PROCESS FOR PREPARING A MOLDING COMPRISING A ZEOLITE CATALYST AND METHOD FOR CONVERTING OXYGENATES TO OLEFINS USING THE CATALYTIC MOLDING

Abstract

The present invention relates to a process for preparing a molding comprising a zeolitic material and one or more oxidic binders, the process particularly comprising preparing a mixture of a zeolitic material, such as Mg-ZSM-5, a source of an oxidic binder, and a first plasticizer; admixing an acid to said mixture; and shaping of the mixture, to obtain a precursor of a molding; wherein in said mixture a specific weight ratio of the source of the oxidic binder to the sum of the zeolitic material and the source of the oxidic binder is applied. Further, the present invention relates to a molding obtainable or obtained by the inventive process, and to a molding itself displaying in particular a comparatively improved crush strength. Yet further, the present invention relates to a method for the conversion of oxygenates to olefins and to a use of the inventive molding.

Claims

1-15. (canceled)

16. A process for preparing a molding comprising a zeolitic material and one or more oxidic binders, wherein the zeolitic material comprises YO.sub.2 and X.sub.2O.sub.3 in its framework structure, wherein Y is Si and X is a trivalent element, the process comprising (i) preparing a mixture comprising a zeolitic material, a source of an oxidic binder, a first plasticizer, and an acid; (v) shaping of the mixture obtained in (i), to obtain a precursor of a molding; wherein in the mixture prepared in (i) the weight ratio of the source of the oxidic binder, calculated as the oxide, to the sum of the zeolitic material and the source of the oxidic binder, calculated as the oxide, is in the range of from 0.05:1 to 0.15:1; wherein the source of the oxidic binder comprises one or more of AlOOH (boehmite) and Al.sub.2O.sub.3; wherein X is selected from the group consisting of B, Al, Ga, In, and a mixture of two or more thereof.

17. The process of claim 16, wherein (i) comprises (i.1.a) preparing a mixture comprising a zeolitic material, a source of an oxidic binder, and a first plasticizer; (i.1.b) admixing an acid to the mixture obtained in (i.1.a); wherein the acid is admixed in (i.1.b), comprising an amount of the acid in the range of from 5 to 50 weight-%; and wherein the weight ratio of the acid admixed in (i.1.b) to the sum of the zeolitic material and the source of the oxidic binder of the mixture prepared in (i) is in the range of from 0.05:1 to 0.15:1.

18. The process of claim 16, wherein (i) comprises (i.2.a) providing a zeolitic material; (i.2.b) providing a mixture comprising a source of an oxidic binder, optionally water, and an acid; (i.2.c) mixing the mixture obtained in (i.2.b) with the zeolitic material provided in (i.2.a); (i.2.d) admixing a first plasticizer to the mixture obtained in (i.2.c); wherein the acid is provided for the mixture of (i.2.b) as an aqueous solution comprising an amount of the acid in the range of from 50 to 80 weight-%, wherein the weight ratio of the acid provided for the mixture of (i.2.b) to the sum of the zeolitic material and the source of the oxidic binder of the mixture prepared in (i) is in the range of from 0.005:1 to 0.05:1.

19. The process of claim 16, wherein the first plasticizer is selected from the group consisting of organic polymers, carbohydrates, graphite, plant additives, and mixtures of two or more thereof.

20. The process of claim 16, wherein the source of the oxidic binder comprises AlOOH (boehmite).

21. The process of claim 16, wherein the zeoltic material has a framework structure type selected from the group consisting of ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFV, AFX, AFY, AHT, ANA, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AVL, AWO, AWW, BCT, BEA, BEC, BIK, BOF, BOG, BOZ, BPH, BRE, BSV, CAN, CAS, CDO, CFI, CGF, CGS, CHA, -CHI, -CLO, CON, CSV, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EEI, EMT, EON, EPI, EM, ESV, ETR, EUO, *-EWT, EZT, FAR, FAU, FER, FRA, GIS, GIU, GME, GON, GOO, HEU, IFO, IFR, -IFU, IFW, IFY, IHW, IMF, IRN, IRR, -IRY, ISV, ITE, ITG, ITH, *-ITN, ITR, ITT, -ITV, ITW, IWR, IWS, IWV, IWW, JBW, JNT, JOZ, JRY, JSN, JSR, JST, JSW, KFI, LAU, LEV, LIO, -LIT, LOS, LOV, LTA, LTF, LTJ, LTL, LTN, MAR, MAZ, MEI, MEL, MEP, MER, MEI, MFS, MON, MOR, MOZ, *MRE, MSE, MSO, MTF, MTN, MTT, MTW, MVY, MWF, MWW, NAB, NAT, NES, NON, NPO, NPT, NSI, OBW, OFF, OKO, OSI, OSO, OWE, -PAR, PAU, PCR, PHI, PON, POS, PSI, PUN, RHO, -RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAF, SAO, SAS, SAT, SAV, SBE, SBN, SBS, SBT, SEW, SFE, SFF, SFG, SFH, SFN, SFO, SFS, *SFV, SFW, SGT, SIV, SOD, SOF, SOS, SSF, *-SSO, SSY, STF, STI, *STO, STT, STW, -SVR, SVV, SZR, TER, THO, TOL, TON, TSC, TUN, UEI, UFI, UOS, UOV, UOZ, USI, UTL, UWY, VET, VFI, VNI, VSV, WEI, -WEN, YUG, ZON, and mixed types of two or more thereof.

