Process for preparing a molded article comprising a zeolite catalyst and process for converting an oxide into an olefin using said catalytic molded article

Abstract

The present invention relates to a method for preparing a molded article comprising a zeolite material and one or more oxide binders, the method particularly comprising preparing a mixture of a zeolite material such as Mg-ZSM-5, a source of the oxide binder, and a first plasticizer; mixing an acid into the mixture; and shaping the mixture to obtain a precursor of the molded article; wherein a specific weight ratio of the source of the oxide binder to the sum of the zeolite material and the source of the oxide binder is applied in the mixture. Furthermore, the present invention relates to a molded article obtainable or obtained by the method of the present invention and to the molded article itself which particularly exhibits a relatively improved crushing strength. The present invention further relates to a method for converting an oxide into an olefin and to the use of the molded article of the present invention.

Description

Technical Field

[0001] The present invention relates to a specific method for preparing molded articles including the use of a plasticizer, molded articles prepared according to said method, and their uses. The molded articles have specific physical and chemical properties and contain a lower amount of binder at the same time.

[0002] Introduction

[0003] In the field of olefin synthesis, due to the increasing availability of C1 feedstocks, especially the conversion of methanol to propylene has played an increasingly important and interesting role. It is known that the synthesis of especially short-chain olefins requires highly specific catalysts to convert the corresponding feedstocks.

[0004] The specific challenges involved in such methods depend not only on the optimal selection of reaction parameters, but more importantly on the use of specific catalysts that allow highly efficient and selective conversion to, for example, the desired olefin fraction. As mentioned above, methods in which methanol is used as a feedstock are particularly important, and their catalytic conversion generally yields mixtures of hydrocarbons and their derivatives, especially olefins, alkanes, and aromatics.

[0005] Therefore, the specific challenges in such catalytic conversions lie in the optimization and fine-tuning of the catalysts used as well as the process framework and parameters. Methods developed over the past few decades for the conversion of oxides to olefins and especially for the conversion of methanol to olefins have become increasingly important in view of the decreasing oil reserves, and accordingly they are named methanol-to-olefin methods (MTO methods for methanol-to-olefin). The optimization of such methods is currently also of interest for reducing carbon dioxide emissions. Among the catalytic materials that have been used for such conversions, zeolite materials have proven to be highly effective, and zeolite materials are especially used.

[0006] WO 2012 / 085154 A1 relates to a method for preparing unsaturated carbohydrates in the presence of a catalyst comprising titanium silicoaluminophosphate (also named TAPSO therein) or titanium aluminophosphate. It is disclosed therein that the titanium silicoaluminophosphate used preferably has a CHA framework structure type.

[0007] US 2014 / 0058180 A1 relates to a method for producing a phosphorus-containing catalyst, wherein the catalyst comprises a zeolite, preferably a zeolite having a framework structure type of TON, MTT, MFI, MEL, MTW, or EUO. It is disclosed therein that the method includes treating the calcined zeolite with an aqueous solution or water treatment, and the aqueous solution can be selected from water, aqueous ammonium chloride solution, dilute hydrochloric acid, dilute acetic acid, and dilute nitric acid. US2014 / 058180A1 especially discloses a method for preparing a molded article comprising a zeolite and a binder in Example 2, wherein the weight ratio of the binder to the sum of the binder and the zeolite is about 0.176.

[0008] US 10,112,188 B2 and US 2014 / 0058181 A1 relate to a method for preparing a phosphorus-containing zeolite-type catalyst based on crystalline aluminosilicate, the catalyst of said method, and the use of said catalyst in the conversion of methanol to olefins. The method includes mixing alumina and an acid into pentasil zeolite powder, where the acid can be sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, or citric acid.

[0009] US 10,005,073 B2 also relates to the production of phosphorus-containing zeolites preferably having a framework structure type of MFI or MEL.

[0010] US 9,511,361 B2 relates to a catalyst containing a pentasil-type aluminosilicate and a binder, where the catalyst is in the form of spheres having a specific average diameter and a specific BET surface area. The catalyst can be used for the conversion of methanol to olefins. In addition, it is disclosed that the prepared catalyst can contain 10 - 40% by weight of the binder relative to the total weight of the aluminosilicate and the binder.

[0011] US 2017 / 0121259 A1 relates to a method for producing a catalyst containing copper, zinc, and aluminum, especially for producing catalyst moldings having enhanced mechanical strength, especially lateral compressive strength.

[0012] WO 2018 / 109083 A1 relates to a tableted catalyst for methanol synthesis having enhanced mechanical stability. The catalyst contains a metal-containing mixture containing copper, zinc, and aluminum, with calcium aluminate as the binder material.

[0013] CN 100503041 C relates to a catalyst for dimethyl ether synthesis and its preparation method, where the catalyst contains a hydrophobic zeolite having protons, cations selected from alkali metals, alkaline earth metals, and ammonium, and an inorganic binder selected from alumina, silica, and silica-alumina. The preparation of the catalyst includes providing a paste prepared from a mixture of an acid and a binder, mixing the paste with the zeolite, and extruding the resulting mixture.

[0014] CN 104511298 B relates to a catalyst system for the conversion of methanol to propylene, where the catalyst is characterized in that it contains a) 30 - 85% by weight of a modified zeolite molecular sieve with an SAR of 100 - 3000, b) 0.001 - 5% by weight of an improver, c) 0.1 - 20% by weight of a promoter component, d) 10 - 50% by weight of hydrophobic silica powder, and e) 3 - 55% by weight of a binder, based on the total weight of the catalyst system.

[0015] Despite the fact that the prior art has made considerable efforts with respect to the synthesis of novel catalytic materials on the one hand by using new and improved synthesis procedures and on the other hand they have various applications such as especially in the field of catalysis, there is still a continuing need to provide new catalytic materials, especially specific moldings, which show further improved properties especially with respect to their mechanical stability in order to achieve improved long life.

[0016] Detailed description

[0017] Accordingly, there is still a need to provide a method for preparing moldings which show improved mechanical properties while maintaining excellent catalytic activity in the conversion of oxides to olefins, especially for the conversion of methanol to propylene. Of particular interest is to provide such moldings which show improved mechanical stability, especially improved crush strength, while maintaining excellent catalytic activity.

[0018] Accordingly, it is an object of the present invention to provide a novel molding which is suitable for the conversion of oxides to olefins, especially for the selective conversion of methanol to propylene, for example under fixed applications, having relatively improved physical properties, especially improved mechanical strength. Similarly, moldings having improved twist with respect to water and improved diffusion coefficients can be prepared according to the novel method. Accordingly, another object of the present invention is to provide a method for preparing such moldings, especially a method having relatively reduced carbon dioxide emissions.

[0019] Surprisingly, it has now been found that a new method for preparing moldings can be provided, resulting in moldings having improved mechanical properties. Furthermore, it has surprisingly been found that moldings showing improved physical and chemical properties, especially improved mechanical strength and also improved twist with respect to water, as well as improved diffusion coefficients, can be prepared according to the present invention. The moldings of the present invention also show excellent catalytic activity in the conversion of methanol to olefins.

[0020] Accordingly, the present invention relates to a method for preparing a molding comprising a zeolite material and one or more oxide binders, wherein the zeolite material comprises YO2 and optionally X2O3 in its framework structure, where Y is a tetravalent element and X is a trivalent element, the method comprising:

[0021] (i) preparing a mixture comprising a zeolite material, a source of an oxide binder, a first plasticizer and an acid;

[0022] (ii) preferably mixing water into the mixture obtained in (i);

[0023] (iii) preferably mixing a second plasticizer into the mixture obtained in (i) or (ii);

[0024] (iv) preferably mixing water into the mixture obtained in (iii);

[0025] (v) Shaping the mixture obtained in (i), (ii), (iii) or (iv) to obtain a precursor of the molded article;

[0026] Wherein the weight ratio of the oxide binder source calculated as an oxide in the mixture obtained in (i) to the sum of the zeolite material and the oxide binder source calculated as an oxide is in the range of 0.05:1 - 0.15:1.

[0027] According to the present invention, a molded article should be understood as a three-dimensional entity obtained by a shaping method; thus, the term "molded article" is used synonymously with the term "shaped body".

[0028] The zeolite material contained in the molded article of the present invention is usually in powder form, and the latter can be prepared, for example, by a specific synthesis method that produces the desired particle size distribution, or by grinding a given zeolite material, or by spray drying a suspension containing the zeolite material, or by spray granulating a suspension containing the zeolite material, or by flash drying a suspension containing the zeolite material or by microwave drying a suspension containing the zeolite material.

[0029] Preferably, (i) of the method according to the first embodiment comprises:

[0030] (i.1.a) Providing a mixture comprising a zeolite material, an oxide binder source and a first plasticizer;

[0031] (i.1.b) Mixing an acid into the mixture obtained in (i.1.a).

[0032] Preferably, (i) of the method according to the second embodiment comprises:

[0033] (i.2.a) Providing a zeolite material;

[0034] (i.2.b) Providing a mixture comprising an oxide binder source, an acid and optionally water;

[0035] (i.2.c) Mixing the mixture obtained in (i.2.b) with the zeolite material provided in (i.2.a);

[0036] (i.2.d) Mixing a first plasticizer into the mixture obtained in (i.2.c).

[0037] In the case where the method includes (i.2.c), the mixing according to (i.2.c) can be carried out by mixing the mixture provided in (i.2.b) into the zeolite material provided in (i.2.a) or by mixing the zeolite material provided in (i.2.a) into the mixture provided in (i.2.b).

[0038] In the case where the method according to the second embodiment comprises (i.2.a), (i.2.b), (i.2.c) and (i.2.d), preferably water is included in the mixture obtained in (i.2.b), wherein the mixture obtained in (i.2.b) more preferably has a weight ratio of water to the oxide binder source calculated as the oxide binder source itself in the range of 1:1 - 10:1, more preferably 4.0:1 - 5.0:1, even more preferably 4.50:1 - 4.70:1.

[0039] More preferably, the present invention relates to a method for preparing a molded article comprising a zeolite material and one or more oxide binders, wherein the zeolite material contains YO2 and optionally X2O3 in its framework structure, where Y is a tetravalent element and X is a trivalent element, and the method comprises:

[0040] (i') preparing a mixture of a zeolite material, an oxide binder source and a first plasticizer;

[0041] (ii') mixing an acid into the mixture obtained in (i');

[0042] (iii') preferably mixing water into the mixture obtained in (ii');

[0043] (iv') preferably mixing a second plasticizer into the mixture obtained in (ii') or (iii');

[0044] (v') preferably mixing water into the mixture obtained in (iv');

[0045] (vi') shaping the mixture obtained in (ii'), (iii'), (iv') or (v') to obtain a precursor of the molded article;

[0046] wherein the weight ratio of the oxide binder source calculated as an oxide in the mixture prepared in (i') to the sum of the zeolite material and the oxide binder source calculated as oxides is in the range of 0.05:1 - 0.15:1.

[0047] Preferably, the mixture prepared in (i) or (i') is mixed in a kneader, a Lodige mixer (German: Mischer) or a mixing roll mill.

[0048] There is no particular limitation on the content of the first plasticizer in the mixture prepared in (i) or (i'). Preferably, the weight ratio of the first plasticizer to the sum of the zeolite material and the oxide binder source calculated as the oxide binder source itself in the mixture prepared in (i) or (i') is in the range of 0.01:1 - 0.1:1, preferably 0.02:1 - 0.08:1, more preferably 0.03:1 - 0.07:1, more preferably 0.04:1 - 0.06:1, and even more preferably 0.045:1 - 0.055:1.

[0049] Any suitable compound can generally be selected as the first plasticizer as long as it fulfills its function. Preferably, the first plasticizer is an organic compound. Particularly preferably, the first plasticizer is selected from organic polymers, carbohydrates, graphite, plant additives, and mixtures of two or more thereof, more preferably selected from polymer vinyl compounds, polyoxyalkenes, polyacrylates, polymethacrylates, polyolefins, polyamides, polyesters, polystyrenes, polysaccharides, and mixtures of two or more thereof, and the first plasticizer is more preferably a polysaccharide.

[0050] In the case where the first plasticizer is a polysaccharide, preferably the polysaccharide is selected from cellulose, cellulose derivatives, and starch, and the polysaccharide is more preferably one or more of methylcellulose and carboxymethylcellulose.

[0051] Further, in the case where the first plasticizer is a polysaccharide, preferably the polysaccharide has a bulk density in the range of 500 - 800 g / l, more preferably 550 - 750 g / l, more preferably 600 - 700 g / l, and even more preferably 630 - 670 g / l.

[0052] Further, in the case where the first plasticizer is a polysaccharide, preferably the polysaccharide has a viscosity in the range of 3000 - 4000 mPas, more preferably 3400 - 3600 mPas, and more preferably 3450 - 3550 mPas.

[0053] There is no particular limitation on the content of the oxide binder source. Preferably, the weight ratio of the oxide binder source calculated as the oxide in the mixture obtained in (i) or (i') to the sum of the zeolite material and the oxide binder source calculated as the oxide is in the range of 0.06:1 - 0.14:1, more preferably 0.07:1 - 0.13:1, more preferably 0.08:1 - 0.12:1, and more preferably 0.09:1 - 0.11:1.

[0054] Any suitable compound can generally be used as the oxide binder source. Preferably, the oxide binder source is one or more of a silica source, an alumina source, and a silica - alumina source, and more preferably an alumina source.

