefins/ C5+ CO.sub.2/ Others/ Stage 1 Catalyst mol-% mol-% mol-% mol-% mol-% mol-% mol-% mol-% E 5.1 E 4.1 4.901 0.000 1.784 8.530 24.563 1.364 50.763 12.996 E 4.2 4.222 0.000 1.641 4.896 25.468 1.902 50.284 15.810 E 4.3 3.568 0.000 2.325 3.089 29.123 1.287 50.498 13.679 E 4.4 5.542 1.680 3.459 2.255 24.094 0.724 60.567 7.222 RE 6.1 3.442 2.636 4.286 8.264 10.823 0.452 71.153 2.387 RE 6.2 5.014 3.775 7.659 5.433 1.866 0.261 80.031 0.975 RE 6.3 6.240 0.000 1.308 6.723 33.422 0.689 49.888 7.971 RE 6.4 5.289 0.000 1.304 6.973 31.507 0.821 49.834 9.562 RE 6.5 4.274 0.000 1.312 7.691 29.645 0.981 49.875 10.497 RE 6.6 4.924 0.000 1.909 19.845 15.109 1.122 51.967 10.048 RE 6.7 10.441 0.000 1.815 7.653 27.132 1.412 49.811 12.177 RE 6.8 3.565 3.154 5.297 1.592 1.997 0.000 86.920 1.040 RE 6.9 2.634 5.592 6.932 0.277 1.904 0.000 83.969 1.326 RE 6.10 2.723 6.457 7.610 0.420 3.404 0.382 79.573 2.154

TABLE-US-00028 TABLE 12 Stage 2 Select. Select. Conv. Select. Select. C2-C4 C2-C4 Select. Select. Select. CO/ MeOH/ CH4 paraf./ olefins/ C5+ CO.sub.2/ Others/ Stage 2 Catalyst mol-% mol-% mol-% mol-% mol-% mol-% mol-% mol-% E 5.1 E 4.1 7.332 0.000 2.784 10.157 29.372 1.177 45.862 10.648 E 4.2 5.474 0.000 2.580 4.524 34.439 1.012 46.636 10.809 E 4.3 4.530 0.000 4.131 3.577 31.861 0.739 51.703 7.989 E 4.4 8.142 9.820 5.213 2.556 14.658 0.595 63.420 3.738 RE 6.1 5.150 10.424 7.092 7.802 2.316 0.000 71.361 1.005 RE 6.2 7.874 10.621 7.884 4.801 1.540 0.000 74.082 1.072 RE 6.3 6.924 4.477 3.160 7.463 13.404 0.591 66.597 4.308 RE 6.4 6.603 2.328 2.643 8.452 23.700 0.673 55.189 7.014 RE 6.5 5.572 1.169 2.058 9.898 29.551 0.680 48.687 7.958 RE 6.6 7.656 0.000 2.602 26.550 15.133 0.994 45.746 8.975 RE 6.7 15.643 0.000 2.933 16.311 20.531 1.446 46.830 11.948 RE 6.8 5.809 9.217 4.780 1.262 1.990 0.000 81.347 1.404 RE 6.9 4.824 14.728 5.985 0.502 2.271 0.000 74.862 1.653 RE 6.10 4.420 15.777 7.387 0.729 3.159 0.574 70.480 1.895

TABLE-US-00029 TABLE 13 Stage 3 Select. Select. Conv. Select. Select. C2-C4 C2-C4 Select. Select. Select CO/ MeOH/ CH4 paraf./ olefins/ C5+ CO.sub.2/ Others/ Stage 3 Catalyst mol-% mol-% mol-% mol-% mol-% mol-% mol-% mol-% E 5.1 E 4.1 7.121 0.000 3.905 8.254 29.699 0.783 48.711 8.647 E 4.2 5.586 0.000 4.168 4.710 33.169 0.878 48.268 8.807 E 4.3 4.683 0.000 5.752 4.673 32.241 0.781 48.254 8.299 E 4.4 6.109 0.000 7.465 5.929 29.707 0.671 49.076 7.153 RE 6.1 2.330 0.000 13.034 16.835 14.779 0.473 51.636 3.244 RE 6.2 3.209 0.000 20.352 14.178 10.276 0.577 51.019 3.598 RE 6.3 9.743 0.000 2.754 6.270 36.728 0.481 48.413 5.355 RE 6.4 7.322 0.000 3.136 7.334 35.415 0.471 48.342 5.302 RE 6.5 6.626 0.000 2.703 7.770 35.219 0.478 48.282 5.549 RE 6.6 7.900 0.000 3.954 25.197 14.523 0.703 48.800 6.823 RE 6.7 17.122 0.000 3.514 12.313 23.948 0.973 48.904 10.348 RE 6.8 1.780 0.000 20.484 6.931 11.335 0.614 55.705 4.931 RE 6.9 1.485 0.000 23.526 3.340 9.804 0.820 56.408 6.102 RE 6.10 1.431 0.000 24.018 3.423 10.341 0.867 55.538 5.813

