EP2866934A2

EP2866934A2 - Catalyst coating and method for the conversion of oxygenates to olefins

Info

Publication number: EP2866934A2
Application number: EP13732467.9A
Authority: EP
Inventors: Kirsten SPANNHOFF; Florina Corina Patcas; Ekkehard Schwab; Alexander Weck; Kerem Bay; Matthias MIELKE; Oliver Seel
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2012-06-29
Filing date: 2013-06-26
Publication date: 2015-05-06
Also published as: CA2877796C; WO2014001412A3; BR112014031094A2; AU2013283349B2; MX2014015736A; JP2015522408A; CN104582841A; RU2015102718A; AU2013283349A1; WO2014001412A2; JP6466325B2; CN109453804A; ZA201500361B; CA2877796A1; BR112014031094A8

Abstract

The present invention relates to a catalyst for the conversion of oxygenates to olefins, comprising a carrier substrate and a layer applied to the substrate, the layer containing one or more zeolites of an MFI-, MEL- and/or MWW-type structure, wherein the one or more zeolites contain one or more alkaline earth metals. The invention also relates to the production and use of said catalyst and to a method for the conversion of oxygenates to olefins using the catalyst.

Description

Catalyst coating and process for the conversion of oxigenates to olefins

The present invention relates to a catalyst in the form of a coated carrier substrate for the conversion of oxygenates to olefins and a process for its preparation. Furthermore, the present invention relates to a process for the conversion of oxygenates to olefins, in particular using the coated carrier substrate according to the invention as catalyst and the use of a catalyst according to the present invention in specific catalytic processes.

INTRODUCTION

Given the increasing scarcity of oil resources that serve as a source for the production of lower hydrocarbons and their derivatives, alternative methods of producing such base chemicals are becoming increasingly important. In alternative processes for the production of lower hydrocarbons and their derivatives, specific catalysts are often used in order to selectively produce lower hydrocarbons and their derivatives, in particular unsaturated lower hydrocarbons, from other raw materials and / or chemicals. In this process, processes in which methanol as the starting chemical is subjected to catalytic conversion play an important role, as a rule resulting in a mixture of olefins, paraffins and aromatics.

In such catalytic conversions, the challenge is, in particular, to refine the catalysts used there, as well as the process control and its parameters, in such a way that as few as possible selectively products are produced as selectively as possible in the catalytic conversion. Thus, these methods are named in particular for the products that are mainly produced. In recent decades, such processes have gained particular importance, which allow the conversion of methanol to olefins and are characterized accordingly as methanol-to-olefin (MTO process for methanol to olefins). For this purpose, in particular catalysts and processes have been developed which convert methanol via the intermediate dimethyl ether to mixtures whose main constituents ethene and propene make up. Antia et al. in Ind. Eng. Chem. Res. 1995, 34, pages 140-147 describes the coating of a carrier substrate with ZSM-5 and its use in a methanol-to-gasoline process (MTG process).

No. 4,692,423 relates to a process for the preparation of a supported zeolite-containing catalyst by applying a mixture of a zeolite in a polymerizable solvent such as tetrahydrofuran to a porous carrier substrate, the latter being made of organic or inorganic material. Ivanova et al. in J. Phys. Chem. C 2007,, pages 4368-4374 relates to a foamed molding and an extrudate of β-silicon carbide, to each of which a ZSM-5 coating is applied, as well as the use of such a coated foam body and extrudate in methanol-zu Olefin process (MTO process). In comparison to the use of the pulverulent zeolite per se, an improvement of the catalytic activity / selectivity is observed, whereby the coated catalysts should show a higher stability against deactivation by coking. Patcas, FC in Journal of Catalysis 2005, 231, pages 194-200 describes ZSM-5 zeolite coated ceramic foams and their use in methanol-to-olefin processes. In particular, it is described that, compared to zeolite-containing pellets, such coated ceramic foams should show an improvement in activity and selectivity. At lower temperatures and higher space velocities, however, lower space yields are described compared to the zeolite-containing pellets.

WO 98/29519 A1 describes non-zeolitic molecular sieves supported on inorganic materials and in particular SAPO and their use in methanol-to-olefin processes. WO 94/25151 A1 describes zeolites carried on monoliths and in particular ZSM-5 and their use as molecular sieves in separation processes.

Hammon et al. in Applied Catalysis 1988, 37, pages 155-174 relates to processes for the preparation of Zeolithextrudaten with little to no binder and their use in methanol-to-olefin process. However, in Hammon et al. the use of monoliths shaped extrudates described as catalysts because of rapid coking and thus associated short downtime as particularly disadvantageous.

Li et al. in Catal. Lett. 2009, 129, pages 408-415 relates to a foamed ZSM-5 monolith and its use in a methanol-to-olefin process.

For example, DD 238733 A1 relates to a zeolite doped with magnesium and its use in the conversion of methanol to lower olefins, especially of the C number range> 3. Mclntosh et al. in Applied Catalysis 1983, 6, p 307-314 specifically describes ZSM-5 catalysts and their use in methanol-to-olefin processes, as well as their doping with various metals and non-metals, such as magnesium or phosphorus, and their Influence on yields and product distribution in the catalytic conversion of methanol. No. 4,049,573 relates to a catalytic process for the conversion of lower alcohols and their ethers and, in particular, methanol and dimethyl ether selectively into a hydrocarbon mixture with a high proportion of C 2 -C 3 -olefins and mononuclear aromatics and, in particular, Para-xylene, wherein the catalysts used therein are doped with boron, magnesium and / or phosphorus.

Goryainova et al. in Petroleum Chemistry 201 1, Vol. 51, No. 3, pp. 169-173 describes the catalytic conversion of dimethyl ether to lower olefins using magnesium-containing zeolites.

Ciambelli et al., "Acid-base catalysis in the conversion of methanol to olefins over Mg-modified ZSM-5 zeolite", Successful Design of Catalysts, Elsevier Science Publishers BV, Amsterdam, 1988, pp. 239-246 examines the influence of magnesium in the MTO process and in particular in cooperation with ZSM-5 zeolite as catalyst.

Okado et al. in Applied Catalysis 1988, 41, pp. 121-135 relates to methanol-to-olefin processes using the ZSM-5 catalyst and thereby examines the influence of various alkaline earth metals with respect to a deactivation of the catalyst during its lifetime.

Although in the prior art with regard to the selectivities and / or activities of the catalysts by changes in their composition and / or their design, in particular in methanol-to-olefin process partially progress could be achieved, there is still a significant need for new catalysts and Processes which, in addition to new and / or improved selectivities, also have a better resistance to the possible deactivation in such processes. This is especially true for such improvements, which can lead to a lower coking of the catalyst, thereby enabling a higher efficiency of existing and new processes.

DETAILED DESCRIPTION Thus, the object of the present invention was to provide an improved catalyst, in particular for the conversion of oxygenates to olefins, which enables a longer service life of the catalyst at comparable space velocity and conversion to oxygenates. Here, the object of the present invention, in particular, was to bring about improvements in the coking of the catalyst, which, for example, in methanol-to-olefin process, the service life of a catalyst, to which the regeneration of the catalyst is required, to the desired selectivity and / or to achieve a sufficient space-time yield.

It has surprisingly been found that a catalyst for the conversion of oxygenates to olefins, which comprises a carrier substrate and a layer applied to the substrate, wherein the catalytically active layer comprises one or more zeolites of the MFI, MEL and / or MWW structure type, each containing one or more alkaline earth metals, includes, not only possesses a considerably improved tool life, but also a surprisingly high selectivity of C3 and _C4 olefins having. In particular, it has unexpectedly been found that the particular combination of doping one or more MFI, MEL and / or MWW structural type zeolites with one or more alkaline earth metals in conjunction with one embodiment of the catalyst as coated with the one or more zeolites Carrier substrate has both an unexpected improvement in the resistance of the catalyst to deactivation during its use in a catalytic process as well as a surprisingly high olefin selectivity when using the catalyst for the conversion of oxygenates result.

Thus, the present invention relates to a catalyst for the conversion of oxygenates to olefins comprising a carrier substrate and

a layer applied to the substrate, the layer containing one or more MFI, MEL and / or MWW-type zeolites and wherein the one or more zeolites contain one or more alkaline-earth metals.