[0055] Particularly preferably, the oxide binder source comprises one or more of AlOOH (boehmite), Al2O3, Al(OH)3, hydrotalcite, silica sol, colloidal silica, wet-process silica and dry-process silica, preferably one or more of AlOOH (boehmite) and Al2O3, more preferably AlOOH (boehmite), wherein the oxide binder source is more preferably AlOOH (boehmite).

[0056] For the embodiment where the oxide binder can be silica, either colloidal silica or the so-called "wet-process" silica and the so-called "dry-process" silica can be used.

[0057] There is no particular limitation on the tetravalent element Y of the zeolite material, and thus any tetravalent element in the periodic system can be used for Y. Preferably, Y is selected from Si, Sn, Ti, Zr, Ge and mixtures of two or more thereof, more preferably selected from Si, Ti and mixtures thereof, and more preferably Y is Si.

[0058] There is no particular limitation on the trivalent element X of the zeolite material, and thus any trivalent element in the periodic system can be used for X. Preferably, X is selected from B, Al, Ga, In and mixtures of two or more thereof, more preferably selected from B, Al and mixtures thereof, and more preferably X is Al.

[0059] There is no particular limitation on the YO2 / X2O3 molar ratio of the zeolite material. Preferably, the zeolite material has a YO2 / X2O3 molar ratio in the range of 50 - 150, more preferably 75 - 125, more preferably 90 - 120, and more preferably 95 - 115. Particularly preferably, the YO2 / X2O3 molar ratio of the zeolite material is the silica / alumina molar ratio.

[0060] There is no restriction on the framework structure type of the zeolite material. Preferably, the zeolite material has a framework structure type selected from 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, ERI, 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, MFI, 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 a mixed type of two or more of them,More preferably selected from MFI, MEL, ITH, IWR, CON and mixed types of two or more of them, more preferably selected from MFI, ITH, IWR, CON and mixed types of two or more of them in terms of framework structure type. Particularly preferably, the zeolite material has an MFI framework structure type.

[0061] In the case where the zeolite material has an MFI framework structure type, preferably the zeolite material is selected from silicalite, ZSM-5, [Fe-Si-O]-MFI, [Ga-Si-O]-MFI, [As-Si-O]-MFI, AMS-1B, AZ-1, Bor-C, Encilite, Boralite C, FZ-1, LZ-105, mutinaite, NU-4, NU-5, TS-1, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B, ZMQ-TB, MnS-1 and FeS-1, including mixtures of two or more of them, more preferably selected from silicalite, ZSM-5, AMS-1B, AZ-1, Encilite, FZ-1, LZ-105, mutinaite, NU-4, NU-5, TS-1, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B and ZMQ-TB, including mixtures of two or more of them, wherein more preferably the zeolite material having an MFI-type framework structure comprises silicalite and / or ZSM-5, preferably ZSM-5, and wherein more preferably the zeolite material having an MFI-type framework structure is zeolite silicalite and / or ZSM-5, preferably ZSM-5.

[0062] Preferably, the zeolite material contains one or more alkaline earth metals M, wherein the one or more alkaline earth metals M are preferably selected from Be, Mg, Ca, Sr, Ba and mixtures of two or more of them, more preferably selected from Mg, Ca and mixtures thereof, wherein more preferably the alkaline earth metal M comprises Mg, and more preferably it is Mg.

[0063] In the case where the zeolite material contains one or more alkaline earth metals M, preferably the zeolite material contains the alkaline earth metal M calculated as an element in an amount in the range of 0.5-4.0 wt%, more preferably 1.0-3.0 wt%, more preferably 1.5-2.7 wt%, more preferably 1.7-2.5 wt% based on the weight of the molded article.

[0064] Further, in the case where the zeolite material contains one or more alkaline earth metals M, preferably the zeolite material contains the alkaline earth metal M calculated as an element in an amount in the range of 0.5-4.0 wt%, more preferably 1.8-2.6 wt%, more preferably 2.0-2.4 wt%, more preferably 2.1-2.3 wt% based on the weight of the zeolite material.

[0065] Preferably, the zeolite material is impregnated with one or more of the alkaline earth metals M.

[0066] There is no particular limitation on the method for impregnating the zeolite material with one or more of the alkaline earth metals M. When the zeolite material is impregnated with one or more of the alkaline earth metals M, it is preferred to impregnate the zeolite material with one or more of the alkaline earth metals M by spray impregnation, attachment impregnation, incipient wetness impregnation or wet impregnation attachment technique.

[0067] There is no particular limitation on the weight ratio of the oxide binder source to the zeolite material in the mixture prepared in (i) or (i'). Preferably, in the mixture prepared in (i) or (i'), the weight ratio of the oxide binder source calculated as the oxide binder source itself to the zeolite material is in the range of 0.05:1 - 0.25:1, more preferably 0.07:1 - 0.22:1, more preferably 0.10:1 - 0.19:1, more preferably 0.11:1 - 0.18:1, more preferably 0.12:1 - 0.17:1, more preferably 0.13:1 - 0.16:1, more preferably 0.14:1 - 0.15:1.

[0068] There is no particular limitation on the chemical or physical properties of the acid mixed in (ii') or contained in the mixture prepared in (i). Preferably, the acid is one or more of inorganic acids and organic acids. When the acid contains an organic acid, preferably the organic acid is one or more of formic acid, acetic acid, propionic acid, oxalic acid and tartaric acid, more preferably formic acid. When the acid contains an inorganic acid, preferably the inorganic acid is one or more of hydrochloric acid, nitric acid and phosphoric acid, more preferably nitric acid. Particularly preferably, the acid contains one or more of formic acid and nitric acid, preferably one or more of formic acid and nitric acid.

[0069] According to the first aspect, preferably as an aqueous solution, more preferably as an aqueous solution containing the acid in an amount of 5 - 50% by weight, more preferably 10 - 40% by weight, more preferably 12.5 - 37.5% by weight, more preferably 15 - 35% by weight, more preferably 17.5 - 32.5% by weight, more preferably 20 - 30% by weight, more preferably 22.5 - 27.5% by weight, more preferably 24 - 26% by weight based on the total weight of the aqueous solution, the acid is mixed in (i.1.b) or provided in (i.2.b) to provide the mixture, wherein the acid is preferably formic acid.

[0070] According to the second embodiment, it is preferably an aqueous solution, more preferably an aqueous solution in which the amount of acid contained based on the total weight of the aqueous solution is in the range of 1-20% by weight, more preferably 3-15% by weight, more preferably 5-13% by weight, more preferably 6-12% by weight, more preferably 7-11% by weight, more preferably 8-10% by weight. The acid is mixed in (i.1.b) or provided in (i.2.b) to provide the mixture, wherein the acid is preferably nitric acid.

[0071] In the case where the first or second embodiment is applied to mix the acid in (i.1.b) or provide it in (i.2.b) to provide the mixture, the weight ratio of the acid mixed in (i.1.b) or provided in (i.2.b) to provide the mixture to the total of the zeolite material and the oxide binder source of the mixture prepared in (i) or (i') is preferably in the range of 0.05:1 - 0.15:1, more preferably 0.06:1 - 0.14:1, preferably 0.07:1 - 0.13:1, more preferably 0.08:1 - 0.12:1, more preferably 0.09:1 - 0.11:1.

[0072] According to the third embodiment, it is preferably an aqueous solution, preferably an aqueous solution in which the amount of acid contained based on the total weight of the aqueous solution is in the range of 50-80% by weight, more preferably 55-75% by weight, more preferably 60-70% by weight, more preferably 63-67% by weight. The acid is mixed in (i.1.b) or provided in (i.2.b) to provide the mixture, wherein the acid is preferably nitric acid.

[0073] In the case where the third embodiment is applied, the weight ratio of the acid mixed in (i.1.b) or provided in (i.2.b) to provide the mixture to the total of the zeolite material and the oxide binder source of the mixture prepared in (i) or (i') is preferably in the range of 0.005:1 - 0.05:1, more preferably 0.010:1 - 0.030:1, more preferably 0.015:1 - 0.025:1.

[0074] Water, preferably deionized water, is preferably mixed into the mixture obtained from (i) or (ii'), preferably obtained in (i) or (ii') in (ii) or (iii').

[0075] In the case where water is mixed into the mixture obtained from (i) or (ii'), preferably the mixture obtained in (i) or (ii'), in (ii) or (iii'), preferably the weight ratio of water to the sum of the oxide binder source and the zeolite material in the mixture in (ii) or (iii') is in the range of 0.1:1 - 1.5:1, more preferably 0.2:1 - 0.8:1, more preferably 0.3:1 - 0.7:1, more preferably 0.3:1 - 0.6:1, more preferably 0.4:1 - 0.5:1, more preferably 0.45:1 - 0.46:1.

[0076] Preferably, a second plasticizer is mixed into the mixture obtained from (i), (ii), (ii') or (iii'), preferably the mixture obtained in (i), (ii), (ii') or (iii'), in (iii) or (iv'), wherein the second plasticizer is preferably different from the first plasticizer.

[0077] In the case where the second plasticizer is mixed into the mixture obtained from (i), (ii), (ii') or (iii'), preferably the mixture obtained in (i), (ii), (ii') or (iii'), preferably the weight ratio of the second plasticizer to the sum of the oxide binder source and the zeolite material in the mixture in (iii) or (iv') is in the range of 0.001:1 - 0.030:1, more preferably 0.005:1 - 0.015:1, more preferably 0.007:1 - 0.013:1, more preferably 0.008:1 - 0.012:1, more preferably 0.009:1 - 0.011:1.

[0078] There is no particular limitation on the chemical or physical properties of the second plasticizer. In the case where the second plasticizer is mixed into the mixture obtained from (i), (ii), (ii') or (iii'), preferably the mixture obtained in (i), (ii), (ii') or (iii'), preferably the second plasticizer is an organic compound. Particularly preferably, the second plasticizer is selected from organic polymers, carbohydrates, graphite, plant additives, and mixtures of two or more thereof, more preferably selected from polymer vinyl compounds, polyoxyalkenes, polyacrylates, polymethacrylates, polyolefins, polyamides, polyesters, polystyrenes, polysaccharides, and mixtures of two or more thereof. Particularly preferably, the second plasticizer is polyoxyethylene or a polysaccharide.

[0079] In the case where the second plasticizer is a polysaccharide, preferably the polysaccharide is selected from cellulose, cellulose derivatives, and starch, and the polysaccharide is more preferably one or more of methyl cellulose and carboxymethyl cellulose.

[0080] Preferably, water, preferably deionized water, is mixed into the mixture obtained from (i), (ii), (iii), (ii'), (iii') or (iv'), preferably obtained in (i), (ii), (iii), (ii'), (iii') or (iv'), in (iv) or (v').

[0081] In the case where water is mixed into the mixture obtained from (i), (ii), (iii), (ii'), (iii') or (iv'), preferably obtained in (i), (ii), (iii), (ii'), (iii') or (iv'), in (iv) or (v'), the weight ratio of water to the sum of the oxide binder source and the zeolite material in the mixture in (iv) or (v') is preferably in the range of 0.1:1 - 1:1, more preferably 0.30:1 - 0.90:1, more preferably 0.50:1 - 0.7:1, more preferably 0.55:1 - 0.65:1, more preferably 0.60:1 - 0.61:1.

[0082] Preferably, the mixture is formed into a wire in (v) or (vi'), more preferably a wire having a hexagonal, rectangular, square, triangular, elliptical or circular cross-section, more preferably a wire having a circular cross-section.

[0083] In the case where the wire has a circular cross-section, the wire having a circular cross-section preferably has a diameter in the range of 0.5 - 7 mm, more preferably 1.5 - 3.5 mm, more preferably 2.1 - 2.9 mm, more preferably 2.3 - 2.7 mm, more preferably 2.4 - 2.6 mm.

[0084] Preferably, the forming in (v) or (vi') includes extruding the mixture.

[0085] Suitable extrusion equipment is described, for example, in "Ullmann’s der Technischen Chemie", 4th Edition, Volume 2, pages 295 et seq., 1972. In addition to using an extruder, an extruding machine can also be used for preparing molded articles. If necessary, the extruder can be appropriately cooled during the extrusion process. The wire exiting the extruder through the die head can be mechanically cut, for example, by a suitable wire or via a discontinuous gas stream.

[0086] Preferably, the forming according to (v) or (vi') further includes drying the precursor of the molded article in a gas atmosphere.

[0087] Preferably, the drying is carried out at a gas atmosphere temperature of 80 - 160 °C, more preferably 100 - 140 °C, more preferably 110 - 130 °C. Preferably, the gas atmosphere contains nitrogen, oxygen or a mixture thereof, and the gas atmosphere is more preferably oxygen, air or lean air.

[0088] The shaping according to (v) or (vi') preferably further comprises calcining the precursor of the molded article, preferably the dried precursor of the molded article, in a gas atmosphere. The calcination is preferably carried out at a gas atmosphere temperature in the range of 500 - 650 °C, more preferably 530 - 570 °C, even more preferably 540 - 560 °C. The gas atmosphere preferably contains nitrogen, oxygen or a mixture thereof, and more preferably the gas atmosphere is oxygen, air or lean air.

[0089] Furthermore, the present invention relates to a molded article obtainable or obtained by the method of any one of the embodiments disclosed herein.

[0090] Furthermore, the present invention relates to a molded article, preferably a molded article prepared by the method of any one of the embodiments disclosed herein, comprising one or more oxide binders and a zeolite material, wherein the zeolite material contains YO2 and optionally X2O3 in its framework structure, where Y is a tetravalent element and X is a trivalent element, wherein the molded article contains the one or more oxide binders in an amount in the range of 5 - 15% by weight calculated as the oxide and wherein the molded article has a crushing strength equal to or greater than 9 N. Preferably, the crushing strength is determined according to Reference Example 5.