22. The process of claim 16, wherein the zeolitic material comprises one or more alkaline earth metals M.

23. The process of claim 16, wherein the acid is one or more of an inorganic acid and an organic acid.

24. The process of claim 16, wherein in (v), the mixture is shaped to a strand.

25. A molding obtainable or obtained by the process of claim 16.

26. A molding comprising one or more oxidic binders and a zeolitic material, wherein the zeolitic material comprises YO.sub.2 and X.sub.2O.sub.3 in its framework structure, wherein Y is Si and X is a trivalent element, wherein the molding comprises the one or more oxidic binders, calculated as the oxide, in an amount in the range of from 5 to 15 weight-%, and wherein the molding exhibits a crush strength of equal or greater than 9 N, determined according to Reference Example 5, wherein the one or more oxidic binders are alumina, wherein X is selected from the group consisting of B, Al, Ga, In, and a mixture of two or more thereof.

27. The molding of claim 26, exhibiting a diffusion coefficient in the range of from 0.40 to 1.30×10.sup.−9 m.sup.2/s, determined according to Reference Example 4.

28. The molding of claim 26, exhibiting a tortuosity parameter relative to water in the range of from 1.00 to 3.75, determined as described in Reference Example 2.

29. A method for the conversion of oxygenates to olefins comprising (a) providing a molding according to claim 25; (b) providing a gas stream comprising one or more oxygenates and optionally one or more olefins and/or optionally one or more hydrocarbons (c) contacting the molding provided in (a) with the gas stream provided in (b) and converting one or more oxygenates to one or more olefins and optionally to one or more hydrocarbons; (d) optionally recycling one or more of the one or more olefins and/or of the one or more hydrocarbons contained in the gas stream obtained in (c) to (b).

30. Use of a molding according to claim 25 as a molecular sieve, as an adsorbent, for ion-exchange, or as a catalyst and/or as a catalyst support.

Description

DESCRIPTION OF FIGURES

[0281] FIG. 1: shows a double logarithmic plot of data from a catalyst support at the various diffusion times used. On the ordinate, the signal is given in arbitrary units and on the abscissa, the value b is given. The slope of each line corresponds to a diffusion coeffi-cient.

[0282] FIG. 2: shows the catalytic performance of a molding prepared in accordance with Comparative Example 9. On the abscissa, the time on stream (TOS) is given in hours and on the ordinate, the conversion relative to methanol as well as the selectivity towards olefins, butylenes, propylene, ethylene, alkanes, and carbon oxides (CO and CO.sub.2) is given in %, determined according to Example 12.

[0283] FIG. 3: shows the catalytic performance of a molding prepared in accordance with Example 10. On the abscissa, the time on stream (TOS) is given in hours and on the ordinate, the conversion relative to methanol as well as the selectivity towards olefins, butylenes, propylene, ethylene, alkanes, and carbon oxides (CO and CO.sub.2) is given in %, determined according to Example 12.

[0284] FIG. 4: shows the catalytic performance of a molding prepared in accordance with Example 11. On the abscissa, the time on stream (TOS) is given in hours and on the ordinate, the conversion relative to methanol as well as the selectivity towards olefins, butylenes, propylene, ethylene, alkanes, and carbon oxides (CO and CO.sub.2) is given in %, determined according to Example 12.

[0285] FIG. 5: shows the catalytic performance of a molding prepared in accordance with Example 12. On the abscissa, the time on stream (TOS) is given in hours and on the ordinate, the conversion relative to methanol as well as the selectivity towards olefins, butylenes, propylene, ethylene, alkanes, and carbon oxides (CO and CO.sub.2) is given in %, determined according to Example 13.

CITED LITERATURE

[0286] WO 2012/085154 A1

[0287] US 2014/0058180 A1

[0288] U.S. Pat. No. 10,112,188 B2

[0289] US 2014/0058181 A1

[0290] U.S. Pat. No. 10,005,073 B2

[0291] U.S. Pat. No. 9,511,361 B2

[0292] US 2017/0121259 A1

[0293] WO 2018/109083 A1

[0294] CN 100503041 C

[0295] CN 104511298 B