With regard to the carrier substrate used in the catalyst according to the invention, there is in principle no restriction as to its shape. Thus, in principle, any conceivable possible form for the carrier substrate can be chosen, provided that it is suitable for being at least partially coated with a layer of the one or more MFI, MEL and / or MWW structure type zeolites. However, in the present invention, it is preferable that the shape of the supporting substrate is selected from the group consisting of granules, pellets, nets, rings, spheres, cylinders, hollow cylinders, monoliths and mixtures and / or combinations of two or more thereof. With regard to the preferred mixtures, these preferably relate to those forms of the carrier substrate which are commonly used for the production of beds, in particular the preferred forms of the carrier substrate selected from the group of granules, pellets, nets, rings, balls, cylinders and hollow cylinders , On the other hand, with regard to the combinations of forms of the carrier substrate according to the present invention, such combinations of beds and monoliths are preferred, the beds preferably carrier substrates selected from the group consisting of granules, pellets, nets, rings, spheres, cylinders, hollow cylinders and mixtures of contain two or more of them. In particular, such combinations of beds and monoliths relate to preferred forms of the catalyst which include a series of one or more monoliths and one or more beds in which the bed (s) and monolith (s) form individual zones of the catalyst. Alternatively, however, embodiments of the catalyst according to the invention are preferred, which contain combinations of monoliths as a form of the carrier substrate, in particular combinations of monoliths according to the particular ren or preferred embodiments as described in the present application. According to particularly preferred embodiments of the present invention, the carrier substrate consists of one or more monoliths, wherein when using a plurality of monoliths preferably a sequence and / or a juxtaposition of single or more monoliths at least in pairs adjacent monoliths is contained in the catalyst.

Thus, according to the present invention, embodiments of the catalyst for the conversion of oxygenates to olefins are preferred in which the shape of the carrier substrate is selected from the group consisting of granules, pellets, nets, rings, spheres, cylinders, hollow cylinders, monoliths and mixtures and / or combinations of two or more thereof, wherein the carrier substrate is preferably one or more monoliths.

With regard to the one or more monoliths, which are preferably present as carrier substrate in the catalyst according to the invention, in principle there is no restriction as to the shape which the one or more monoliths can assume. In the present invention, monoliths are preferred which are selected from the group consisting of honeycombs, braids, foams, and combinations of two or more thereof, more preferably, the one or more monoliths containing one or more honeycombs and / or braids. Particularly preferably according to the present invention, the one or more monoliths which are preferably used as the carrier substrate have honeycomb shape.

Thus, in accordance with the present invention, embodiments of the catalyst for the conversion of oxygenates to olefins in which the one or more monoliths are selected as the preferred carrier substrate are selected from the group consisting of honeycombs, braids, foams, and combinations of two or more thereof wherein the one or more monoliths are preferably honeycomb. According to the preferred embodiments, which contain one or more honeycomb monoliths, there are no particular restrictions on the honeycomb shape, provided that it is suitable, at least in part, for the one or more zeolites of the MFI, MEL and / or MWW zeolites. Structure type to be coated. According to particularly preferred embodiments, the honeycomb consists of a plurality of parallel running channels which are separated by the walls of the monolith, preferably the shape of the channels and / or preferably the thickness of the walls of the monolith separating the channels from each other to a certain tolerance both with regard to the shape of the channels and with regard to the wall thickness, which is usually given by the substance used for the production of the monolith or by the method of production of the honeycomb or of the honeycomb form. Thus, for example, channels are preferred which have a polygonal shape, preferably the shape of a regular polyhedron with three or more corners, preferably with three, four or six corners and more preferably with four corners. Regarding the dimensions of the channels in the preferred embodiments of the honeycomb monoliths is in principle not limited, provided that the dimensions selected at least partially coating the honeycomb monolith as the carrier substrate in the catalyst according to the invention with the one or more zeolites MFI, MEL and / or allowed by the MWW structure type.

Thus, for example, honeycomb monoliths having 62 to 186 channels per square centimeter (400 to 1,200 cpsi = cells per square inch) may be used in the present invention, with honeycomb monoliths being preferred at 78 to 171 channels per square centimeter (FIG. 500 to 1100 cpsi), more preferably those having 93 to 163 (600 to 1 .050 cpsi), more preferably those having 109 to 155 (700 to 1,000 cpsi), more preferably those having 124 to 147 (800 to 950 cpsi) and more preferably those with 132 to 144 (850 to 930 cpsi). According to particularly preferred embodiments of the present invention wherein the support substrate contains one or more honeycomb monoliths, those having 136 to 141 channels per square centimeter (880 to 910 cpsi) are used. According to alternative embodiments of the present invention, and more particularly according to preferred embodiments in which the catalyst-coated layer of the present invention further contains a binder, honeycomb monoliths having 8 to 124 channels per square centimeter (50 to 800 cpsi) are used honeycomb monoliths having from 23 to 109 channels per square centimeter (150 to 700 cpsi), more preferably those having 31 to 93 (200 to 600 cpsi), more preferably those having 39 to 85 (250 to 550 cpsi), and further preferably those with 47 to 78 (300 to 500 cpsi). According to the alternative embodiments of the present invention, embodiments according to which the one or more honeycomb-type monoliths have 54 to 70 channels per square centimeter (350 to 450 cpsi) are particularly preferred.

According to alternative embodiments of the present invention, which use one or more monoliths as a carrier substrate in the catalyst, no foam-like substrates are contained therein. Thus, embodiments of the catalyst are also preferred in which the carrier substrate contains no foams and in particular no foams as monolith.

As far as the material constituting the support substrate, and in particular the beds and / or monoliths contained therein, according to the present invention are not limited in this respect, provided it is suitable for use with the one or more zeolites of the MFI, MEL - And / or the MWW structure type to be at least partially coated. Thus, in principle, any suitable material and / or composite may be used as the substrate for the support substrate, preferably using those materials which have high temperature resistance and / or are highly inert with respect to their chemical reactivity. Thus, preference is given to using ceramic and / or metallic substances as well as composite materials of ceramic and / or metallic substances as carrier substrate in the catalyst according to the invention, preference being given to ceramic Substances are used as a carrier substrate. With respect to the preferred ceramic materials, one or more of these materials are preferably selected from the group consisting of alumina, silica, silicates, aluminosilicates, silicon carbide, cordierite, mullite, zircon, spinels, magnesia, titania, and mixtures of two or more thereof. According to particularly preferred embodiments of the present invention, the ceramic materials preferably used for the carrier substrate are selected from the group consisting of α-alumina, silicon carbide, cordierite and mixtures of two or more thereof. According to particularly preferred embodiments, the carrier substrate contains cordierite, wherein more preferably the carrier substrate is a cordierite substrate.

Thus, according to the present invention, embodiments of the catalyst for the conversion of oxygenates to olefins are preferred in which the carrier substrate ceramic and / or metallic materials, preferably ceramics, more preferably one or more substances selected from the group consisting of alumina, silica, silicates , Aluminosilicates, silicon carbide, cordierite, mullite, zircon, spinels, magnesia, titania and mixtures of two or more thereof, preferably from the group consisting of alpha alumina, silicon carbide, cordierite and mixtures of two or more thereof, wherein the support substrate particularly preferred is a cordierite substrate. With respect to the one or more zeolites contained in the catalyst, there are no limitations whatsoever on the nature or the number of zeolites which can be used herein, provided that they are zeolites of one or more of the structural types MFI, MEL and MWW. If one or more of the zeolites contained in the catalyst are of the MWW structure type, again there is no restriction on the type and / or number of MWW zeolites which can be used according to the present invention. Thus, for example, these may be selected from the group of MWW structure type zeolites consisting of MCM-22, MCM-36, [Ga-Si-O] -MWW, [Ti-Si-O] -MWW, ERB-1, ITQ-1 , PSH-3, SSZ-25 and mixtures of two or more thereof, preference being given to using MWW structure-type zeolites which are suitable for the conversion of oxygenates to olefins, in particular MCM-22 and / or MCM- 36th

The same applies correspondingly to the zeolites of the MEL structure type which can be used in the catalyst according to the present invention, these being selected, for example, from the group consisting of ZSM-1 1, [Si-B-0] -MEL, boron-D (MFI / MEL solid solution), Boralite D, SSZ-46, Silicalite 2, TS-2, and mixtures of two or more thereof. Again, those zeolites of the MEL structure type which are suitable for the conversion of oxygenates to olefins, in particular [Si-B-0] -MEL, are preferably used. However, according to the present invention, especially MFI-type zeolites are used in the catalyst of the present invention for the conversion of oxygenates to olefins. With respect to these preferred embodiments of the present invention also no restriction as to the type and / or number of zeolites used in this type of structure, wherein the one or more MFI-type zeolites used in the catalyst according to the invention are preferably selected from the group consisting of ZSM-5, ZBM-10, [As-Si-O] MFI, [Fe-Si-O] MFI, [Ga-Si-O] MFI, AMS-1 B, 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 -1 B, ZMQ-TB and mixtures of two or more thereof. More preferably according to the present invention, the catalyst contains ZSM-5 and / or ZBM-10 as an MFI-type zeolite, more preferably ZSM-5 is used as a zeolite. With regard to the zeolitic material ZBM-10 and its preparation, reference is made, for example, to EP 0 007 081 A1 and to EP 0 034 727 A2, the contents of which, in particular with regard to the preparation and characterization of the material, are included in the present invention.