[0091] Preferably, the molded article has a crushing strength equal to or greater than 10 N, more preferably equal to or greater than 15 N, even more preferably equal to or greater than 18 N, even more preferably equal to or greater than 19 N, even more preferably equal to or greater than 20 N. Preferably, the crushing strength is determined according to Reference Example 5. Specifically preferably, the molded article has a crushing strength in the range of 15 - 50 N, more preferably 17 - 30 N.

[0092] Preferably, the molded article has a diffusion coefficient in the range of 0.40 - 1.30×10 -9 m 2 / s, more preferably 0.60 - 1.10×10 -9 m 2 / s, even more preferably 0.72 - 0.98×10 -9 m 2 / s. Preferably, the diffusion coefficient is determined according to Reference Example 4.

[0093] Preferably, the molded article has a distortion parameter with respect to water in the range of 1.00 - 3.75, more preferably 1.2 - 3.0, even more preferably 1.4 - 2.8. Preferably, the distortion parameter with respect to water is determined as described in Reference Example 2.

[0094] There are no particular restrictions on the chemical or physical properties of the one or more oxide binders contained in the molded article. Preferably, the one or more oxide binders are selected from silica, alumina, silica-alumina, and mixtures of two or more thereof, and preferably the one or more oxide binders are alumina.

[0095] Preferably, the molded article contains the one or more oxide binders calculated as oxides in an amount in the range of 6-14% by weight, more preferably 7-13% by weight, more preferably 8-12% by weight, and even more preferably 9-11% by weight.

[0096] There are no particular restrictions on the tetravalent element Y of the zeolite material contained in the molded article, so any tetravalent element in the periodic system of elements can be used for Y. Preferably, Y is selected from Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof, more preferably selected from Si, Ti, and mixtures thereof, and more preferably Y is Si.

[0097] There are no particular restrictions on the trivalent element X of the zeolite material contained in the molded article, so any trivalent element in the periodic system of elements can be used for X. Preferably, X is selected from B, Al, Ga, In, and mixtures of two or more thereof, more preferably selected from B, Al, and mixtures thereof, and more preferably X is Al.

[0098] There is no restriction on the framework structure type of the zeolite material contained in the molded article. Preferably, the zeolite material contained in the molded article has a framework structure type selected from 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, ERI, 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, MFI, 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 a mixed type of two or more of them,More preferably selected from MFI, MEL, ITH, IWR, CON, and mixed types of two or more of them, and more preferably selected from MFI, ITH, IWR, CON, and mixed types of two or more of them for the framework structure type. Particularly preferably, the zeolite material has an MFI framework structure type.

[0099] Preferably, the zeolite material contained in the molded article contains X2O3. In the case where the zeolite material contained in the molded article contains X2O3, preferably, the zeolite material has a YO2 / X2O3 molar ratio in the range of 50 - 150, more preferably 75 - 125, more preferably 90 - 120, more preferably 95 - 115.

[0100] In the case where the zeolite material contained in the molded article has a framework structure type of MFI, preferably, the zeolite material having an MFI framework structure type contains one or more of ZSM-5, ZBM-10, [As-Si-O]-MFI, [Fe-Si-O]-MFI, [Ga-Si-O]-MFI, AMS-1B, AZ-1, boron-C, boralite C, encilite, FZ-1, LZ-105, monoclinic H-ZSM-5, mordenite, NU-4, NU-5, silicalite, TS-1, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B, and ZMQ-TB, more preferably one or more of ZSM-5 and ZBM-10, and more preferably ZSM-5.

[0101] Preferably, 99 - 100 wt%, more preferably 99.5 - 100 wt%, more preferably 99.9 - 100 wt% of the zeolite material contained in the molded article is composed of Y, optionally X, O, and H.

[0102] Preferably, the zeolite material contained in the molded article contains one or more alkaline earth metals M.

[0103] In the case where the zeolite material contained in the molded article contains one or more alkaline earth metals M, preferably, the one or more alkaline earth metals M are selected from Be, Mg, Ca, Sr, Ba, and mixtures of two or more of them, more preferably selected from Mg, Ca, and their mixtures, and more preferably, the one or more alkaline earth metals M contain Mg and are more preferably composed of Mg.

[0104] Further, in the case where the zeolite material contained in the molded article contains one or more alkaline earth metals M, preferably, the zeolite material contains the one or more alkaline earth metals M calculated as elements in an amount in the range of 0.1 - 5 wt%, more preferably 1.5 - 2.5 wt%, more preferably 1.7 - 2.3 wt% based on the weight of the molded article.

[0105] Furthermore, in the case where the zeolite material contained in the molded article contains one or more alkaline earth metals M, preferably the zeolite material contains the one or more alkaline earth metals M calculated as elements in an amount in the range of 0.5 - 4.0% by weight, more preferably 1.0 - 3.0% by weight, more preferably 1.5 - 2.7% by weight, more preferably 1.7 - 2.5% by weight, more preferably 1.7 - 2.3% by weight, based on the weight of the zeolite material.

[0106] Furthermore, in the case where the zeolite material contained in the molded article contains one or more alkaline earth metals M, it is preferred to impregnate the zeolite material with the one or more alkaline earth metals M, preferably by spray impregnation.

[0107] Furthermore, in the case where the zeolite material contained in the molded article contains one or more alkaline earth metals M, preferably 99 - 100% by weight, more preferably 99.5 - 100% by weight, more preferably 99.9 - 100% by weight of the zeolite material consists of Y, optionally X, O, H, and the one or more alkaline earth metals M.

[0108] Preferably, the molded article contains less than 1% by weight, more preferably less than 0.1% by weight, more preferably less than 0.01% by weight of sodium.

[0109] Preferably, the molded article has a BET specific surface area in the range of 300 - 400 m 2 / g, more preferably 325 - 375 m 2 / g, more preferably 350 - 360 m 2 / g. Preferably, the BET specific surface area is measured as described in Reference Example 1.

[0110] Preferably, the molded article has a total pore volume in the range of 0.2 - 0.75 ml / g, more preferably 0.45 - 0.53 ml / g, more preferably 0.47 - 0.51 ml / g, more preferably 0.48 - 0.50 ml / g. Preferably, the total pore volume is measured according to Reference Example 3.

[0111] Preferably, the molded article has an acid site density in the range of 0.20 - 0.75 mmol / g, more preferably 0.25 - 0.65 mmol / g, more preferably 0.44 - 0.52 mmol / g, more preferably 0.46 - 0.50 mmol / g, more preferably 0.47 - 0.49 mmol / g at temperatures below 250°C. Preferably, the acid site density is measured according to Reference Example 6.

[0112] Preferably, the molded article has an acid site density of equal to or less than 0.5 mmol / g, more preferably equal to or less than 0.30 mmol / g, still more preferably equal to or less than 0.25 mmol / g, even more preferably equal to or less than 0.1 mmol / g, and most preferably equal to or less than 0.01 mmol / g at a temperature above 250 °C, preferably in the range of greater than 250 °C to 650 °C. Preferably, the acid site density is determined according to Reference Example 6.

[0113] Preferably, 99-100% by weight, more preferably 99.5-100% by weight, still more preferably 99.9-100% by weight of the molded article is composed of the zeolite material and the oxide binder.

[0114] Preferably, the molded article is a wire rod, preferably having a hexagonal, rectangular, square, triangular, elliptical or circular cross-section, more preferably a circular cross-section, wherein the cross-section has a diameter preferably in the range of 1.5-3.5 mm, more preferably 2.0-3.0 mm, still more preferably 2.2-2.8 mm, even more preferably 2.4-2.6 mm.

[0115] Preferably, the molded article has an olefin selectivity in the range of 50-90%, more preferably 55-80%, still more preferably 60-75%. Preferably, the olefin selectivity is determined according to Example 13.

[0116] Preferably, the molded article has a butene selectivity in the range of 10-30%, more preferably 15-25%, still more preferably 18-22%, preferably a selectivity for one or more of 1-butene, (2Z)-but-2-ene, (2E)-but-2-ene, 2-methylprop-1-ene. Preferably, the olefin selectivity is determined according to Example 13.

[0117] Preferably, the molded article has a propylene selectivity in the range of 20-100%, preferably 25-90%, more preferably 30-70%, preferably 35-65%, more preferably 37-50%, still more preferably 38-47%. Preferably, the olefin selectivity is determined according to Example 13.

[0118] Preferably, the molded article has an ethylene selectivity in the range of 1-15%, more preferably 4-12%, still more preferably 5-10%. Preferably, the olefin selectivity is determined according to Example 13.

[0119] The present invention further relates to a method for converting an oxide into an olefin, comprising:

[0120] (a) providing a molded article according to any one of the embodiments disclosed herein;

[0121] (b) providing a gas stream comprising one or more oxides and optionally one or more olefins and / or optionally one or more hydrocarbons;

[0122] (c) Contact the molded article provided in (a) with the gas stream provided in (b) and convert one or more oxides into one or more olefins and optionally one or more hydrocarbons;

[0123] (d) Optionally recycle one or more of the one or more olefins and / or the one or

[0124] more hydrocarbons contained in the gas stream obtained in (c) back to (b).

[0125] Preferably, the molded article is provided in a fixed bed or a fluidized bed.

[0126] The method may include other method steps, especially for the activation or regeneration of the molded article. Preferably, the method further includes, after (a) and before (b):

[0127] (a') Treat the molded article provided in (a) with a gas stream containing water.

[0128] Preferably, the gas stream in (a') has a temperature in the range of 450 - 510 °C, more preferably 460 - 500 °C, even more preferably 470 - 490 °C.

[0129] Preferably, the gas stream provided in (b) contains one or more selected from aliphatic alcohols, ethers, carbonyl compounds, and mixtures of two or more thereof, more preferably selected from C1 - C6 alcohols, di - C1 - C3 alkyl ethers, C1 - C6 aldehydes, C2 - C6 ketones, and mixtures of two or more thereof, even more preferably selected from C1 - C4 alcohols, di - C1 - C2 alkyl ethers, C1 - C4 aldehydes, C2 - C4 ketones, and mixtures of two or more thereof, even more preferably selected from methanol, ethanol, n - propanol, isopropanol, butanol, dimethyl ether, diethyl ether, ethyl methyl ether, diisopropyl ether, di - n - propyl ether, formaldehyde, dimethyl ketone, and mixtures of two or more thereof, even more preferably selected from oxides of methanol, ethanol, dimethyl ether, diethyl ether, ethyl methyl ether, and mixtures of two or more thereof, and the gas stream more preferably contains methanol and / or dimethyl ether, even more preferably methanol.

[0130] Preferably, the content of oxides in the gas stream provided in (b) is in the range of 2 - 100% by volume, more preferably 3 - 99% by volume, even more preferably 4 - 95% by volume, even more preferably 5 - 80% by volume, even more preferably 6 - 50% by volume, even more preferably 10 - 40% by volume, even more preferably 15 - 25% by volume, even more preferably 18 - 22% by volume, based on the total volume.

[0131] Preferably, the gas stream provided in (b) contains water, and the water content in the gas stream provided in (b) is more preferably in the range of 1 - 90% by volume, more preferably 2 - 80% by volume, even more preferably 5 - 75% by volume, even more preferably 10 - 70% by volume.

[0132] Preferably, the gas stream provided in (b) further comprises one or more dilution gases, more preferably in an amount in the range of 0.1 - 90% by volume, more preferably 1 - 85% by volume, more preferably 5 - 80% by volume, more preferably 10 - 75% by volume, more preferably 425 - 525 °C, more preferably 450 - 500 °C, more preferably 475 - 495 °C, more preferably 480 - 490 °C.

[0133] Preferably, the one or more dilution gases are selected from H2O, helium, neon, argon, krypton, nitrogen, carbon monoxide, carbon dioxide, and mixtures of two or more thereof, more preferably selected from H2O, argon, nitrogen, carbon dioxide, and mixtures of two or more thereof, wherein more preferably the one or more dilution gases comprise H2O or nitrogen, and wherein more preferably the one or more dilution gases are H2O or nitrogen.

[0134] Preferably, the contacting in (c) is carried out at a temperature in the range of 225 - 700 °C, preferably 275 - 650 °C, more preferably 325 - 600 °C, more preferably 375 - 550 °C, more preferably 425 - 525 °C, more preferably 450 - 500 °C, more preferably 475 - 495 °C, more preferably 480 - 490 °C.

[0135] According to one embodiment, preferably, the contacting in (c) is carried out at a pressure in the range of 0.01 - 25 bar, more preferably 0.1 - 20 bar, more preferably 0.25 - 15 bar, more preferably 0.5 - 10 bar, more preferably 0.75 - 5 bar, more preferably 0.8 - 2 bar, more preferably 0.85 - 1.5 bar, more preferably 0.9 - 1.1 bar.

[0136] According to another embodiment, preferably, the contacting in (c) is carried out at a pressure in the range of 0.1 - 25 bar (gauge), preferably 0.25 - 20 bar (gauge), more preferably 0.5 - 15 bar (gauge), more preferably 1.0 - 10 bar (gauge), more preferably 2.0 - 7.0 bar (gauge), more preferably 3.0 - 5.0 bar (gauge), more preferably 3.9 - 4.1 bar (gauge).

[0137] In the case where the method is a continuous method, preferably, the gas hourly space velocity (GHSV) of the contacting in (c) is in the range of 1 - 30,000 h -1 , more preferably 1,000 - 25,000 h -1 , preferably 10,000 - 23,000 h -1 , more preferably 15,000 - 21,500 h -1 , more preferably 20,000 - 20,500 h -1 range.