TABLE-US-00030 TABLE 14 Stage 4 Select. Select. Conv. Select. Select. C2-C4 C2-C4 Select. Select. Select. CO/ MeOH/ CH4 paraf./ olefins/ C5+ CO.sub.2 / Others/ Stage 4 Catalyst mol-% mol-% mol-% mol-% mol-% mol-% mol-% mol-% E 5.1 E 4.1 14.023 0.000 5.446 17.678 20.859 1.169 45.283 9.566 E 4.2 10.383 0.000 4.980 7.964 31.255 1.093 44.901 9.808 E 4.3 9.827 0.000 7.786 10.943 28.054 0.820 44.532 7.866 E 4.4 9.877 0.000 9.211 10.783 26.611 0.637 46.226 6.532 RE 6.1 5.430 0.445 13.878 26.966 10.013 0.406 46.094 2.197 RE 6.2 5.923 0.708 18.740 23.458 8.003 0.337 47.001 1.754 RE 6.3 15.315 0.000 3.812 10.481 33.531 0.633 45.237 6.306 RE 6.4 13.972 0.000 3.761 11.898 32.637 0.588 45.179 5.936 RE 6.5 11.936 0.000 3.926 14.625 30.069 0.617 44.771 5.991 RE 6.6 14.998 0.000 4.619 43.152 3.470 1.083 44.977 2.699 RE 6.7 30.463 0.000 4.542 32.875 7.842 1.053 45.958 7.730 RE 6.8 2.761 2.495 24.213 9.401 8.701 0.470 51.862 2.858 RE 6.9 2.091 1.843 28.247 4.795 7.637 0.509 53.892 3.076 RE 6.10 2.169 1.963 28.576 4.506 8.635 0.487 52.601 3.233

[0346] The selectivities of the catalyst of example E 4.2 with respect to the hydrocarbons are listed in Table 15:

TABLE-US-00031 TABLE 15 Average selectivities (S) in % at CO conversions as indicated of the catalyst of example 4.2 Product Stage 1 Stage 2 Stage 3 Stage 4 CO Conversion % 3.885 5.149 5.013 10.264 S(methane) 1.930 2.922 4.675 5.069 S(ethane) 0.503 0.981 1.645 2.281 S(propane) 2.265 2.705 2.228 4.906 S(butane) 0.858 0.835 0.509 1.076 S(ethene) 9.608 13.709 11.026 9.257 S(propene) 18.443 18.776 20.748 19.441 S(butene) 2.066 1.672 1.672 1.785 S(Meho) 0 0 0 0 S(CO2) 49.511 47.252 48.229 45.034

[0347] The selectivity's of the catalyst of example E 4.2 with respect to the olefins/paraffin based on the total hydrocarbon (CO.sub.2 subtracted) are listed in Table 16.

TABLE-US-00032 TABLE 16 Average selectivities (S).sub.ion % of the catalyst of example 4.2 Product Stage 1 Stage 2 Stage 3 Stage 4 S(MeOH) 0 0 0 0 S(methane) 1.930 2.922 4.675 5.069 S(C2-C4 paraffins) 3.626 4.520 4.381 8.26. S(C2-C4 olefins) 30.116 34.157 33.445 30.483 S(C5+) 1.458 0.957 0.832 1.146

BRIEF DESCRIPTION OF THE FIGURES

[0348] FIG. 1: shows the results NH3-TPD analysis of the zeolitic material 0.5% Mg-SAPO-34 according to Reference Example 2.1

[0349] FIG. 2: shows the results NH3-TPD analysis of the zeolitic material 1.1% Mg-SAPO-34 according to Reference Example 2.2

[0350] FIG. 3: shows the results NH3-TPD analysis of the zeolitic material 2.0% Mg-SAPO-34 according to Reference Example 2.3

[0351] FIG. 4: shows the results NH3-TPD analysis of the zeolitic material SAPO-34 according to Reference Example 3

[0352] FIG. 5: shows the results NH3-TPD analysis of the zeolitic material 0.48% Mg-CHA according to Example 1

[0353] FIG. 6: shows the results NH3-TPD analysis of the zeolitic material 1.2% Mg-CHA according to Example 2

[0354] FIG. 7: shows the results NH3-TPD analysis of the zeolitic material 1.6% Mg-CHA according to Example 3

[0355] FIG. 8: shows the XRP pattern of the mixed metal oxide of Reference Example 5.1

[0356] FIG. 9: shows the XRP pattern of the mixed metal oxide of Reference Example 5.2

[0357] FIG. 10: shows the XRP pattern of the mixed metal oxide of Reference Example 5.3

CITED PRIOR ART

[0358] U.S. Pat. No. 4,049,573 [0359] Goryainova et al., in: Petroleum Chemistry, vol. 51, no. 3 (2011) pp. 169-173 [0360] Wan, V. Y., Methanol to Olefins/Propylene Technologies in China, Process Economics Program, 261A (2013) [0361] Li, J., X. Pan and X. Bao, Direct conversion of syngas into hydrocarbons over a core-shell CrZn@SiO2@SAPO-34 catalyst, Chinese Journal of Catalysis vol. 36 no. 7 (2015), pp. 1131-1135