Thus, according to the present invention, embodiments of the catalyst for the conversion of oxygenates to olefins are preferred in which the one or more zeolites are of the MFI structure type, and are preferably selected from the group consisting of ZSM-5, ZBM-10, As-Si-0] MFI, [Fe-Si-O] MFI, [Ga-Si-O] MFI, AMS-1 B, 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- 1 B, ZMQ-TB and mixtures of two or more thereof, more preferably from the group consisting of ZSM-5, ZBM-10, and mixtures thereof, wherein the MFI-type zeolite is preferably ZSM-5.

According to a preferred embodiment of the present invention, the catalyst does not contain significant amounts of one or more non-zeolitic materials and, in particular, no substantial amounts of one or more aluminosilicophosphates (SAPO). For the purposes of the present invention, the catalyst is substantially free of or does not contain substantial amounts of a specific material in cases where this specific material is present in an amount of 0.1% by weight or less in the catalyst relative to 100% by weight % of the total amount and the one or more MFI, MEL and / or MWW structural type zeolites, preferably in an amount of 0.05% by weight or less, more preferably 0.001% by weight or less, further preferably, 0.0005 wt% or less, and more preferably, 0.0001 wt% or less. A specific material within the meaning of the present invention particularly denotes a particular element or a particular combination of elements, a specific substance or a specific substance mixture, as well as combinations and / or mixtures of two or more thereof.

For the purposes of the present invention, the aluminosilicophosphates (SAPO) include in particular the SAPO materials SAPO-1 1, SAPO-47, SAPO-40, SAPO-43, SAPO-5, SAPO-31, SAPO-34, SAPO-37, SAPO-35, SAPO-42, SAPO-56, SAPO-18, SAPO-41, SAPO-39 and CFSAPO-1A. According to the present invention, the one or more MFI, MEL and / or MWW type zeolites contain one or more alkaline earth metals. In general, the present invention has no limitation whatsoever on the type and / or amount of alkaline earth metals contained in the one or more zeolites, nor on the manner in which they are contained in the one or more zeolites are included. Thus, the one or more zeolites may contain one or more alkaline earth metals, for example, selected from the group consisting of magnesium, calcium, strontium, barium and combinations of two or more thereof. However, in accordance with the present invention, the one or more alkaline earth metals are preferably selected from the group consisting of magnesium, calcium, strontium, and combinations of two or more thereof, and in particularly preferred embodiments of the catalyst of the present invention, the alkaline earth metal is magnesium. In accordance with alternative preferred embodiments of the present invention, the catalyst contains no or no substantial amounts of calcium and / or strontium.

Thus, according to the present invention, embodiments of the catalyst for the conversion of oxygenates to olefins are preferred in which the alkaline earth metals contained in the one or more MFI, MEL and / or MWW structural type zeolites are selected from the group consisting of Mg, Ca, Sr, Ba and combinations of two or more thereof, preferably consisting of Mg, Ca, Sr and combinations of two or more thereof, wherein the alkaline earth metal is more preferably Mg.

With regard to the manner in which the one or more alkaline earth metals are contained in the one or more zeolites of the catalyst, they may in principle be contained in the micropores of the one or more zeolites and / or as part of the zeolitic one Skeleton present, in particular at least partially in isomorphous substitution to an element of the zeolite skeleton preferably to silicon and / or aluminum as a constituent of the zeolite skeleton and particularly preferably at least partially in isomorphous substitution to aluminum. With regard to the presence of the one or more alkaline earth metals in the micropores of the one or more zeolites, these may be present there as an independent compound such as salt and / or oxide and / or as a positive counterion to the zeolite framework. According to the present invention, the one or more alkaline earth metals are present at least partially in the pores and preferably in the micropores of the one or more zeolites, more preferably wherein the one or more alkaline earth metals are at least partially present as the counterion of the zeolite framework, such as This may arise, for example, in the preparation of the one or more zeolites in the presence of the one or more alkaline earth metals and / or may be effected by carrying out an ion exchange with the one or more alkaline earth metals on the zeolite already prepared.

As already noted above, as regards the amount of one or more alkaline earth metals, there are no particular limitations to the present invention. visibly the amount in which they are present in the one or more zeolites. Thus, in principle, any amount of the one or more alkaline earth metals may be present in the one or more zeolites, such as a total amount of the one or more alkaline earth metals of from 0.1 to 20% by weight, based on the total amount of one or more several zeolites. However, in the present invention, it is preferred that the one or more alkaline earth metals be present in a total amount in the range of 0.5-15% by weight based on 100% by weight of the total amount of the one or more zeolites from 1 to 10% by weight, more preferably from 2 to 7% by weight, more preferably from 3 to 5% by weight, and even more preferably from 3.5 to 4.5% by weight. According to particularly preferred embodiments of the present invention, the one or more alkaline earth metals are present in a total amount in the range of 3.8-4.2 wt% in the one or more zeolites. In all of the above-mentioned weight percentages of alkaline earth metal in the one or more zeolites, these are calculated as starting from the one or more alkaline earth metals as metal.

Thus, in accordance with the present invention, embodiments of the catalyst for the conversion of oxygenates to olefins are preferred in which the one or more MFI, MEL and / or MWW structural type zeolites contain the one or more alkaline earth metals in a total amount in the range of zero , 1 to 20 wt .-%, preferably from 0.5 to 15 wt .-%, more preferably from 1 to 10 wt .-%, more preferably from 2 to 7 wt .-%, more preferably from 3 to 5 wt .-%, more preferably from 3.5 to 4.5 wt .-%, and more preferably in the range of 3.8 to 4.2 wt .-%, each based on the total amount of the one or more zeolites of MFI, MEL and / or MWW structure type and calculated as metal.

With regard to the components which may be present in the layer of the catalyst according to the invention applied to the substrate, there are no restrictions if the catalyst is suitable for the conversion of at least one oxygenate to at least one olefin. Thus, in certain embodiments, the layer applied to the substrate may be comprised of the one or more MFI, MEL, and / or MWW structure type zeolites containing one or more alkaline earth metals. According to further embodiments of the catalyst according to the invention, the layer applied to the substrate contains one or more further components to said zeolites. With regard to the additional components to the one or more zeolites of the MFI, MEL and / or MWW structure type, there are no restrictions, so that the layer applied to the substrate, for example, further catalytically active components, co-catalysts, fillers, vehicles and / or binders and combinations of two or more of them. According to preferred embodiments, the layer applied to the substrate further contains a binder. According to these preferred embodiments, any suitable binder may be included in the layer so that one or more additional components may be included in the applied layer which act as a binder and in particular the cohesion of the further components and in particular the one or more zeolites improve. Thus, for example, one or more components in the layer may be contained as a binder selected from the group consisting of S1O2, Al2O3, ΤΊΟ2, ZrÜ2, MgO, clay minerals and mixtures of two or more thereof, wherein according to a particularly preferred embodiment, the layer S1O2 as a binder in addition to the one or more zeolites of the MFI, MEL and / or MWW structure type.

With regard to the amount in which the one or more zeolites of the MFI, MEL and / or MWW structure type are applied to the carrier substrate in the catalyst according to the present invention, there is in principle no restriction, provided that a layer, which contains the one or more zeolites, can be formed at least partially on the carrier substrate. Thus, catalysts of the invention example ³ have the one or more zeolites of the MFI, MEL and / or the type of structure to MWW- in a total loading of 0.005-1 g / cm. In the present invention, the term "loading" means the amount of applied components of a layer in grams of dry matter per total volume of the carrier substrate, where volume refers to the volume of the coated carrier substrate, and in hollow bodies and / or cavities containing bodies and molds According to an alternative definition according to the present invention, the volume in the loading of the carrier substrate in embodiments containing fillings refers to the respective volume of the fill including the interstices and cavities contained therein According to preferred embodiments of the present invention the catalyst contains the one or more MFI, MEL and / or MWW-type zeolites in a total loading of 0.01-0.5 g / cm ^3, based on the volume of the coated carrier substrate and in particular on its Vo lumen according to the abovementioned specific and preferred definitions, more preferably in a total loading of 0.02-0.2 g / cm ³ , more preferably of 0.04-0.1 g / cm ³ , further preferably of 0.055-0, 08 g / cm ³ and more preferably 0.065-0.075 g / cm ³ . According to particularly preferred embodiments of the present invention, the catalyst contains the one or more MFI, MEL and / or MWW-type zeolites in a total loading of 0.07-0.072 g / cm ^3, based on the volume of the coated support substrate according to the particular and preferred definitions of the present application.