[0138] Further, in the case where the method is a continuous method, the weight hourly space velocity (WHSV) of the contact in (c) is preferably in the range of 0.5 - 50 h -1 , more preferably 1 - 30 h -1 , even more preferably 2 - 20 h -1 , preferably 5 - 15 h -1 , more preferably 8 - 12 h -1 , even more preferably 9 - 11 h -1 .

[0139] Preferably, the one or more olefins and / or one or more hydrocarbons optionally provided in (b) and / or optionally recycled to (b) include those selected from ethylene, C4 - C7 olefins, C4 - C7 hydrocarbons, and mixtures of two or more thereof, preferably one or more selected from ethylene, C4 - C5 olefins, C4 - C5 hydrocarbons, and mixtures of two or more thereof.

[0140] As disclosed above, the method may include other method steps. Preferably, the method further includes:

[0141] (e) regenerating the molded article in a gas stream containing one or more of oxygen and nitrogen, preferably air or lean air.

[0142] Preferably, it is carried out at the regeneration site in (e).

[0143] Preferably, the temperature of the gas stream containing a mixture of air and nitrogen in (e) has a temperature in the range of 450 - 550 °C, more preferably 470 - 510 °C, even more preferably 480 - 500 °C.

[0144] The present invention further relates to the use of the molded article according to any one of the embodiments disclosed herein as a molecular sieve, as an adsorbent, for ion exchange, or as a catalyst and / or as a catalyst support, preferably as a catalyst for selective catalytic reduction (SCR) of nitrogen oxides NO x ; for the oxidation of NH3, especially for the oxidation of escaped NH3 in a diesel engine system; for the decomposition of N2O; as an additive in a fluid catalytic cracking (FCC) process; and / or as a catalyst in an organic conversion reaction, preferably as a hydrocracking catalyst, as an alkylation catalyst, as an isomerization catalyst, or in the conversion of alcohols to olefins, more preferably as a catalyst in the conversion of oxides to olefins.

[0145] The molded article is preferably used in a methanol - to - olefins process (MTO process), in a dimethyl ether - to - olefins process (DTO process), in a methanol - to - gasoline process (MTG process), in a methanol - to - hydrocarbons process, in a methanol - to - aromatics process, in a biomass - to - olefins and / or biomass - to - aromatics process, in a methane - to - benzene process, in aromatics alkylation or in a fluid catalytic cracking process (FCC process), preferably in a methanol - to - olefins process (MTO process) and / or in a dimethyl ether - to - olefins process (DTO process), more preferably in a methanol - to - propylene process (MTP process), in a methanol - to - propylene / butene process (MT3 / 4 process), in a dimethyl ether - to - propylene process (DTP process), in a dimethyl ether - to - propylene / butene process (DT3 / 4 process) and / or in a dimethyl ether - to - ethylene / propylene process (DT2 / 3 process).

[0146] In the context of the present invention, the weight of one or more alkaline earth metals is calculated as the weight of the corresponding alkaline earth metal as an element or as the total weight of the corresponding alkaline earth metals as elements. For example, if the one or more alkaline earth metals is Mg, the weight of the alkaline earth metal is calculated as the element Mg. As another example, if the one or more alkaline earth metals consists of Mg and Ba, the weight of the alkaline earth metal is calculated as the elements Mg and Ba.

[0147] In the context of the present invention, unless otherwise specified, the weight of the oxide binder is calculated as the weight of the corresponding oxide binder as an oxide or as the total weight of the corresponding oxide binder as oxides. For example, if the oxide binder is silica, the weight of the oxide binder is calculated as SiO2. As another example, if the oxide binder consists of a mixed oxide containing Ti and Al, the weight of the oxide binder is calculated as the sum of TiO2 and Al2O3.

[0148] In the context of the present invention, unless otherwise specified, the term "based on the weight of the zeolite material" relates to the weight of the zeolite material including metal ions exchanged, such as Mg.

[0149] The unit bar (abs) means an absolute pressure of 10 5 Pa.

[0150] The present invention is further illustrated by the following set of embodiments and by the combinations of embodiments obtained from the shown dependencies and back-references. In particular, it should be noted that in all cases where a range of embodiments is mentioned, for example, in the case of terms such as "a molded article according to any one of Embodiments 1 - 4", each and every embodiment within that range is intended to be clearly disclosed to a person skilled in the art, i.e., the wording of the term should be understood by a person skilled in the art as being synonymous with "a molded article according to any one of Embodiments 1, 2, 3, and 4". Furthermore, it should be clearly noted that the following set of embodiments is not the set of claims that define the scope of protection, but rather represents a suitable component of the description that relates to the general and preferred aspects of the present invention.

[0151] 1. A method for preparing a molded article comprising a zeolite material and one or more oxide binders, wherein the zeolite material comprises YO2 and optionally X2O3 in its framework structure, where Y is a tetravalent element and X is a trivalent element, the method comprising:

[0152] (i) preparing a mixture comprising a zeolite material, a source of an oxide binder, a first plasticizer, and an acid;

[0153] (ii) preferably mixing water into the mixture obtained from (i);

[0154] (iii) preferably mixing a second plasticizer into the mixture obtained from (i) or (ii), preferably the mixture obtained in (i) or (ii);

[0155] (iv) preferably mixing water into the mixture obtained from (iii), preferably the mixture obtained in (iii);

[0156] (v) shaping the mixture obtained from (i), (ii), (iii), or (iv) to obtain a precursor of the molded article;

[0157] wherein the weight ratio of the source of the oxide binder, calculated as an oxide, to the sum of the zeolite material and the source of the oxide binder, calculated as an oxide, in the mixture obtained in (i) is in the range of 0.05:1 - 0.15:1.

[0158] 2. The method according to Embodiment 1, wherein (i) comprises:

[0159] (i.1.a) preparing a mixture comprising a zeolite material, a source of an oxide binder, and a first plasticizer;

[0160] (i.1.b) mixing the acid into the mixture obtained in (i.1.a).

[0161] 3. The method according to Embodiment 1, wherein (i) comprises:

[0162] (i.2.a) providing the zeolite material;

[0163] (i.2.b) Provide a mixture comprising a source of oxide binder, optional water and an acid;

[0164] (i.2.c) Mix the mixture obtained in (i.2.b) with the zeolite material provided in (i.2.a);

[0165] (i.2.d) Incorporate a first plasticizer into the mixture obtained in (i.2.c),

[0166] wherein the mixing according to (i.2.c) preferably comprises incorporating the mixture provided in (i.2.b) into the zeolite material provided in (i.2.a) or incorporating the zeolite material provided in (i.2.a) into the mixture provided in (i.2.b).

[0167] 4. The method of embodiment 3, wherein water is included in the mixture obtained in (i.2.b), and wherein the mixture obtained in (i.2.b) preferably has a weight ratio of water to the oxide binder source calculated as the oxide binder source itself in the range of 1:1 - 10:1, more preferably 4.0:1 - 5.0:1, even more preferably 4.50:1 - 4.70:1.

[0168] 5. The method of any one of embodiments 1 - 4, wherein the mixture prepared in (i) is mixed in a kneader, a Lodige mixer (German: Mischer) or a mixing roll mill.

[0169] 6. The method of any one of embodiments 1 - 5, wherein the weight ratio of the first plasticizer to the sum of the zeolite material and the oxide binder source calculated as the oxide binder source itself in the mixture prepared in (i) is in the range of 0.01:1 - 0.1:1, preferably 0.02:1 - 0.08:1, more preferably 0.03:1 - 0.07:1, even more preferably 0.04:1 - 0.06:1, even more preferably 0.045:1 - 0.055:1.

[0170] 7. The method of any one of embodiments 1 - 6, wherein the first plasticizer is selected from organic polymers, carbohydrates, graphite, plant additives and mixtures of two or more thereof, preferably selected from polymer vinyl compounds, polyoxyalkenes, polyacrylates, polymethacrylates, polyolefins, polyamides, polyesters, polystyrenes, polysaccharides and mixtures of two or more thereof, and wherein the first plasticizer is more preferably a polysaccharide.

[0171] 8. The method of embodiment 7, wherein the polysaccharide is selected from cellulose, cellulose derivatives and starch, and wherein the polysaccharide is preferably one or more of methylcellulose and carboxymethylcellulose.

[0172] 9. The method according to embodiment 7 or 8, wherein the polysaccharide has a bulk density in the range of 500 - 800 g / l, preferably 550 - 750 g / l, more preferably 600 - 700 g / l, even more preferably 630 - 670 g / l.

[0173] 10. The method according to any one of embodiments 7 - 9, wherein the polysaccharide has a viscosity in the range of 3000 - 4000 mPas, preferably 3400 - 3600 mPas, more preferably 3450 - 3550 mPas.

[0174] 11. The method according to any one of embodiments 1 - 10, wherein the weight ratio of the oxide binder source, calculated as the oxide, in the mixture obtained in (i) to the sum of the zeolite material and the oxide binder source, calculated as the oxide, is in the range of 0.06:1 - 0.14:1, preferably 0.07:1 - 0.13:1, more preferably 0.08:1 - 0.12:1, even more preferably 0.09:1 - 0.11:1.

[0175] 12. The method according to any one of embodiments 1 - 11, wherein the oxide binder source is one or more of a silica source, an alumina source, and a silica - alumina source, preferably an alumina source.

[0176] 13. The method according to any one of embodiments 1 - 12, wherein the oxide binder source comprises one or more of AlOOH (boehmite), Al2O3, Al(OH)3, hydrotalcite, silica sol, colloidal silica, wet silica, and dry silica, preferably one or more of AlOOH (boehmite) and Al2O3, more preferably AlOOH (boehmite), and the oxide binder source is more preferably AlOOH (boehmite).

[0177] 14. The method according to any one of embodiments 1 - 13, wherein Y is selected from Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof, preferably selected from Si, Ti, and mixtures thereof, and more preferably Y is Si.

[0178] 15. The method according to any one of embodiments 1 - 14, wherein X is selected from B, Al, Ga, In, and mixtures of two or more thereof, preferably selected from B, Al, and mixtures thereof, and more preferably X is Al.

[0179] 16. The method according to any one of embodiments 1 - 15, wherein the zeolite material has a YO2 / X2O3 molar ratio in the range of 50 - 150, preferably 75 - 125, more preferably 90 - 120, even more preferably 95 - 115.

[0180] 17. The method of any one of embodiments 1-16, wherein the zeolite material has a framework type selected from 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, ERI, 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, MFI, 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,Preferably selected from MFI, MEL, ITH, IWR, CON, and mixed types of two or more thereof, more preferably a framework structure type selected from MFI, ITH, IWR, CON, and mixed types of two or more thereof, wherein the zeolite material more preferably has an MFI framework structure type.

[0181] 18. The method of any one of embodiments 1-17, wherein the zeolite material has an MFI-type framework structure, and the zeolite material is selected from silicalite, ZSM-5, [Fe-Si-O]-MFI, [Ga-Si-O]-MFI, [As-Si-O]-MFI, AMS-1B, AZ-1, Bor-C, Encilite, Boralite C, FZ-1, LZ-105, mutinaite, NU-4, NU-5, TS-1, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B, ZMQ-TB, MnS-1, and FeS-1, including mixtures of two or more thereof, preferably selected from silicalite, ZSM-5, AMS-1B, AZ-1, Encilite, FZ-1, LZ-105, mutinaite, NU-4, NU-5, TS-1, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B, and ZMQ-TB, including mixtures of two or more thereof, wherein more preferably the zeolite material having an MFI-type framework structure comprises silicalite and / or ZSM-5, preferably ZSM-5, and wherein more preferably the zeolite material having an MFI-type framework structure is zeolite silicalite and / or ZSM-5, preferably ZSM-5.

[0182] 19. The method of any one of embodiments 1-18, wherein the zeolite material contains one or more alkaline earth metals M, and the one or more alkaline earth metals M are preferably selected from Be, Mg, Ca, Sr, Ba, and mixtures of two or more thereof, preferably selected from Mg, Ca, and mixtures thereof, and wherein more preferably the alkaline earth metal M comprises Mg, and more preferably is Mg.

[0183] 20. The method of embodiment 19, wherein the zeolite material contains the alkaline earth metal M calculated as an element in an amount in the range of 0.5-4.0 wt%, preferably 1.0-3.0 wt%, more preferably 1.5-2.7 wt%, more preferably 1.7-2.5 wt% based on the weight of the molded article.

[0184] 21. The method of embodiment 19 or 20, wherein the zeolite material contains alkaline earth metal M calculated as an element in an amount in the range of 0.5-4.0 wt%, preferably 1.8-2.6 wt%, more preferably 2.0-2.4 wt%, even more preferably 2.1-2.3 wt% based on the weight of the zeolite material calculated as the zeolite material without alkaline earth metal M.

[0185] 22. The method of any one of embodiments 19-21, wherein the zeolite material is impregnated with the one or more alkaline earth metals M.

[0186] 23. The method of embodiment 22, wherein the zeolite material is impregnated by spray impregnation, attachment impregnation, incipient wetness impregnation or wet impregnation attachment technique.

[0187] 24. The method of any one of embodiments 1-23, wherein the weight ratio of the oxide binder source calculated as the oxide binder source itself to the zeolite material in the mixture prepared in (i) is in the range of 0.05:1 - 0.25:1, preferably 0.07:1 - 0.22:1, more preferably 0.10:1 - 0.19:1, even more preferably 0.11:1 - 0.18:1, even more preferably 0.12:1 - 0.17:1, even more preferably 0.13:1 - 0.16:1, even more preferably 0.14:1 - 0.15:1.

[0188] 25. The method of any one of embodiments 1-24, wherein the acid is one or more of an inorganic acid and an organic acid, wherein the organic acid is preferably one or more of formic acid, acetic acid, propionic acid, oxalic acid and tartaric acid, more preferably formic acid, wherein the inorganic acid is preferably one or more of hydrochloric acid, nitric acid and phosphoric acid, more preferably nitric acid, wherein the acid more preferably comprises one or more of formic acid and nitric acid, preferably one or more of formic acid and nitric acid.

[0189] 26. The method of any one of embodiments 2-25, wherein as an aqueous solution, preferably as an aqueous solution containing the acid in an amount in the range of 5-50 wt%, more preferably 10-40 wt%, more preferably 12.5-37.5 wt%, more preferably 15-35 wt%, more preferably 17.5-32.5 wt%, more preferably 20-30 wt%, more preferably 22.5-27.5 wt%, more preferably 24-26 wt% based on the total weight of the aqueous solution, the acid is mixed in (i.1.b) or provided in (i.2.b) to provide the mixture, wherein the acid is preferably formic acid.

[0190] 27. The method according to any one of embodiments 2-26, wherein as an aqueous solution, preferably as an aqueous solution containing an acid in an amount in the range of 1-20% by weight, preferably 3-15% by weight, more preferably 5-13% by weight, more preferably 6-12% by weight, more preferably 7-11% by weight, more preferably 8-10% by weight based on the total weight of the aqueous solution, the acid is incorporated in (i.1.b) or provided in (i.2.b) to provide the mixture, wherein the acid is preferably nitric acid.

[0191] 28. The method according to embodiment 26 or 27, wherein the weight ratio of the acid incorporated in (i.1.b) or provided in (i.2.b) to provide the mixture to the sum of the zeolite material and the oxide binder source of the mixture prepared in (i) is in the range of 0.05:1 - 0.15:1, preferably 0.06:1 - 0.14:1, preferably 0.07:1 - 0.13:1, more preferably 0.08:1 - 0.12:1, more preferably 0.09:1 - 0.11:1.

[0192] 29. The method according to any one of embodiments 2-28, wherein as an aqueous solution, preferably as an aqueous solution containing an acid in an amount in the range of 50-80% by weight, more preferably 55-75% by weight, more preferably 60-70% by weight, more preferably 63-67% by weight based on the total weight of the aqueous solution, the acid is incorporated in (i.1.b) or provided in (i.2.b) to provide the mixture, wherein the acid is preferably nitric acid.

[0193] 30. The method according to embodiment 29, wherein the weight ratio of the acid incorporated in (i.1.b) or provided in (i.2.b) to provide the mixture to the sum of the zeolite material and the oxide binder source of the mixture prepared in (i) is in the range of 0.005:1 - 0.05:1, more preferably 0.010:1 - 0.030:1, more preferably 0.015:1 - 0.025:1.

[0194] 31. The method according to any one of embodiments 1-30, wherein in (ii), water, preferably deionized water, is incorporated into the mixture obtained from (i), preferably the mixture obtained in (i).

[0195] 32. The method according to embodiment 31, wherein the weight ratio of water to the sum of the oxide binder source and the zeolite material in the mixture in (ii) is in the range of 0.1:1 - 1.5:1, preferably 0.2:1 - 0.8:1, more preferably 0.3:1 - 0.7:1, preferably 0.3:1 - 0.6:1, more preferably 0.4:1 - 0.5:1, more preferably 0.45:1 - 0.46:1.

[0196] 33. The method according to any one of embodiments 1-32, wherein in (iii), a second plasticizer is incorporated into the mixture obtained from (i) or (ii), preferably obtained in (i) or (ii), wherein the second plasticizer is preferably different from the first plasticizer.

[0197] 34. The method according to embodiment 33, wherein the weight ratio of the second plasticizer to the sum of the oxide binder source and the zeolite material in the mixture in (iii) is in the range of 0.001:1 - 0.030:1, preferably 0.005:1 - 0.015:1, preferably 0.007:1 - 0.013:1, more preferably 0.008:1 - 0.012:1, still more preferably 0.009:1 - 0.011:1.

[0198] 35. The method according to embodiment 33 or 34, wherein the second plasticizer is selected from organic polymers, carbohydrates, graphite, plant additives, and mixtures of two or more thereof, preferably selected from polymer vinyl compounds, polyoxyalkenes, polyacrylates, polymethacrylates, polyolefins, polyamides, polyesters, polystyrenes, polysaccharides, and mixtures of two or more thereof, wherein the second plasticizer is more preferably polyoxyethylene or a polysaccharide.

[0199] 36. The method according to embodiment 35, wherein the polysaccharide is selected from cellulose, cellulose derivatives, and starch, and the polysaccharide is preferably one or more of methyl cellulose and carboxymethyl cellulose.

[0200] 37. The method according to any one of embodiments 1-36, wherein in (iv), water, preferably deionized water, is incorporated into the mixture obtained from (i), (ii), or (iii), preferably obtained in (i), (ii), or (iii).

[0201] 38. The method according to embodiment 37, wherein the weight ratio of water to the sum of the oxide binder source and the zeolite material in the mixture in (iv) is in the range of 0.1:1 - 1:1, preferably 0.30:1 - 0.90:1, more preferably 0.50:1 - 0.7:1, still more preferably 0.55:1 - 0.65:1, even more preferably 0.60:1 - 0.61:1.

[0202] 39. The method according to any one of embodiments 1-38, wherein in (v), the mixture is formed into a wire, preferably having a hexagonal, rectangular, square, triangular, elliptical, or circular cross-section, more preferably a circular cross-section.

[0203] 40. The method of embodiment 39, wherein the wire stock having a circular cross-section has a diameter in the range of 0.5 - 7 mm, preferably 1.5 - 3.5 mm, more preferably 2.1 - 2.9 mm, more preferably 2.3 - 2.7 mm, more preferably 2.4 - 2.6 mm.

[0204] 41. The method of any one of embodiments 1 - 40, wherein the shaping in (v) comprises extruding the mixture.

[0205] 42. The method of any one of embodiments 1 - 41, wherein the shaping according to (v) further comprises drying the precursor of the molded article in a gas atmosphere.

[0206] 43. The method of embodiment 42, wherein the drying is carried out at a gas atmosphere temperature in the range of 80 - 160 °C, preferably 100 - 140 °C, more preferably 110 - 130 °C.

[0207] 44. The method of embodiment 42 or 43, wherein the gas atmosphere comprises nitrogen, oxygen or a mixture thereof, and wherein the gas atmosphere is preferably oxygen, air or lean air.

[0208] 45. The method of any one of embodiments 1 - 44, preferably any one of embodiments 42 - 44, wherein the shaping according to (v) further comprises calcining the precursor of the molded article in a gas atmosphere, preferably the dried precursor of the molded article.

[0209] 46. The method of embodiment 45, wherein the calcining is carried out at a gas atmosphere temperature in the range of 500 - 650 °C, preferably 530 - 570 °C, more preferably 540 - 560 °C.

[0210] 47. The method of embodiment 45 or 46, wherein the gas atmosphere comprises nitrogen, oxygen or a mixture thereof, and wherein the gas atmosphere is preferably oxygen, air or lean air.

[0211] 48. A molded article obtainable or obtained by the method of any one of embodiments 1 - 47.

[0212] 49. A molded article, preferably a molded article prepared according to the method of any one of embodiments 1 - 48, comprising one or more oxide binders and a zeolite material, wherein the zeolite material comprises YO2 and optionally X2O3 in its framework structure, wherein Y is a tetravalent element and X is a trivalent element, wherein the molded article comprises the one or more oxide binders in an amount in the range of 5 - 15% by weight calculated as the oxide and wherein the molded article has a crushing strength equal to or greater than 9 N as determined according to reference example 5.

[0213] 50. The molded article of embodiment 49 has a crushing strength of equal to or greater than 10 N, preferably equal to or greater than 15 N, preferably equal to or greater than 18 N, more preferably equal to or greater than 19 N, more preferably equal to or greater than 20 N as determined according to reference example 5, wherein the molded article more preferably has a crushing strength in the range of 15 - 50 N, more preferably 17 - 30 N.

[0214] 51. The molded article of embodiment 49 or 50 has a diffusion coefficient in the range of 0.40 - 1.30×10 -9 m 2 / s, preferably 0.60 - 1.10×10 - 9 m 2 / s, more preferably 0.72 - 0.98×10 -9 m 2 / s, which is preferably determined according to reference example 4.

[0215] 52. The molded article of any one of embodiments 49 - 51 has a distortion parameter relative to water in the range of 1.00 - 3.75, preferably 1.2 - 3.0, more preferably 1.4 - 2.8, which is preferably determined as described in reference example 2.

[0216] 53. The molded article of embodiment 52, wherein the one or more oxide binders are selected from silica, alumina, silica - alumina, and mixtures of two or more thereof, and wherein the one or more oxide binders are preferably alumina.

[0217] 54. The molded article of any one of embodiments 49 - 53 contains the one or more oxide binders calculated as oxides in an amount in the range of 6 - 14% by weight, more preferably 7 - 13% by weight, more preferably 8 - 12% by weight, more preferably 9 - 11% by weight.

[0218] 55. The molded article of any one of embodiments 49 - 54, wherein Y is selected from Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof, preferably selected from Si, Ti, and mixtures thereof, and wherein more preferably Y is Si.

[0219] 56. The molded article of any one of embodiments 49 - 55, wherein X is selected from B, Al, Ga, In, and mixtures of two or more thereof, preferably selected from B, Al, and mixtures thereof, and wherein more preferably X is Al.

[0220] 57. A molded article according to any one of embodiments 49 - 56, wherein the zeolite material has a framework type selected from 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, ERI, 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, MFI, 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,Preferably selected from MFI, MEL, ITH, IWR, CON, and mixed types of two or more thereof, more preferably a framework structure type selected from MFI, ITH, IWR, CON, and mixed types of two or more thereof, wherein the zeolite material more preferably has a framework structure type of MFI.

[0221] 58. The molded article according to any one of embodiments 49 - 57, wherein the zeolite material contains X2O3 and wherein the zeolite material has a YO2 / X2O3 molar ratio in the range of 50 - 150, preferably 75 - 125, more preferably 90 - 120, and even more preferably 95 - 115.

[0222] 59. The molded article according to any one of embodiments 49 - 58, wherein the zeolite material has a framework structure type of MFI, and the zeolite material having an MFI framework structure type preferably contains one or more of ZSM - 5, ZBM - 10, [As - Si - O] - MFI, [Fe - Si - O] - MFI, [Ga - Si - O] - MFI, AMS - 1B, AZ - 1, boron - C, boralite C, encilite, FZ - 1, LZ - 105, monoclinic H - ZSM - 5, mutinaite, NU - 4, NU - 5, silicalite, TS - 1, TSZ, TSZ - III, TZ - 01, USC - 4, USI - 108, ZBH, ZKQ - 1B, and ZMQ - TB, preferably one or more of ZSM - 5 and ZBM - 10, and more preferably ZSM - 5.

[0223] 60. The molded article according to any one of embodiments 49 - 59, wherein 99 - 100% by weight, more preferably 99.5 - 100% by weight, and even more preferably 99.9 - 100% by weight of the zeolite material is composed of Y, optionally X, O, and H.

[0224] 61. The molded article according to any one of embodiments 49 - 60, wherein the zeolite material contains one or more alkaline earth metals M.

[0225] 62. The molded article of embodiment 61, wherein the one or more alkaline earth metals M are selected from Be, Mg, Ca, Sr, Ba, and mixtures of two or more thereof, preferably selected from Mg, Ca, and mixtures thereof, and more preferably the one or more alkaline earth metals M contain Mg and are more preferably composed of Mg.

[0226] 63. The molded article of embodiment 61 or 62, wherein the zeolite material contains the one or more alkaline earth metals M calculated as an element in an amount in the range of 0.1 - 5% by weight, preferably 1.5 - 2.5% by weight, and more preferably 1.7 - 2.3% by weight based on the weight of the molded article.

[0227] 64. A molded article according to embodiment 61 or 62, wherein the zeolite material contains the one or more alkaline earth metals M calculated as an element in an amount in the range of 0.5-4.0% by weight, preferably 1.0-3.0% by weight, more preferably 1.5-2.7% by weight, more preferably 1.7-2.5% by weight, more preferably 1.7-2.3% by weight, based on the weight of the zeolite material.

[0228] 65. A molded article according to any one of embodiments 61-64, wherein the zeolite material is impregnated with the one or more alkaline earth metals M, preferably spray impregnated.

[0229] 66. A molded article according to any one of embodiments 61-65, wherein 99-100% by weight, more preferably 99.5-100% by weight, more preferably 99.9-100% by weight of the zeolite material consists of Y, optionally X, O, H, and the one or more alkaline earth metals M.

[0230] 67. A molded article according to any one of embodiments 49-66, containing less than 1% by weight, preferably less than 0.1% by weight, more preferably less than 0.01% by weight of sodium.

[0231] 68. A molded article according to any one of embodiments 49-67, having a BET specific surface area in the range of 300-400 m 2 / g, preferably 325-375 m 2 / g, more preferably 350-360 m 2 / g, which is preferably determined as described in reference example 1.