Thus, in accordance with the present invention, embodiments of the catalyst for the conversion of oxygenates to olefins are preferred in which the catalyst comprises the one or more zeolites of the MFI, MEL and / or MWW structure type in a total loading of 0.005 to 1 g / cm ³ based on the volume of the coated carrier substrate, preferably in a total loading of 0.01 to 0.5 g / cm ³ , more preferably from 0.02 to 0.2 g / cm ³ , more preferably from 0.04 to 0, 1 g / cm ³ , more preferably from 0.055 to 0.08 g / cm ³ , more preferably from 0.065 to 0.075 g / cm ³ , and further preferably in a total loading of from 0.07 to 0.072 g / cm ³ . According to alternative embodiments of the present invention which are more preferred, and in particular according to preferred embodiments in which the layer applied to the substrate in the catalyst according to the invention further contains a binder, the catalyst for the conversion of oxygenates to olefins contains the one or more zeolites from the MFI , MEL and / or of the MWW structure type in a total loading of 0.01 to 0.8 g / cm ³ based on the volume of the coated carrier substrate, preferably in a total loading of 0.05 to 0.5 g / cm ³ , on preferably from 0.08 to 0.3 g / cm ³ , more preferably from 0.12 to 0.25 g / cm ³ , more preferably from 0.15 to 0.23 g / cm ³ , further preferably from 0.17 to 0.21 g / cm ³ , and more preferably in a total loading of 0.18 to 0.2 g / cm ³ .

The catalyst according to the present invention may be prepared in any suitable manner, provided it contains one or more zeolites of the MFI, MEL and / or MWW structure type contained in a layer applied to a support substrate according to the present invention Invention and in particular according to one of the specific and preferred embodiments of the invention, as described in the present application.

Thus, the present invention also relates to a process for preparing a catalyst according to the present invention, and more particularly according to one of the particular or preferred embodiments thereof

Providing the carrier substrate and the one or more zeolites MFI, MEL and / or MWW structure type;

Impregnating the one or more zeolites of the MFI, MEL and / or MWW stucco type with a solution containing the one or more alkaline earth metals, preferably by means of spray impregnation;

optionally drying the one or more impregnated zeolites obtained in (ii);

optionally calcining the one or more impregnated zeolites obtained in (ii) or (iii);

(v) preparing a mixture containing the one or more impregnated and optionally dried and / or calcined zeolites of MFI, MEL and / or MWW structure type and one or more solvents;

Homogenizing the mixture obtained in (v);

Coating the carrier substrate with the homogenized mixture obtained in (vi);

(viii) optionally drying the coated support substrate obtained in (vii);

(ix) optionally calcining the coated carrier substrate obtained in (vii) or (viii). With respect to the manner of impregnation in step (ii) of the method according to the invention, the impregnation may be carried out by any suitable method, such as impregnation by impregnation, spray impregnation and / or capillary impregnation. According to particularly preferred embodiments of the method according to the invention, however, the impregnation in step (ii) is achieved by spray impregnation.

According to the inventive method for producing the catalyst according to the invention, in particular according to the specific and preferred embodiments described in the present application, there is in principle no restriction on the nature and in particular the particle sizes and / or morphologies of the one or more zeolites provided in step (i) MFI, MEL and / or MWW structure type. Depending on the particle size of the zeolites provided in step (i), however, one or more steps are optionally carried out during the process according to the invention, preferably after the impregnation in step (ii) or after the mixture has been prepared in step (v) to bring several zeolites to a preferred particle size. In this context, there is initially no particular restriction as regards the particle size of the one or more zeolites, provided that it is suitable for carrying out the further steps in the process according to the invention, in particular according to the particular and preferred embodiments of the present invention, wherein the particle size especially suitable for carrying out the coating in step (vii), in particular depending on the type and form of the carrier substrate used according to the present invention and in particular according to the particular or preferred embodiments of the carrier substrate as described in the present application. Thus, in certain embodiments of the process according to the invention, one or more steps are carried out after impregnation in step (ii) or after preparation of the mixture in step (v), preferably after preparation of the mixture in step (v) and particularly preferably in step ( vi) homogenizing the mixture obtained in (v) to obtain the one or more impregnated and optionally dried and / or calcined zeolites of the MFI, MEL and / or MWW type to a particle size D ₅ o in the range of 0, 01 to 200 μηη bring. According to further preferred embodiments of the method according to the invention, the one or more zeolites according to one or more of the aforementioned steps in one or more steps to a particle size D ₅ o in the range of 0.03 to 150 μηη, more preferably from 0.05 to 100 μηη, more preferably from 0.1 to 50 μηη, more preferably from 0.3 to 30 μηη and even more preferably brought from 0.4 to 20 μηη. According to still further preferred embodiments of the process according to the invention, the one or more impregnated and optionally dried and / or calcined zeolites are prepared after preparing the mixture in step (v) and preferably in step (vi) homogenizing the mixture obtained in (v) one or more steps to a particle size D ₅ o in the range of 0.5 to 15 μηη brought.

According to further embodiments of the method according to the invention which are preferred, and in particular according to preferred embodiments according to which a binder in the method according to the invention, one or more steps are carried out after impregnation in step (ii) or after preparation of the mixture in step (v), preferably after preparation of the mixture in step (v) and particularly preferably in step (vi) homogenizing the mixture obtained in (v) to obtain the one or more impregnated and optionally dried and / or calcined zeolites of the MFI, MEL and / or MWW structure type to a particle size Dgo in the range of 0.5 to 50 μm bring to. According to further preferred embodiments of the method according to the invention, the one or more zeolites according to one or more of the aforementioned steps in one or more steps to a particle size Dgo in the range of 1 to 30 μηη, more preferably from 3 to 20 μηη, more preferably from 5 to 15 μηη, and more preferably from 9 to 1 1 μηη brought. According to still further preferred embodiments of the process according to the invention, the one or more impregnated and optionally dried and / or calcined zeolites are prepared after preparing the mixture in step (v) and preferably in step (vi) homogenizing the mixture obtained in (v) one or more steps brought to a particle size Dgo in the range of 7 to 13 μηη.

With regard to the number of steps and the manner in which the one or more zeolites are brought to a particular or preferred particle size D ₅ o and / or Dgo, there are no restrictions according to the present invention, so that any suitable method for this purpose in principle can be used. However, in accordance with the present invention, the one or more zeolites are preferably subjected to one or more of the milling steps of one or more of steps (ii) and (v), wherein the one or more zeolites are most preferably processed through homogenization in step (vi), in particular according to the particular and preferred embodiments of the present invention, to one of the particular or preferred particle sizes D ₅ o is brought.

Thus, according to the present invention, embodiments of the method for producing a catalyst according to the present invention, and in particular a catalyst according to one of the particular or preferred embodiments thereof, are preferred, according to which after impregnation in step (ii) or after preparation of the mixture in step (v), preferably after preparing the mixture in step (v) and more preferably in step (vi) homogenizing the mixture obtained in (v) containing one or more impregnated zeolites from the MFI, MEL and / or MWW structure type to a particle size D ₅ o in the range of 0.01 to 200 μηη, more preferably from 0.03 to 150 μηη, more preferably from 0.05 to 100 μηη, more preferably from 0.1 to 50 μηη, further preferably from 0.3 to 30 μηη, more preferably from 0.4 to 20 μηη, even more preferably from 0.5 to 15 μηη are brought. Accordingly, according to the present invention, embodiments of the method for producing a catalyst, and in particular a catalyst according to one of the particular or preferred embodiments thereof, are also preferred according to which after impregnation in step (ii) or after preparation of the mixture in step (v ), preferably after preparing the mixture in step (v) and more preferably in step (vi) homogenizing the mixture obtained in (v), the one or more impregnated zeolites of the MFI, MEL and / or of the MWW structure type to a particle size D90 in the range from 0.5 to 50 μm, more preferably from 1 to 30 μηη, more preferably from 3 to 20 μηη, more preferably from 5 to 15 μηη, more preferably from 9 to 1 1 μηη, and even more preferably from 7 to 13 μηη be brought.

According to the present invention, a step of drying after step (iii) and / or (viii) is carried out in the process according to the invention. With regard to the manner in which the optional drying is achieved in one or more of these steps, in principle there is no restriction, so that the drying can be carried out at any suitable temperature and in any suitable atmosphere. Thus, the optional drying can be carried out under a protective gas atmosphere or in air, wherein the optional drying is preferably carried out in air. With respect to the temperature at which the drying takes place, for example, a temperature can be selected which is in the range of 50 to 220 ° C. According to the present invention, the optional drying after step (iii) and / or (viii) is carried out at a temperature in the range from 70 to 180 ° C, more preferably from 80 to 150 ° C, more preferably from 90 to 130 ° C and more preferably in the range of 100 to 125 ° C. According to particularly preferred embodiments of the method according to the invention, the drying after step (iii) and / or (viii) takes place at a temperature in the range of 1 10 to 120 ° C. With regard to the duration of the one or more optional drying steps, in particular according to particular and preferred embodiments of the method according to the invention, there is no particular restriction, provided that drying suitable for the further process steps can be achieved, for example after a drying step with a duration of 1 to 50 hours. According to particular embodiments of the process according to the invention, the optional drying is carried out for a period of from 5 to 40 hours, more preferably from 8 to 30 hours, more preferably from 10 to 25 hours, more preferably from 12 to 20 hours and even more preferably from 14 to 18 h.

Thus, according to the present invention, embodiments of the process for preparing a catalyst according to the present invention, and in particular a catalyst according to one of the particular or preferred embodiments thereof, are preferred according to which the drying in (iii) and / or (viii) in a Temperature in the range of 50 to 220 ° C, preferably from 70 to 180 ° C, more preferably from 80 to 150 ° C, more preferably from 90 to 130 ° C, more preferably from 100 to 125 ° C, and further preferably from 1 10 to 120 ° C takes place.

With regard to the optional steps of calcination according to the present invention, the same applies in principle as with respect to the optional steps of drying, so that there is no particular restriction here, neither in terms of temperature nor in terms of the atmosphere in which the calcination is carried out, and finally not with regard to the duration of a calcination according to the particular and preferred embodiments of the present invention, as long as the product of the calcination is an intermediate which is suitable to be processed in the further steps of the method according to the invention to a catalyst according to the present invention. Thus, for example, with respect to the temperature of the optional calcination in step (iv) and / or (ix), a temperature in the range of 300 to 850 ° C may be selected, preferably a temperature in the range of 350 to 750 ° C, more preferably of 400 to 700 ° C, more preferably from 450 to 650 ° C and even more preferably from 480 to 600 ° C is selected. According to even more preferred embodiments of the present invention, the calcination in the optional step (iv) and / or (ix) is carried out at a temperature of 500 to 550 ° C. With regard to the atmosphere in which the optional calcination is carried out according to one or more of the aforementioned steps of the process according to the invention, this may be either an inert atmosphere or air, the optional calcination in step (iv) and / or or (ix) is preferably carried out in air. Finally, there is no restriction whatsoever on the duration of the calcining step in the optional step (iv) and / or (ix) if the product of the calcination is suitable for further use, in particular as an intermediate according to the optional step (iv), in the process according to the invention for the preparation of a catalyst, in particular a catalyst according to one of the specific or preferred embodiments of the present application. Thus, the duration of calcination after one or more of the optional calcination steps in (iv) and / or (ix) may be, for example, 0.5 to 20 hours, with a duration of 1 to 15 hours being preferred, more preferably 2 to 10 hours , more preferably from 3 to 7 hours and a duration of 4 to 5 hours is particularly preferred.

Thus, according to the present invention, embodiments of the process for producing a catalyst according to the present invention, and in particular a catalyst according to one of the particular or preferred embodiments thereof, are preferred according to which the calcination in (iv) and / or (ix) in a Temperature in the range of 300 to 850 ° C, preferably from 350 to 750 ° C, more preferably from 400 to 700 ° C, more preferably from 450 to 650 ° C, more preferably from 480 to 600 ° C, and further preferably from 500 up to 550 ° C takes place.

According to step (ii) of the process according to the invention, the one or more zeolites of the MFI, MEL and / or MWW structure type are first impregnated with a solution containing one or more alkaline earth metals. According to the present invention, there is no limitation in step (ii) as regards the type and / or number of solvents used therefor. Thus, in principle any suitable solvent or solvent mixture can be used in step (ii), provided that it is suitable to bring about a corresponding impregnation of the materials defined there, in particular according to the particular and preferred embodiments of the present invention. This also applies to the one or more solvents used in step (v) for preparing the mixture defined therein, if the one or more solvents used are suitable, homogenizing in step (vi) and coating in step (vii) to enable. Thus, for example, in step (ii) and / or (v) one or more solvents, selected from the group consisting of alcohols, water, mixtures of two or more alcohols, and mixtures of water and one or more alcohols. According to preferred embodiments of the present invention, the one or more solvents used in (ii) and / or (v) are selected from the group consisting of (C 1 -C 6) -alcohols, water, mixtures of two or more (C 1 -C 6) Alcohols and mixtures of water and one or more (C 1 -C 6) -alcohols, where the one or more solvents are more preferably selected from the group consisting of (C 1 -C 4) -alcohols, water, mixtures of two or more (C 1 -C 4) -alcohols. C4) alcohols and mixtures of water and one or more (Ci-C4) alcohols. According to further preferred embodiments, the one or more solvents in steps (ii) and / or (v) are selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, water and mixtures of two or more thereof, more preferably from the group consisting of methanol, ethanol, water and mixtures of two or more thereof, wherein even more preferably the solvent is water, preferably distilled water.

Thus, according to the present invention, embodiments of the method for producing a catalyst according to the present invention, and in particular a catalyst according to one of the particular or preferred embodiments thereof, are preferred according to which the solution used in (ii) and / or that produced in (v) Mixture contains one or more solvents selected from the group consisting of alcohols, water, mixtures of two or more alcohols, and mixtures of water and one or more alcohols, preferably from the group consisting of (C1-C6) alcohols, water, mixtures of two or more (Ci-Ce) alcohols, and mixtures of water and one or more (Ci-Ce) alcohols, more preferably (C1-C4) alcohols, water, mixtures of two or more (C1-C4) alcohols, and Mixtures of water and one or more (C 1 -C 4) alcohols, more preferably consisting of methanol, ethanol, n-propanol, isopropanol, water r and mixtures of two or more thereof, more preferably consisting of methanol, ethanol, water and mixtures of two or more thereof, wherein more preferably the solvent is water, preferably distilled water.

With respect to the solid concentration of the mixture provided in (v), no particular limitation is imposed by the present invention, provided that homogenization of the mixture according to step (vi) and use of the homogenized mixture obtained in (vi) for coating in (vii) is possible. Thus, the solids concentration of the mixture provided in (v) may be, for example, in the range of 5-50% by weight, the solids concentration according to the present invention preferably in the range of 10-30% by weight and more preferably in the range of 15 -25 wt .-% is. According to particularly preferred embodiments of the method according to the invention for the preparation of a catalyst, the solids concentration of the mixture provided in (v) is in the range of 18-22% by weight. Thus, according to the present invention, embodiments of the process for producing a catalyst according to the present invention, and in particular a catalyst according to one of the particular or preferred embodiments thereof, are preferred according to which the solid concentration of the mixture prepared in (v) is in the range of 5 to 50 wt %, preferably from 10 to 30% by weight, more preferably from 15 to 25% by weight, and more preferably from 18 to 22% by weight.

According to further embodiments which are alternatively preferred, and in particular preferred embodiments according to which a binder is used in the process according to the invention, the solids concentration of the mixture provided in (v) is in the range of 10-70% by weight, the solids concentration according to the present invention preferably in the range of 20-50 wt .-% and more preferably in the range of 30-40 wt .-% is. According to particularly preferred embodiments of the method according to the invention for the preparation of a catalyst, the solids concentration of the mixture provided in (v) is in the range of 32-36% by weight.

Also, with respect to the homogenization in step (vi), there is no particular limitation on the present invention, so that any conceivable procedure can be selected to produce a homogeneous mixture of the mixture prepared in step (v) using, for example, one or more methods may be selected from the group consisting of stirring, kneading, shaking, vibration or combination of two or more thereof. According to the present invention, the mixture prepared in step (v) is preferably homogenized by stirring and / or vibration in step (vi), more preferably the homogenization in step (vi) is by vibration, preferably by ultrasound such as by using an ultrasonic bath into which the mixture to be homogenized is brought.