[0232] 69. A molded article according to any one of embodiments 49-68, having a total pore volume in the range of 0.2-0.75 ml / g, preferably 0.45-0.53 ml / g, more preferably 0.47-0.51 ml / g, more preferably 0.48-0.50 ml / g, as determined according to reference example 3.

[0233] 70. A molded article according to any one of embodiments 49-69, having an acid site density at a temperature below 250 °C in the range of 0.20-0.75 mmol / g, preferably 0.25-0.65 mmol / g, more preferably 0.44-0.52 mmol / g, more preferably 0.46-0.50 mmol / g, more preferably 0.47-0.49 mmol / g, as determined according to reference example 6.

[0234] 71. The molded article according to any one of embodiments 49 - 70 has an acid site density at a temperature above 250 °C, preferably in the range of greater than 250 °C to 650 °C, which is equal to or less than 0.5 mmol / g, preferably equal to or less than 0.30 mmol / g, more preferably equal to or less than 0.25 mmol / g, more preferably equal to or less than 0.1 mmol / g, and more preferably equal to or less than 0.01 mmol / g as determined according to Reference Example 6.

[0235] 72. The molded article according to any one of embodiments 49 - 71, wherein 99 - 100% by weight, more preferably 99.5 - 100% by weight, and more preferably 99.9 - 100% by weight of the molded article is composed of the zeolite material and the oxide binder.

[0236] 73. The molded article according to any one of embodiments 49 - 72 is a wire rod, preferably having a hexagonal, rectangular, square, triangular, elliptical or circular cross-section, more preferably a circular cross-section, wherein the cross-section has a diameter preferably in the range of 1.5 - 3.5 mm, more preferably 2.0 - 3.0 mm, more preferably 2.2 - 2.8 mm, and more preferably 2.4 - 2.6 mm.

[0237] 74. The molded article according to any one of embodiments 49 - 73 has an olefin selectivity in the range of 50 - 90%, preferably 55 - 80%, and more preferably 60 - 75%, which is preferably determined according to Example 13.

[0238] 75. The molded article according to any one of embodiments 49 - 74 has a butene selectivity in the range of 10 - 30%, preferably 15 - 25%, and more preferably 18 - 22%, preferably a selectivity to one or more of 1-butene, (2Z)-but-2-ene, (2E)-but-2-ene, and 2-methylprop-1-ene, which is preferably determined according to Example 13.

[0239] 76. The molded article according to any one of embodiments 49 - 75 has a propylene selectivity in the range of 20 - 100%, preferably 25 - 90%, more preferably 30 - 70%, preferably 35 - 65%, more preferably 37 - 50%, and more preferably 38 - 47%, which is preferably determined according to Example 13.

[0240] 77. The molded article according to any one of embodiments 49 - 76 has an ethylene selectivity in the range of 1 - 15%, preferably 4 - 12%, and more preferably 5 - 10%, which is preferably determined according to Example 13.

[0241] 78. A method for converting an oxide to an olefin, comprising:

[0242] (a) providing a molded article according to any one of embodiments 48 - 77;

[0243] (b) Provide a gas stream comprising one or more oxides and optionally one or more olefins and / or optionally one or more hydrocarbons;

[0244] (c) Contact the molded article provided in (a) with the gas stream provided in (b) and convert one or more oxides into one or more olefins and optionally one or more hydrocarbons;

[0245] (d) Optionally recycle one or more of the one or more olefins and / or one or more of the one or more hydrocarbons contained in the gas stream obtained in (c) to (b).

[0246] 79. The method of embodiment 78, wherein the molded article is provided in a fixed bed or a fluidized bed.

[0247] 80. The method of embodiment 78 or 79, wherein the method further comprises, after (a) and before (b):

[0248] (a') Treat the molded article provided in (a) with a gas stream comprising water.

[0249] 81. The method of embodiment 80, wherein the gas stream has a temperature in the range of 450 - 510 °C, preferably 460 - 500 °C, more preferably 470 - 490 °C.

[0250] 82. The method of any one of embodiments 78 - 81, wherein the gas stream provided in (b) comprises one or more selected from aliphatic alcohols, ethers, carbonyl compounds, and mixtures of two or more thereof, preferably selected from C1 - C6 alcohols, di - C1 - C3 alkyl ethers, C1 - C6 aldehydes, C2 - C6 ketones, and mixtures of two or more thereof, more preferably selected from C1 - C4 alcohols, di - C1 - C2 alkyl ethers, C1 - C4 aldehydes, C2 - C4 ketones, and mixtures of two or more thereof, more preferably selected from methanol, ethanol, n - propanol, isopropanol, butanol, dimethyl ether, diethyl ether, ethyl methyl ether, diisopropyl ether, di - n - propyl ether, formaldehyde, dimethyl ketone, and mixtures of two or more thereof, more preferably selected from oxides of methanol, ethanol, dimethyl ether, diethyl ether, ethyl methyl ether, and mixtures of two or more thereof, the gas stream more preferably comprises methanol and / or dimethyl ether, more preferably methanol.

[0251] 83. The method of any one of embodiments 78 - 82, wherein the oxide content in the gas stream provided in (b) is in the range of 2 - 100 vol%, preferably 3 - 99 vol%, more preferably 4 - 95 vol%, more preferably 5 - 80 vol%, more preferably 6 - 50 vol%, more preferably 10 - 40 vol%, more preferably 15 - 25 vol%, more preferably 18 - 22 vol% based on the total volume.

[0252] The method according to any one of embodiments 78 - 83, wherein the gas stream provided in (b) contains water, and the water content in the gas stream provided in (b) is preferably in the range of 1 - 90% by volume, more preferably 2 - 80% by volume, more preferably 5 - 75% by volume, more preferably 10 - 70% by volume.

[0253] The method according to any one of embodiments 78 - 84, wherein the gas stream provided in (b) further contains one or more dilution gases, preferably in an amount in the range of 0.1 - 90% by volume, more preferably 1 - 85% by volume, more preferably 5 - 80% by volume, more preferably 10 - 75% by volume.

[0254] The method according to embodiment 85, wherein the one or more dilution gases are selected from H2O, helium, neon, argon, krypton, nitrogen, carbon monoxide, carbon dioxide, and mixtures of two or more thereof, preferably selected from H2O, argon, nitrogen, carbon dioxide, and mixtures of two or more thereof, more preferably the one or more dilution gases contain H2O or nitrogen, and more preferably the one or more dilution gases are H2O or nitrogen.

[0255] The method according to any one of embodiments 78 - 86, wherein the contact in (c) is carried out at a temperature in the range of 225 - 700 °C, preferably 275 - 650 °C, more preferably 325 - 600 °C, more preferably 375 - 550 °C, more preferably 425 - 525 °C, more preferably 450 - 500 °C, more preferably 475 - 495 °C, more preferably 480 - 490 °C.

[0256] The method according to any one of embodiments 78 - 87, wherein the contact in (c) is carried out at a pressure in the range of 0.01 - 25 bar, preferably 0.1 - 20 bar, more preferably 0.25 - 15 bar, more preferably 0.5 - 10 bar, more preferably 0.75 - 5 bar, more preferably 0.8 - 2 bar, more preferably 0.85 - 1.5 bar, more preferably 0.9 - 1.1 bar.

[0257] The method according to any one of embodiments 78 - 87, wherein the contact in (c) is carried out at a pressure in the range of 0.1 - 25 bar (gauge pressure), preferably 0.25 - 20 bar (gauge pressure), more preferably 0.5 - 15 bar (gauge pressure), more preferably 1.0 - 10 bar (gauge pressure), more preferably 2.0 - 7.0 bar (gauge pressure), more preferably 3.0 - 5.0 bar (gauge pressure), more preferably 3.9 - 4.1 bar (gauge pressure).

[0258] The method according to any one of embodiments 78 - 89, wherein the method is a continuous method, and the gas hourly space velocity (GHSV) of the contact in (c) is preferably in the range of 1 - 30,000 h-1 , preferably 1,000 - 25,000 h -1 , preferably 10,000 - 23,000 h -1 , more preferably 15,000 - 21,500 h -1 , more preferably 20,000 - 20,500 h -1 within the range.

[0259] 91. The method according to any one of embodiments 78 - 90, wherein the method is a continuous method, and the weight hourly space velocity (WHSV) of the contact in (c) is preferably in the range of 0.5 - 50 h -1 , preferably 1 - 30 h -1 , more preferably 2 - 20 h -1 , preferably 5 - 15 h -1 , more preferably 8 - 12 h -1 , more preferably 9 - 11 h -1 within the range.

[0260] 92. The method according to any one of embodiments 78 - 91, wherein the one or more olefins and / or one or more hydrocarbons optionally provided in (b) and / or optionally recycled to (b) comprise one or more selected from ethylene, C4 - C7 olefins, C4 - C7 hydrocarbons, and mixtures of two or more thereof, preferably one or more selected from ethylene, C4 - C5 olefins, C4 - C5 hydrocarbons, and mixtures of two or more thereof.

[0261] 93. The method according to any one of embodiments 78 - 92, wherein the method further comprises:

[0262] (e) regenerating the molded article in a gas stream comprising one or more of oxygen and nitrogen, preferably air or lean air.

[0263] 94. The method of embodiment 93, wherein the regeneration is carried out in situ in (e).

[0264] 95. The method of embodiment 93 or 94, wherein the temperature of the gas stream comprising the mixture of air and nitrogen has a temperature in the range of 450 - 550 °C, preferably 470 - 510 °C, more preferably 480 - 500 °C.

[0265] 96. The molded article according to any one of embodiments 48 - 77 as a molecular sieve, as an adsorbent, for ion exchange, or as a catalyst and / or as a catalyst support, preferably as a selective catalytic reduction (SCR) of nitrogen oxides NO xA catalyst; for oxidizing NH3, especially for oxidizing escaped NH3 in a diesel system; for decomposing N2O; as an additive in a fluid catalytic cracking (FCC) process; and / or as a catalyst in an organic conversion reaction, preferably as a hydrocracking catalyst, as an alkylation catalyst, as an isomerization catalyst, or in the conversion of alcohols to olefins, more preferably as a catalyst in the conversion of oxides to olefins.

[0266] The use according to embodiment 96, wherein the molded article is used in a methanol-to-olefins process (MTO process), in a dimethyl ether-to-olefins process (DTO process), in a methanol-to-gasoline process (MTG process), in a methanol-to-hydrocarbons process, in a methanol-to-aromatics process, in a biomass-to-olefins and / or biomass-to-aromatics process, in a methane-to-benzene process, in aromatic alkylation, or in a fluid catalytic cracking process (FCC process), preferably in a methanol-to-olefins process (MTO process) and / or in a dimethyl ether-to-olefins process (DTO process), more preferably in a methanol-to-propylene process (MTP process), in a methanol-to-propylene / butene process (MT3 / 4 process), in a dimethyl ether-to-propylene process (DTP process), in a dimethyl ether-to-propylene / butene process (DT3 / 4 process), and / or in a dimethyl ether-to-ethylene / propylene process (DT2 / 3 process).

[0267] The present invention is further illustrated by the following examples and comparative examples.

[0268] Experimental section

[0269] Comparative example 1: Determination of BET specific surface area and Langmuir specific surface area

[0270] The BET specific surface area and Langmuir specific surface area were determined by physical adsorption of nitrogen at 77 K according to the method disclosed in DIN 66131. The N2 adsorption isotherm at liquid nitrogen temperature was measured using a Micrometrics ASAP 2020M and a Tristar system for determining the BET specific surface area. Comparative example 2: Determination of the distortion parameter relative to water

[0271] PFG NMR enables non-destructive detection of the thermal molecular motion of adsorbed molecules in free gases and liquids, in macromolecular and supramolecular solutions, and in porous systems. The principle and application are as described in US20070099299A1. The distortion factor was calculated from the diffusion coefficient obtained by NMR according to Comparative example 4. The distortion factor of a porous material is determined by the self-diffusion coefficient (D) of the probe molecule in the porous system eff) and the self-diffusion coefficient (D0) of the free liquid are determined according to Equation I (see S. Kolitcheff, E. Jolimaitre, A. Hugon, J. Verstraete, M. Rivallan, P-L. Carrette, F. Couenne, and M. Tayakout-Fayolle, Catal. Sci. Technol., 2018, 8, 4537; and F. Elwinger, P. Pourmand, and I. Furo, J. Phys. Chem. C. 2017, 121, 13757-13764):

[0272]

[0273] The free diffusion coefficient of water is taken as 2.02×10 -9 m 2 s -1 (see M. Holz, S.R. Heil, and A. Sacco. Phys. Chem. Chem. Phys., 2000, 2, 4740-4742).

[0274] Reference Example 3: Determination of the total pore volume

[0275] The total pore volume is determined according to DIN 66133 via the mercury intrusion method.

[0276] Reference Example 4: Determination of the diffusion coefficient by NMR

[0277] Samples for NMR analysis are prepared by drying a small amount (0.05 - 0.2 g) of the catalyst overnight at T > 350 °C and under vacuum in an NMR measurement tube. Then the sample is filled with ultrapure water (Millipore Advantage A10) via a vacuum line to 90% of the pore volume of the catalyst support (determined by the mercury intrusion method). Then the filled sample is flame-sealed in the measurement tube and left overnight before measurement.

[0278] The NMR analysis for determining D of water in the catalyst material eff is carried out at 20 °C and 1 bar at a 1H resonance frequency of 400 MHz using a Bruker Avance III NMR spectrometer. A Bruker Diff50 probe head with a Bruker Great 60A gradient amplifier is used. The temperature of 20 °C is maintained by a water-cooled gradient coil. The pulse program for PFG NMR self-diffusion analysis is based on US20070099299A1 Figure 1b Stimulated spin echo with pulsed field gradient. For each sample, the spin echo decay curve was measured at different diffusion times (between 20 - 100 ms) by gradually increasing the intensity of the field gradient (up to a maximum gmax = 3 T / m). The gradient pulse length was 1 ms. The spin echo decay curve was fitted to Equation 6 of US 2007 / 0099299 A. As an example, the double logarithmic plot of data from the catalyst support at various diffusion times is shown in Figure X. The slope of each line corresponds to the diffusion coefficient. The average diffusion coefficient over all diffusion times was used to calculate the tortuosity of each catalyst support according to Equation I (see Reference Example 2).

[0279] Reference Example 5: Determination of crush strength

[0280] The crush strength mentioned in the context of the present invention should be understood as having been determined via the crush strength testing machine Z2.5 / TS1S, supplier Zwick GmbH&Co., D-89079 Ulm, Germany. Regarding the basic principle of this machine and its operation, reference is made to the corresponding instruction manual "Register 1: Betriebsanleitung / Sicherheitshandbuch für die Material-Prüfmaschine Z2.5 / TS1S", version 1.5, December 2001, Zwick GmbH&Co. Technische Dokumentation, August-Nagel-Strasse 11, D-89079 Ulm, Germany. The machine is equipped with a fixed horizontal workbench on which the wire material is located. A plunger with a diameter of 3 mm that can move freely in the vertical direction drives the wire material against this fixed workbench. The device operates with a preliminary force of 0.5 N, a shear rate under the preliminary force of 10 mm / min, and a subsequent test rate of 1.6 mm / min. The vertically movable plunger is connected to a force sensor to extract the force and moves towards the fixed turntable on which the molded article (wire material) to be studied is placed during the measurement, thereby driving the wire material against the table. The plunger is applied perpendicular to the longitudinal axis of the wire material. The given wire material described below is subjected to an increasing force via the plunger using the said machine until the wire material is crushed. The force required to crush the wire material is called the crush strength of the wire material.

[0281] The test is controlled by a computer that records and evaluates the measurement results. The value obtained is in each case the average of the measurements on 20 or 30 wire materials. Specifically, 20 wire materials were used for Comparative Example 9 and Example 10, and 30 wire materials were used for Examples 11 and 12 to determine the crush strength. Reference Example 6: Temperature-programmed desorption of ammonia (NH3-TPD)

[0282] Temperature-programmed desorption of ammonia (NH3-TPD) was carried out in an automated chemisorption analysis unit (Micromeritics AutoChem II 2920) equipped with a thermal conductivity detector. Continuous analysis of the desorbed species was accomplished using an on-line mass spectrometer (OmniStar QMG200 from Pfeiffer Vacuum). A sample (0.1 g) was introduced into a quartz tube and analyzed using the following procedure. Temperature was measured with a Ni / Cr / Ni thermocouple located immediately above the sample in the quartz tube. He with a purity of 5.0 was used for the analysis. A blank sample was analyzed for calibration prior to any measurement.

[0283] 1. Preparation: Start recording; measure once per second. Wait for 10 minutes at 25 °C and a He flow rate of 30 cm 3 / min (room temperature (ca. 25 °C) and 1 atm); heat to 600 °C at a heating rate of 20 K / min; hold for 10 minutes. Cool to 100 °C (furnace slope temperature) at a cooling rate of 20 K / min under He flow (30 cm 3 / min); cool to 100 °C (sample slope temperature) at a cooling rate of 3 K / min under He flow (30 cm 3 / min).

[0284] 2. Saturation with NH3: Start recording; measure once per second. Change the gas flow to a 10% NH3 in He mixture (75 cm 3 / min; 100 °C and 1 atm) at 100 °C; hold for 30 minutes.

[0285] 3. Removal of excess amount: Start recording; measure once per second. Change the gas flow to a He flow of 75 cm 3 / min (100 °C and 1 atm) at 100 °C; hold for 60 minutes.

[0286] 4. NH3-TPD: Start recording; measure once per second. Heat to 600 °C at a heating rate of 10 K / min under He flow (flow rate: 30 cm 3 / min); hold for 30 minutes.

[0287] 5. End of measurement.

[0288] The desorbed ammonia was measured with an on-line mass spectrometer, which indicated that the signal from the thermal conductivity detector was caused by the desorbed ammonia. This involved using the m / z = 16 signal from ammonia to monitor the desorption of ammonia. The amount of adsorbed ammonia (mmol / g sample) was determined using Micromeritics software by integrating the TPD signal with respect to the horizontal baseline.

[0289] Reference Example 7: Synthesis of ZSM-5 zeolite with a SiO2:Al2O3 molar ratio of 100

[0290] Stir 757.0 kg of tetraethyl orthosilicate (TEOS) in a container. Mix a mixture of 350 kg of deionized water and an aqueous solution of 366.0 kg of tetrapropylammonium hydroxide in water (TPAOH; Sachem; 40 wt% TPAOH in water). Stir the resulting mixture for 60 minutes. Then mix in 120 kg of deionized water. Stir the resulting mixture for 1 hour to hydrolyze the TEOS. Heat the mixture to an internal temperature of 90 °C, with the external temperature thus being 120 °C. Ethanol is removed via distillation as an azeotropic mixture of water and ethanol until a storage temperature of 95 °C is reached. 856 kg of water / ethanol is thus removed from the mixture. Then cool the mixture to 30 °C. Then mix in 856 kg of water to replace the lost liquid. Mix a solution of 24.2 kg of aluminum sulfate octadecahydrate (Al2(SO4)3·18H2O; Sigma-Aldrich) and 40 kg of deionized water into the mixture. Seal the container and heat it to a temperature of 170 °C within 4 hours. Heat the mixture in an autoclave at 170 °C for 48 hours. Then cool the mixture to a temperature of 50 °C. Treat the mixture with 177.5 kg of an aqueous nitric acid solution (BASF; 10 wt% in water) until a pH value of 7.6 is reached. Filter the resulting suspension after stirring for 30 minutes. Wash the filter cake with deionized water, pre-dry it under a nitrogen stream for 6 hours, and then dry it in a dryer at a temperature of 120 °C for 36 hours. 217 kg of dry material is obtained. Grind the dry powder and then calcine it (5 hours, 500 °C).

[0291] The resulting material has a silica / alumina ratio of 100 and a crystallinity greater than 90%. It shows a BET specific surface area of 427 m 2 / g and a Langmuir specific surface area of 589 m 2 / g. In addition, the resulting material has a TOC of less than 0.1 g / 100 g, a Si content of 44 g / 100 g, an Al content of 0.87 g / 100 g, and an alkali metal content of less than 0.01 g / 100 g.

[0292] Reference Example 8: Preparation of a zeolite material containing Mg (Mg-ZSM-5)

[0293] Spray-impregnate the ZSM-5 powder obtained from Reference Example 7 with a magnesium nitrate solution. The amount of Mg weighed in should be such that the powder contains 2 - 3 wt% Mg after calcination.

[0294] To impregnate the ZSM-5 zeolite prepared according to Reference Example 7, 5 kg of zeolite powder was introduced into a drum mixer. 1.2 kg of magnesium nitrate hexahydrate (Merck) was dissolved in 1.16 kg of deionized water. The resulting magnesium nitrate solution was then sprayed onto the ZSM-5 powder through a glass nozzle while rotating over a period of 95 minutes. The mixture was then rotated for an additional 15 minutes. The impregnated powder was then dried in a circulating oven at a temperature of 120 °C for 4 hours and then calcined in a static oven at 500 °C under air for 5 hours (the heating rate of the static oven was 2 °C / min).

[0295] The resulting material contained 2.2 g of Mg / 100 g.

[0296] Comparative Example 9: Preparation of extrudates containing Mg-ZSM-5

[0297] The Mg-ZSM-5 powder prepared by spray impregnation according to Reference Example 8 was further processed with boehmite (Pural SB; Sasol) as a binder to obtain extrudates. The amounts of the starting materials were selected such that the extrudates contained 10 wt% Al2O3 as a binder.

[0298] 4970 g of zeolite powder and 790 g of boehmite (Pural SB; Sasol) were weighed into a koller and mixed for 5 minutes. 124 g of an aqueous formic acid solution (24 g of formic acid in 100 g of deionized water) was mixed therein. Then, four portions of 455 g of water each were mixed in at intervals of approximately 5 minutes over the first 35 minutes. Then, 110 g of polyethylene oxide (PEO E160) was mixed in and subsequently four portions of 455 g of water each were mixed in at intervals of approximately 5 minutes until a total kneading time of 50 minutes was reached. The kneaded material was pressed through a 2.5 mm die at 120 - 200 bar with an extruder. The resulting extrudates were then dried in a circulating oven at a temperature of 120 °C for 4 hours and then calcined in a static oven at 550 °C for 5 hours. The extrudates could be manually broken to the desired length.

[0299] The resulting extrudates had a crushing strength of 5.5 N. The Mg content of the resulting extrudates was 2.0 g Mg / 100 g and the BET specific surface area was 345 m 2 / g. In addition, the resulting extrudates showed a total pore volume of 0.52 ml / g. Furthermore, the acid site density was 0.70 mmol / g at temperatures below 250 °C and 0.05 mmol / g at temperatures above 250 °C as determined by NH3-TPD disclosed herein.

[0300] Example 10: Preparation of extrudates containing Mg-ZSM-5 (SiO2:Al2O3 molar ratio of 100)

[0301] The Mg-ZSM-5 powder prepared by spray impregnation according to Reference Example 8 was further processed with boehmite (Pural SB; Sasol) as a binder to obtain an extrudate. The amounts of the raw materials were selected such that the extrudate contained 10 wt% Al2O3 as a binder.

[0302] 4900 g of zeolite powder, 726 g of boehmite (Pural SB; Sasol) and 281 g of polysaccharide (Zusoplast PS1) were weighed into a koller and mixed for 5 minutes. 2252 g of an aqueous formic acid solution (25 wt% formic acid in deionized water) was mixed therein. Then, four portions of 455 g of water each were mixed in at intervals of about 5 minutes within the first 35 minutes. Then, 110 g of polyethylene oxide (PEOE160) was mixed in and subsequently four portions of 455 g of water each were mixed in at intervals of about 5 minutes until a total kneading time of 50 minutes was reached. The kneaded material was pressed through a 2.5 mm die at 120 - 200 bar with an extruder. Then, the obtained extrudate was dried in a circulating oven at a temperature of 120 °C for 4 hours and then calcined in a static oven at 550 °C for 5 hours. The extrudate could be manually broken to the desired length.

[0303] The obtained extrudate had a crushing strength of 21 N. The Mg content of the obtained extrudate was 1.9 g Mg / 100 g and the BET specific surface area was 356 m 2 / g. In addition, the obtained extrudate showed a total pore volume of 0.49 ml / g. In addition, the acid site density was 0.48 mmol / g at temperatures below 250 °C and less than 0.01 mmol / g at temperatures above 250 °C as determined by NH3-TPD disclosed herein.

[0304] From the results of the determination of mechanical strength, it can be seen that the novel molded articles prepared according to the present invention showed a relatively higher crushing strength than the molded articles prepared according to the prior art but having a similar composition. In particular, it has been shown that the molded article prepared according to Example 10 of the present invention showed a crushing strength of 21 N, while the molded article according to the prior art showed a crushing strength of 5.5 N.

[0305] Example 11: Preparation of an extrudate containing Mg-ZSM-5 (SiO2:Al2O3 molar ratio of 100)

[0306] The Mg-ZSM-5 powder prepared by spray impregnation according to Reference Example 8 was further processed with boehmite (Pural SB; Sasol) as a binder to obtain an extrudate. The amounts of the raw materials were selected such that the extrudate contained 10 wt% Al2O3 as a binder.

[0307] Weigh 120 g of zeolite powder into a kneader and knead for 5 minutes. Separately, prepare a suspension of 17.78 g of boehmite (Pural SB; Sasol) in 80 g of deionized water. Mix 4.24 g of an aqueous nitric acid solution (65 wt% nitric acid in deionized water) into this suspension and stir the resulting suspension for 1 minute to form a gel. Then add the formed gel to the zeolite material in the kneader and knead the resulting mixture for 30 minutes. Add 2.76 g of polysaccharide (Zusoplast PS1) and 0.69 g of polyethylene oxide (PEO E160) and knead the resulting mixture for 5 minutes. Then mix in a portion of 10 g of water and knead the resulting mixture for 5 minutes. Press the kneaded material through a 2.5 mm die at a pressure of 93 - 148 bar using an extruder. Then dry the resulting extrudate in a circulating oven at a temperature of 120 °C for 4 hours (whereby the heating slope is set to 2 °C / min), and then calcine it in a static oven at 550 °C for 5 hours (whereby the heating slope is set to 2 °C / min). The extrudate can be manually broken into the desired length.

[0308] The resulting extrudate has a crushing strength of 17.7 N. The Mg content of the resulting extrudate is 1.8 g Mg / 100 g, the Al content is 5.8 g / 100 g, the Si content is 38 g / 100 g, the C content is less than 0.1 g / 100 g and the BET specific surface area is 350 m 2 / g. In addition, the resulting extrudate shows a total pore volume of 0.50 ml / g. Furthermore, the acid site density is 0.325 mmol / g at temperatures below 250 °C and 0.218 mmol / g at temperatures in the range greater than 250 °C to 650 °C as determined by NH3 - TPD disclosed herein.