Thus, according to the present invention, embodiments of the process for producing a catalyst according to the present invention, and in particular a catalyst according to one of the particular or preferred embodiments thereof, are preferred according to which the homogenization in (vi) is effected by stirring, kneading, shaking, vibration or combinations of two or more thereof, preferably by stirring and / or vibration, more preferably by vibration, and more preferably by ultrasound.

With regard to the components which may be present in the mixture prepared in (v) and homogenized in (vi), there is in principle no restriction if a coated carrier substrate is obtained in (vi). Thus, in certain embodiments, the mixture produced in (v) and / or homogenized in (vi) may be one or more impregnated and optionally dried and / or calcined zeolites of the MFI, MEL and / or MWW structure type and one or more Solvent exist. According to further embodiments of the catalyst according to the invention, the mixture produced in (v) and / or homogenized in (vi) contains one or more further components to the zeolites and the solvent. With regard to the additional components which in the (v) There may be no restrictions whatsoever so that the mixture in (v) and / or (vi) contains, for example, further catalytic components, co-catalysts, fillers, auxiliaries, vehicles, binders and combinations of may contain two or more of them. According to particularly preferred embodiments, the mixture in (v) and / or in (vi) contains a binder, wherein the binder may contain one or more substances. In principle, the binder can be added to the mixture in

(v) to the mixture in (vi), or both to the mixture in (v) and to the mixture in

(vi) are added, wherein according to preferred embodiments, the binder is added to the mixture in (vi).

In principle, according to the preferred embodiments in which the binder in (vi) is added, this may be added either before homogenizing the mixture or at any time during homogenization, as long as a homogenized mixture is obtained in (vi). With regard to preferred embodiments in which the one or more zeolites in step (vi) are brought to a specific D ₅ o and / or D90 particle size, embodiments are particularly preferred in which the addition of one or more further components to the zeolites and the solvent , And in particular in which the addition of an aid takes place, takes place only after the adjustment of the particle size.

With regard to the binders which are optionally added in the process, there are no limitations, so that in principle any substance suitable for this purpose and any suitable substance mixture can be used, provided this leads to the desired increase in the cohesion of the layer in the coated carrier substrate. Thus, for example, according to the present invention, S1O2, Al2O3, T1O2, ZrO2, MgO, clay minerals, and mixtures of two or more thereof, as well as their respective precursor compounds and mixtures of two or more thereof, as well as mixtures of two or more of the former with two or more the precursor compounds thereof are used as binders in the process according to the invention.

For example, clay minerals and naturally occurring or synthetic aluminas, such as alpha, beta, gamma, delta, eta, kappa, chi or theta alumina, and their inorganic and / or metalorganic precursor compounds can be used as the Al 2 O 3 binder and its precursor compounds such as gibbsite, bayerite, boehmite, pseudoboehmite, or trialkoxyaluminates such as aluminum triisopropylate.

Other binders that can be used in the process are montmorillonite, kaolin, bentonite, halloysite, dickite, or nacrite.

Preferred binders contain S1O2 and / or one or more of their precursor bonds, particularly preferably S1O2, preference being given to using colloidal S1O2. According to embodiments which are more preferred, colloidal S1O2 is added as a binder in (v) and / or (vi) and preferably in (vi). With respect to the concentration of the binder in the homogenized mixture obtained in (vi), there are no limitations, so that in principle any suitable amount of binder can be used, as long as the resulting catalyst can be used for the reaction of at least one oxygenate to at least one olefin. Thus, for example, the binder may be present in an amount of from 0.1 to 50% by weight in (v) and / or (vi) and preferably in (vi) based on the total solids content of the homogenized mixture obtained in (vi). According to further preferred embodiments, from 0.5 to 35% by weight of binder in (v) and / or (vi) and preferably in (vi) is added based on the total solids content of the homogenized mixture obtained in (vi), more preferably from From 1 to 30% by weight, more preferably from 5 to 25% by weight, more preferably from 7 to 20% by weight, more preferably from 9 to 17% by weight, more preferably from 10 to 15% by weight. %, and more preferably from 1 1 to 13% by weight. With regard to the coating of the carrier substrate in step (vii) of the method according to the invention, in principle there is no restriction as regards its implementation, provided that a corresponding layer is at least partially formed on the carrier substrate. Thus, any suitable form of coating may be employed in the process of the present invention for preparing the catalyst of the present invention, wherein the coating in step (vii) is preferably by spray coating and / or wash coating. According to particularly preferred embodiments of the method according to the invention, the coating in step (vii) is carried out by washcoating, the washcoating preferably taking place by dip coating. Such a preferred dip coating is carried out, for example, by immersing the carrier substrate one or more times in the mixture prepared in step (v) and homogenized in step (vi), wherein according to the present invention, the dip coating is preferably followed by a treatment to remove excess mixture from the carrier substrate. In preferred embodiments of dip-coating in which the substrate is immersed several times in the mixture prepared in step (v) and homogenized in step (vi), the further preferred treatment for removing excess mixture may, in principle, be after repeated dipping and / or between two or more dipping steps, wherein preferably after each step of the immersion excess mixture is removed by a suitable treatment from the coated carrier substrate. More preferably, however, according to the present invention, a step of immersion is carried out in the mixture prepared in step (v) and homogenized in step (vi), followed by a corresponding treatment for removing excess mixture. As for the particularly preferable removal of excess mixture according to the particular embodiments of the present method in which dip coating is carried out in step (vii), there is basically no limitation on the manner in which excess mixture is removed. Thus, removal may be achieved, for example, by appropriately suspending and / or leaving the coated support substrate and / or directly or indirectly by mechanical or other means, such as mechanical Stripping and / or by removal with a suitable gas blower and / or by appropriate application of centripetal forces, such as by suitably directed centrifugal forces. However, according to the present invention, it is particularly preferred to remove the removal of excess mixture by a gas blower, more preferably by means of compressed air, by suitable blowing out of the excess mixture.

Thus, according to the present invention, preferred are embodiments of the process for producing a catalyst according to the present invention, and in particular a catalyst according to one of the particular or preferred embodiments thereof according to which coating in (vii) by spray coating and / or wash coating by washcoating, wherein the washcoating is preferably carried out by dip coating, which is preferably followed by a treatment to remove excess mixture, wherein the removal of excess mixture preferably takes place at least partially with compressed air.

In accordance with the method according to the invention, in principle it is possible according to the present invention to provide the carrier substrate with several layers of the same and / or different composition, in particular with respect to the one or more zeolites of MFI, MEL and / or MWW structure type. Thus, embodiments of the inventive method for producing a catalyst according to the present invention are preferred in which step (vii) is repeated one or more times, preferably step (viii) and / or step (ix) and preferably both step (viii) and Step (ix) between repetitions. In such preferred embodiments of the method according to the invention, in which two or more layers of different composition, in particular with respect to the one or more zeolites, are applied to the carrier substrate, the steps (v) and (vi) are also correspondingly repeated in the preparation of the different compositions of the invention Mixture in step (v), which may refer not only to the chemical composition, but also to other properties of the mixture, such as the average particle size and / or the optional drying and / or the optional calcination of one or the several zeolites of MFI, MEL and / or MWW structure type. The differences in the mixtures prepared in step (v) for producing the different layers on the carrier substrate according to these preferred embodiments also relate to the impregnation of the MFI, MEL and / or MWW structure type zeolites in step ( ii) the process of the invention and / or optional drying and / or optional calcining, as well as the manner of impregnation in step (ii) and / or drying in step (iii) and / or calcination in step (iv), according to these embodiments, the steps (ii) and optionally (iii) and / or (iv) are repeated accordingly. According to particularly preferred embodiments of the method according to the invention, steps (vii) and (viii) and / or (ix) preferably steps (vii) - (ix) are repeated one or more times in order to coat the carrier several times. gersubstrats with a prepared in step (v) and in step (vi) homogenized mixture.

With regard to the number of repetitions, which are carried out according to the preferred embodiments of the method according to the invention for the preparation of a catalyst according to the present invention, there is no restriction in principle, wherein the steps in the repetitions according to the particular and preferred embodiments of the method according to the invention are preferably repeated once to five times, more preferably once to four times, more preferably once to three times and more preferably once or twice.