[0309] From the results of the mechanical strength determination, it can be seen that the novel molded articles prepared according to the present invention show a relatively higher crushing strength compared to molded articles prepared according to the prior art but having a similar composition. In particular, it has been shown that the molded article prepared according to Example 11 of the present invention shows a crushing strength of 17.7 N, while the molded article according to the prior art shows a crushing strength of 5.5 N.

[0310] Example 12: Preparation of an extrudate containing Mg - ZSM - 5 (SiO2:Al2O3 molar ratio of 100)

[0311] The Mg - ZSM - 5 powder prepared by spray impregnation according to Reference Example 8 is further processed with boehmite (Pural SB; Sasol) as a binder to obtain an extrudate. The amounts of the raw materials are selected such that the extrudate contains 10 wt% Al2O3 as a binder.

[0312] Weigh 120 g of zeolite powder into a kneader and knead for 5 minutes. Separately, prepare a suspension of 17.78 g of boehmite (Pural SB; Sasol) in 80 g of deionized water. Mix 3.18 g of aqueous nitric acid solution (65 wt% nitric acid in deionized water) into this suspension and stir the resulting suspension for 1 minute to form a gel. Then add the formed gel to the zeolite material in the kneader and knead the resulting mixture for 30 minutes. Add 2.76 g of polysaccharide (Zusoplast PS1) and 0.69 g of polyethylene oxide (PEO E160) and knead the resulting mixture for 5 minutes. Then mix in a portion of 10 g of water and knead the resulting mixture for 2 minutes. Then mix in a portion of 1 g of water and knead the resulting mixture for 2 minutes. Press the kneaded material through a 2.5 mm die at a pressure of 93 - 148 bar using an extruder. Then dry the resulting extrudate in a circulating oven at a temperature of 120 °C for 4 hours (setting the heating slope to 2 °C / min), and then calcine it in a static oven at 550 °C for 5 hours (setting the heating slope to 2 °C / min). The extrudate can be manually broken to the desired length.

[0313] The resulting extrudate has a crushing strength of 17.1 N. The Mg content of the resulting extrudate is 1.9 g Mg / 100 g, the Al content is 5.9 g / 100 g, the Si content is 38 g / 100 g, the C content is less than 0.1 g / 100 g and the BET specific surface area is 354 m 2 / g. In addition, the resulting extrudate shows a total pore volume of 0.49 ml / g. In addition, the acid site density is 0.286 mmol / g at temperatures below 250 °C and 0.261 mmol / g at temperatures in the range greater than 250 °C to 650 °C as determined by NH3 - TPD disclosed herein.

[0314] From the determination results of the mechanical strength, it can be seen that the novel molded article prepared according to the present invention shows a relatively higher crushing strength than the molded article prepared according to the prior art but having a similar composition. In particular, it has been shown that the molded article prepared according to Example 12 of the present invention shows a crushing strength of 17.1 N, while the molded article according to the prior art shows a crushing strength of 5.5 N.

[0315] Example 13: Catalytic test - Methanol - to - Olefins reaction

[0316] The Methanol - to - Olefins (MTO) reaction is carried out in a fixed - bed reactor at a temperature of 490 °C and a pressure of 4 bar (gauge pressure). Heat the sample (2.7 g, 1.6 - 2.0 mm sieved fraction) in flowing nitrogen (10 Nl / h) at 490 °C for 3 hours. Feed a feed stream containing 20 vol% methanol, 70 vol% water and 10 vol% nitrogen at 10 h -1Weight hourly space velocity (WHSV) and 20224 h -1 The gas hourly space velocity (GHSV) of -1 was continuously fed into the catalyst bed. The continuous operation period was about 70 hours. The products were analyzed by an on-line gas chromatograph (Agilent 7890A) equipped with a TCD detector, 2 FID detectors and using Select Permanent CO2 HR, Restek Stabilwax and Al2O3 MAPD columns.

[0317] The methanol conversion X was calculated according to Equation II:

[0318] X = 1 – (MeOH 出 / MeOH 入 )(II)

[0319] In Equation II, MeOH 出 is the methanol at the reactor outlet and MeOH 入 is the methanol at the reactor inlet.

[0320] The selectivities of different products were given according to Equation III:

[0321]

[0322] In Equation III, NC i is the number of carbon atoms in component i, n i is the number of moles of component i, (out) refers to the outlet stream of the reactor and (in) refers to the inlet stream of the reactor.

[0323] The molded articles prepared according to Comparative Example 9 and the molded articles prepared according to Example 10 were tested in the conversion of methanol to olefins.

[0324] The results of the catalytic tests are shown below Figure 1 and 3 in. As can be seen Figure 2 , the molded articles according to Comparative Example 9 reflecting the prior art showed a methanol conversion in the range of 90 - 100% within the first 20 hours, decreased to about 80% within the subsequent 40 hours and continued to decrease to about 70%. The methanol conversion fluctuated violently after 40 hours of production. The olefin selectivity was slightly higher than 70% within the first 40 hours and then decreased to a value in the range of 50 - 68%. The butene selectivity was about 20% throughout the test time, the propylene selectivity was about 39 - 42% within the first 60 hours and then decreased to a value in the range of 30 - 40% and the ethylene selectivity was about 6 - 10% throughout the test time.

[0325] In contrast, the molded article prepared according to Example 10 of the present invention shows a methanol conversion rate in the range of 90 - 100% within the first 40 hours and remains at about 90% within the subsequent 20 hours, and then slightly decreases to a value in the range of 80 - 90%. The olefin selectivity is slightly higher than 70% within the first 40 hours and then slightly decreases to a value in the range of 60 - 70%. The butene selectivity is about 20% throughout the test time, the propylene selectivity is about 39 - 45% throughout the test time, and the ethylene selectivity is about 6 - 10% throughout the test time.

[0326] In addition, the molded articles prepared according to Examples 11 and 12 of the present invention respectively show a methanol conversion rate in the range of 90 - 100% within the first 50 hours and remain at about 90% within the subsequent 30 hours. The olefin selectivity is about 70% throughout the test period. The butene selectivity is about 20% throughout the test time, the propylene selectivity is about 39 - 45% throughout the test time, and the ethylene selectivity is about 7 - 10% throughout the test time.

[0327] Therefore, it can be seen from the results of the catalytic tests that the molded articles of the present invention achieve overall excellent performance not only in terms of the degree of methanol conversion and the specific selectivity for the desired olefins, but also in terms of long-term performance. Therefore, it can be seen from the results that the molded articles of the present invention show longer catalytic activity to a relatively higher degree. Description of the Drawings

[0328] Figure 1 A double logarithmic plot showing data from the catalyst support at various diffusion times used. The signal is given in arbitrary units on the ordinate and the b value is given on the abscissa. The slope of each line corresponds to the diffusion coefficient.

[0329] Figure 2 Description of the catalytic performance of the molded article prepared according to Comparative Example 9. The continuous operating time on stream (TOS) is given in hours on the abscissa and the conversion rate relative to methanol and the selectivities for olefins, butenes, propylene, ethylene, paraffins, and carbon oxides (CO and CO2) are given in % on the ordinate, which are determined according to Example 13.

[0330] Figure 3 Description of the catalytic performance of the molded article prepared according to Example 10. The continuous operating time on stream (TOS) is given in hours on the abscissa and the conversion rate relative to methanol and the selectivities for olefins, butenes, propylene, ethylene, paraffins, and carbon oxides (CO and CO2) are given in % on the ordinate, which are determined according to Example 13.

[0331] Figure 4Describe the catalytic performance of the molded article prepared according to Example 11. The continuous operating period (TOS) is given in hours on the abscissa and the conversion rate relative to methanol and the selectivities of olefins, butenes, propylene, ethylene, paraffins, and carbon oxides (CO and CO2) are given in % on the ordinate, which are determined according to Example 13.

[0332] Figure 5 Describe the catalytic performance of the molded article prepared according to Example 12. The continuous operating period (TOS) is given in hours on the abscissa and the conversion rate relative to methanol and the selectivities of olefins, butenes, propylene, ethylene, paraffins, and carbon oxides (CO and CO2) are given in % on the ordinate, which are determined according to Example 13.

[0333] Cited references

[0334] -WO 2012 / 085154 A1

[0335] -US 2014 / 0058180 A1

[0336] -US 10,112,188B2

[0337] -US 2014 / 0058181 A1

[0338] -US 10,005,073B2

[0339] -US 9,511,361 B2

[0340] -US 2017 / 0121259 A1

[0341] -WO 2018 / 109083 A1

[0342] -CN 100503041 C

[0343] -CN 104511298 B

Claims

1. A method for preparing a molded article comprising a zeolite material and one or more oxide binders, wherein the zeolite material contains YO2 and X2O3 in its framework structure, where Y is Si and X is a trivalent element, the method comprising: (i) Prepare a mixture comprising a zeolite material, a source of oxide binder, a first plasticizer, and an acid; (iii) Incorporate a second plasticizer different from the first plasticizer into the mixture obtained in (i); (v) Shape the mixture obtained in (iii) to obtain a precursor of the molded article; wherein the weight ratio of the oxide binder source, calculated as oxide, to the sum of the zeolite material and the oxide binder source, calculated as oxide, in the mixture prepared in (i) is in the range of 0.05:1 - 0.15:1; wherein the oxide binder source comprises one or more of AlOOH (boehmite) and Al2O3; wherein X is selected from B, Al, Ga, In, and mixtures of two or more thereof, and wherein the molded article has a crushing strength equal to or greater than 9 N.

2. The method of claim 1, wherein (i) comprises: (i.1.a) Prepare a mixture comprising a zeolite material, a source of oxide binder, and a first plasticizer; (i.1.b) Incorporate an acid into the mixture obtained in (i.1.a); wherein the amount of the acid incorporated in (i.1.b) is in the range of 5 - 50 wt%; and wherein the weight ratio of the acid incorporated in (i.1.b) to the sum of the zeolite material and the oxide binder source of the mixture prepared in (i) is in the range of 0.05:1 - 0.15:

1.

3. The method of claim 1, wherein (i) comprises: (i.2.a) Provide a zeolite material; (i.2.b) Provide a mixture comprising a source of oxide binder, optional water, and an acid; (i.2.c) Mix the mixture obtained in (i.2.b) with the zeolite material provided in (i.2.a); (i.2.d) Incorporate a first plasticizer into the mixture obtained in (i.2.c); wherein the acid is provided as an aqueous solution containing the acid in an amount in the range of 50 - 80 wt% for the mixture of (i.2.b); wherein the weight ratio of the acid provided for the mixture of (i.2.b) to the sum of the zeolite material and the oxide binder source of the mixture prepared in (i) is in the range of 0.005:1 - 0.05:

1.

4. The method of claim 1, wherein the first plasticizer is selected from organic polymers, carbohydrates, graphite, plant additives, and mixtures of two or more thereof.

5. The method of claim 2, wherein the first plasticizer is selected from organic polymers, carbohydrates, graphite, plant additives, and mixtures of two or more thereof.

6. The method of claim 3, wherein the first plasticizer is selected from organic polymers, carbohydrates, graphite, plant additives, and mixtures of two or more thereof.

7. The method of any one of claims 1 - 6, wherein the oxide binder source comprises AlOOH (boehmite).

8. The method according to any one of claims 1 - 6, wherein the zeolite material has a framework structure type selected from 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, ERI, 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, MFI, 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 a mixed type framework structure type of two or more thereof.

9. The method of claim 7, wherein the zeolite material has a framework structure type selected from 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, ERI, 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, MFI, 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 thereof of two or more of these framework structure types.

10. The method according to any one of claims 1 - 6, wherein the zeolite material comprises one or more alkaline earth metals M.

11. The method according to claim 9, wherein the zeolite material comprises one or more alkaline earth metals M.

12. The method according to any one of claims 1 - 6, wherein the acid is one or more of an inorganic acid and an organic acid.

13. The method according to claim 11, wherein the acid is one or more of an inorganic acid and an organic acid.

14. The method according to any one of claims 1 - 6, wherein in (v) the mixture is formed into a wire.

15. The method according to claim 13, wherein in (v) the mixture is formed into a wire.

16. A molded article obtainable or obtained by the method according to any one of claims 1 - 15.

17. A molded article comprising one or more oxide binders and a zeolite material, wherein the zeolite material comprises YO2 and X2O3 in its framework structure, where Y is Si and X is a trivalent element, wherein the molded article comprises the one or more oxide binders in an amount in the range of 5 - 15% by weight calculated as the oxide and wherein the molded article has a crushing strength equal to or greater than 9 N, wherein the one or more oxide binders are alumina, and wherein X is selected from B, Al, Ga, In and mixtures of two or more thereof.

18. The molded article according to claim 17, having a diffusion coefficient in the range of 0.40 - 1.30×10 -9 m 2 / s.

19. The molded article according to claim 17 or 18, having a distortion parameter with respect to water in the range of 1.00 - 3.

75.

20. A method for converting an oxide into an olefin, comprising: (a) Provide a molded article according to any one of claims 16 - 19; (b) Provide a gas stream comprising one or more oxides and optionally one or more olefins and / or optionally one or more hydrocarbons; (c) Contact the molded article provided in (a) with the gas stream provided in (b) and convert one or more oxides into one or more olefins and optionally one or more hydrocarbons; (d) Optionally recycle one or more of the one or more olefins and / or one or more of the one or more hydrocarbons contained in the gas stream obtained in (c) to (b).

21. Use of the molded article according to any one of claims 16 - 19 as a molecular sieve, as an adsorbent, for ion exchange or as a catalyst and / or as a catalyst support.

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