Thus, according to the present invention, embodiments of the process for producing a catalyst according to the present invention, and in particular a catalyst according to one of the particular or preferred embodiments thereof, are preferred according to which step (vii) is repeated one or more times, preferably the steps ( vii) and (viii), more preferably steps (vii) to (ix), wherein the steps are preferably repeated once to five times, more preferably once to four times, more preferably once to three times, more preferably once or twice, and most preferably repeated twice. With regard to the temperature at which the coated carrier substrate obtained in (vii) in (viii) dried and the duration of drying is in principle no restriction. For example, the optional drying in (viii) may be at a temperature in the range of 50 to 220 ° C, preferably drying at a temperature in the range of 80 to 200 ° C, more preferably in the range of 100 to 180 ° C , more preferably in the range of 1 10 to 170 ° C, more preferably in the range of 120 to 160 ° C, more preferably in the range of 130 to 150 ° C, and more preferably in the range of 135 to 145 ° C. There is also no restriction on the duration of the drying so that it can be carried out, for example, for a period of 0.1 to 5 h, wherein the drying in step (viii) is preferably carried out for a period of 0.2 to 2 h, more preferably from 0.3 to 1.5 h, more preferably from 0.4 to 1.2 h, more preferably from 0.5 to 1 h, further preferably from 0.6 to 0.9 h, and further preferably from 0.7 to 0.8 h.

With regard to the temperature at which the coated carrier substrate obtained in (vii) or (viii) is calcined in (ix) and the duration of the calcination, in principle there is no restriction whatsoever. Thus, the optional calcination in (ix) can be carried out, for example, at a temperature in the range from 250 to 1 .100 ° C., the calcination preferably taking place at a temperature in the range from 350 to 900 ° C., more preferably in the range from 400 to 800 ° C, more preferably in the range of 450 to 750 ° C, more preferably in the range of 500 to 700 ° C, more preferably in the range of 550 to 650 ° C, and more preferably in the range of 580 to 600 ° C. There is also no restriction on the duration of the calcination, so that it can be carried out, for example, for a period of 0.5 to 20 h, wherein the calcination in step (ix) is preferably carried out for a period of 0.75 to 15 h, further from 1 to 10 h, more preferably from 1.5 to 5 h, more preferably from 2 to 4 h, more preferably from 2.5 to 3.5 h, and more preferably from 2.8 to 3.2 h.

According to particularly preferred embodiments of the process according to the invention, the coated substrate obtained in (vii) is both dried and subsequently calcined.

In addition to a catalyst for the conversion of oxygenates to olefins according to the present invention as described in the present application, and in particular according to the particular and preferred embodiments thereof, the present invention also relates to such catalysts for the conversion of oxygenates to olefins, which are obtainable according to the manufacturing method of the invention , d. H. also catalysts per se, which can be obtained, for example, according to the manufacturing method according to the invention, without having to be prepared by this method. In particular, the present invention thus relates to catalysts for the conversion of oxygenates to olefins which can be obtained according to the process of the invention, in particular according to the particular and preferred embodiments described in the present application, but which can or have been prepared by another suitable process , Thus, according to the present invention, embodiments of the catalyst for the conversion of oxygenates to olefins are preferred in which the catalyst, and in particular the catalyst according to one of the particular or preferred embodiments of the present invention, is obtainable by the process according to the invention for the preparation of a catalyst according to one of the particular or preferred embodiments of the method according to the invention.

In addition to a catalyst for the conversion of oxygenates to olefins and a process for the preparation of such a catalyst, the present invention also relates to a process for the conversion of oxygenates to olefins. In particular, the present invention relates to such a method comprising:

(1) providing a gas stream containing one or more oxygenates;

(2) contacting the gas stream with a catalyst according to the present invention.

With regard to the catalyst, which can be used in the process according to the invention for the conversion of oxygenates to olefins, there is in principle no restriction, provided that it is a catalyst according to the present invention, as it is also obtainable by the process according to the invention, and if this catalyst is suitable for the conversion of at least one oxygenate to at least one olefin. This applies in particular to the embodiments of the catalyst according to the invention according to the particularly preferred embodiments of the present invention. The same applies correspondingly to the one or more oxygenates contained in the gas stream according to (1), so that according to the process according to the invention there is in principle no restriction whatsoever if the one or more oxygenates which are present in the Gas stream according to (1) can be converted from one of the catalysts according to the present invention and in particular according to their particular and preferred embodiments to at least one olefin in the contacting according to (2). However, in the present invention, it is preferred that the one or more oxygenates contained in the gas stream of (1) are selected from the group consisting of aliphatic alcohols, ethers, carbonyl compounds and mixtures of two or more thereof. More preferably, the one or more oxygenates is selected from the group consisting of (Ci-C6) alcohols, di (Ci-C3) alkyl ethers, (Ci-Ce) -Aldehyden, (C2-Ce) -Ketonen and mixtures of two or more thereof, more preferably consisting of (C 1 -C ₄ ) -alcohols, di- (C 1 -C 2) -alkyl ethers, (C 1 -C ₄ ) -aldehydes, (C ₂ -C ₄ ) -ketones and mixtures of two or more thereof. According to even more preferred embodiments of the present invention, the gas stream according to (1) contains one or more oxygenates selected from the group consisting of 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 wherein the one or more oxygenates are selected from the group consisting of methanol, ethanol, dimethyl ether, diethyl ether, ethyl methyl ether and mixtures of two or more thereof. According to particularly preferred embodiments of the process according to the invention for the conversion of oxygenates to olefins, the gas stream according to (1) contains methanol and / or dimethyl ether as the one or more oxygenates, with dimethyl ether being particularly preferably the oxygenate contained in the gas stream according to (1).

Thus, in accordance with the present invention, embodiments of the process for converting oxygenates to olefins are preferred in which the gas stream of (1) contains one or more oxygenates selected from the group consisting of aliphatic alcohols, ethers, carbonyl compounds and mixtures of two or more thereof , preferably consisting ethers from (Ci-C ₆₎ alcohols, di- (Ci-C ₃₎ _(Ci-C6) aldehydes, (C ₂ -C ₆₎ keto NEN, and mixtures of two or more thereof, more preferably consisting of (C 1 -C 4) alcohols, di (C 1 -C 2) alkyl ethers, (C 1 -C 4) aldehydes, (C 2 -C 4) ketones and mixtures of two or more thereof, more preferably from the group consisting of 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 from the group consisting of methanol, ethanol, dimethyl ether, diethyl ether, ethyl methyl ether and mixtures of two or more thereof, the gas stream more preferably containing methanol and / or dimethyl ether, and more preferably dimethyl ether.

On the other hand, as regards the content of oxygenates in the gas stream according to (1) in the process according to the invention for the conversion of oxygenates to olefins, according to the present invention Here again, there is no restriction whatsoever on the invention of the invention, provided that at least one oxygenate can be converted to at least one olefin when contacting the gas stream in (2) with a catalyst according to the present invention. According to preferred embodiments, the content of oxygenates in the gas stream according to (1) in the range of 30 to 100 vol.% Based on the total volume, wherein the content in particular to a gas stream at a temperature in the range of 200 to 700 ° C and at a pressure of 101, 3 kPa, preferably at a temperature in the range from 250 to 650 ° C, more preferably from 300 to 600 ° C, more preferably from 350 to 560 ° C, more preferably from 400 to 540 ° C, more preferably from 430 to 520 ° C, and more preferably in the range from 450 to 500 ° C and at a pressure of 101, 3 kPa. According to the present invention, it is further preferable that the content of oxygenates in the gas stream of (1) is in the range of 30 to 99% by volume, more preferably 30 to 95% by volume, further preferably 30 to 90% by volume %, more preferably from 30 to 80% by volume, more preferably from 30 to 70% by volume, further preferably from 30 to 60% by volume and more preferably from 30 to 50% by volume. According to particularly preferred embodiments of the process according to the invention for the conversion of oxygenates to olefins, the content of oxygenates in the gas stream according to (1) is in the range from 30 to 45% by volume.

Thus, according to the present invention, embodiments of the process for converting oxygenates to olefins are preferred in which the content of oxygenates in the gas stream according to (1) is in the range from 30 to 100% by volume, based on the total volume From 30 to 99% by volume, more preferably from 30 to 95% by volume, more preferably from 30 to 90% by volume, more preferably from 30 to 80% by volume, further preferably from 30 to 70% by volume %, more preferably from 30 to 60% by volume, more preferably from 30 to 50% by volume, and further preferably from 30 to 45% by volume.

With regard to the other components in the gas stream according to (1) in the process according to the invention, there is in principle no restriction, provided that the gas stream is altogether suitable for converting at least one of the oxygenates to at least one olefin in step (2) when brought into contact with a catalyst according to the present invention , Further, for example, besides the one or more oxygenates in the gas stream according to (1), one or more inert gases may be contained therein, such as one or more noble gases, nitrogen, water and mixtures of two or more thereof. According to particular embodiments of the present invention, the gas stream according to (1) of the process according to the invention contains water in addition to the one or more oxygenates.

With regard to those preferred embodiments in which, in addition to the one or more oxygenates, water is contained in the gas stream according to (1), in principle there is no restriction with regard to the content of water which may be contained therein, provided that the conversion of at least one oxygenate in the Gas stream to at least one olefin in step (2) of contacting the gas stream with a catalyst according to the present invention Invention can take place. However, according to these preferred embodiments, it is preferable that the content of water in the gas stream is in the range of 5 to 60% by volume based on the total volume, and the content of water is more preferably in the range of 10 to 55% by volume. is more preferably from 20 to 50 vol .-% and more preferably from 30 to 45 vol .-%.

Thus, according to the present invention, preferred are embodiments of the process for converting oxygenates to olefins in which water is contained in the gas stream according to (1), preferably in the range of 5 to 60% by volume based on the total volume from 10 to 55% by volume, more preferably from 20 to 50% by volume, and more preferably from 30 to 45% by volume.

According to particularly preferred embodiments of the process according to the invention for the conversion of oxygenates to olefins, the gas stream provided in (1) originates from a pre-reaction, preferably from the conversion of one or more alcohols to one or more ethers, in particular from the conversion of one or more alcohols from the group consisting of methanol, ethanol, n-propanol, isopropanol and mixtures of two or more thereof, more preferably from the group consisting of methanol, ethanol, n-propanol and mixtures of two or more thereof, particularly preferably the in (1) provided gas stream of a pre-reaction of methanol and / or ethanol and more preferably methanol is at least partially converted to one or more di (Ci- C2) alkyl ethers, preferably to one or more di (Ci-C2) alkyl ethers selected from the group consisting of dimethyl ether, diethyl ether, ethyl methyl ether and mixtures of two or more of that. Thus, according to a particularly preferred embodiment, the gas stream provided in (1) originates from a preliminary reaction of the conversion of methanol to dimethyl ether.

In the particularly preferred embodiments of the process according to the invention, in which the gas stream provided in (1) originates from a preliminary reaction of one or more alcohols, there is in principle no particular restriction with regard to the reaction and thus the reaction product of the conversion of one or more alcohols, provided this results in a gas stream containing one or more oxygenates which, when contacted in (2) with a catalyst according to the present invention, allows the conversion of at least one of the oxygenates to at least one olefin. According to these particular embodiments, it is further preferred that the pre-reaction leads to the conversion of at least one alcohol to at least one ether and in particular to at least one dialkyl ether, wherein the pre-reaction is particularly preferably a dehydration in which water is the co-product one or more dialkyl ethers is obtained. According to the particular and preferred embodiments of the present invention, in which the gas stream provided in (1) originates from a pre-reaction, it is particularly preferred in accordance with the method according to the invention that one of such a pre-reaction tion gas stream is fed directly and without processing the process of the invention in step (1).

With regard to the manner in which the gas stream is brought into contact with a catalyst of the present invention in step (2) of the process according to the invention for the conversion of oxygenates to olefins, there is in principle no restriction provided that the conversion of at least one oxygenate to at least one olefin can be realized , This applies, for example, to the temperature at which contacting (2) takes place. Thus, for example, the contacting in step (2) of the process according to the invention may take place at a temperature in the range from 200 to 700 ° C., preferably temperatures in the range from 250 to 650 ° C., more preferably from 300 to 600 ° C., more preferably from 350 to 560 ° C, more preferably from 400 to 540 ° C and more preferably from 430 to 520 ° C are selected. According to particularly preferred embodiments of the present invention, the contacting according to (2) of the inventive method is carried out at a temperature in the range of 450 to 500 ° C.

Thus, according to the present invention, embodiments of the process for converting oxygenates to olefins are preferred in which the contacting according to (2) at a temperature in the range from 200 to 700 ° C, preferably from 250 to 650 ° C, more preferably from 300 to 600 ° C, more preferably from 350 to 560 ° C, more preferably from 400 to 540 ° C, more preferably from 430 to 520 ° C, and more preferably from 450 to 500 ° C.

The same applies correspondingly to the pressure at which the gas stream in step (2) of the process according to the invention is brought into contact with the catalyst according to the present invention. Thus, contacting may in principle take place at any pressure, provided that it permits the conversion of at least one oxygenate to at least one olefin by contacting the gas flow with the catalyst. Thus, the pressure, for example, when contacting in step (2) in the range of 0, 1 to 10 bar, the pressure in the present application indicates the absolute pressure, so that a pressure of 1 bar when contacting corresponding to the normal pressure of 1, 03 kPa corresponds. According to the present invention, the contacting in step (2) preferably takes place at a pressure of 0.3 to 7 bar, more preferably from 0.5 to 5 bar, more preferably from 0.7 to 3 bar, further preferably from 0.8 to 2.5 bar and more preferably from 0.9 to 2.2 bar instead. According to particularly preferred embodiments of the process according to the invention for the conversion of oxygenates to olefins, the contacting takes place in step (2) at a pressure of 1 to 2 bar.

Thus, according to the present invention, embodiments of the process for the conversion of oxygenates to olefins are preferred in which the contacting according to (2) at a pressure in the range of 0.1 to 10 bar, preferably from 0.3 to 7 bar, more preferably from 0.5 to 5 bar, more preferably from 0.7 to 3 bar, more preferably from 0.8 to 2.5 bar, more preferably from 0.9 to 2.2 bar, and more preferably from 1 to 2 bar , Furthermore, there are no particular limitations on the mode of carrying out the process according to the invention for the conversion of oxygenates to olefins, so that both a continuous and a non-continuous process can be used, wherein the non-continuous process can be carried out for example in the form of a batch process. According to the present invention, however, it is preferred to carry out the process according to the invention for the conversion of oxygenates as a continuous process. Thus, in accordance with the present invention, embodiments of the process for converting oxygenates to olefins are preferred in which the process is a continuous process.

With respect to these preferred embodiments of a continuous process, there are no limitations on the chosen space velocity, provided that the conversion of an oxygenate to an olefin can occur. Thus, for example, space velocities in the contacting in step (2) can be selected which are in the range of 0.5 to 50 hr ^1, wherein preferred space velocities (WHSV = weight hourly space yelocity is defined as the ratio of oxygenates-reactant stream in kg / h to the amount calculated from zeolite in the reactor in kg) from 1 to 30 hr ¹ , more preferably from 3 to 25 hr ¹ , more preferably from 5 to 20 hr ¹ , even more preferably from 7 to 15 hr ¹ and more preferably from 8 to 12 hr ¹ . According to particularly preferred embodiments of the process according to the invention for the conversion of oxygenates, space velocities for contacting the gas stream in step (2) are chosen in the range from 9 to 11 hr ^-1 . According to alternative embodiments of the continuous process, and in particular according to preferred embodiments according to which in the catalyst the layer applied to the substrate further contains a binder, space velocities in contacting in step (2) can be chosen which range from 0.1 to 20 hr ^-1 space velocities of 0.5 to 15 hr ¹ are preferably selected, more preferably from 1 to 10 hr ¹ , more preferably from 1.5 to 8 hr ¹ , more preferably from 2 to 7 hr ¹ , further preferably from 2, 5 to 6 hr ¹ , more preferably from 3 to 5 hr ¹ , and more preferably from 3.5 to 4.5 hr ¹ .

Thus, according to the present invention, embodiments of the process for converting oxygenates to olefins are preferred in which the space velocity in contacting in (2) is in the range of 0.5 to 50 hr ¹ , preferably 1 to 30 hr ¹ , more preferably 3 is up to 25 hr ^1, more preferably 5 to 20 hr ^1, more preferably 7-15 hr ^1, more preferably 8 to 12 hr ^1, and more preferably from 9 to 1 1 hr. ¹ Accordingly, in accordance with the present invention, embodiments of the process for converting oxygenates to olefins are also preferred in which the space velocity in contacting in step (2) is in the range from 0.1 to 20 hr ¹ , preferably from 0.5 to 15 hr ¹ , more preferably from 1 to 10 hr ¹ , more preferably from 1.5 to 8 hr ¹ , more preferably from 2 to 7 hr ¹ , even more preferably from 2.5 to 6 hr ¹ , more preferably from 3 to 5 hr ¹ , and more preferably from 3.5 to 4.5 hr ¹ . As described above and in the examples of the present application, in a process for the conversion of oxygenates as described in the present application, particularly long service lives can be achieved with the catalyst according to the invention, in particular with regard to the particular and preferred embodiments of the process according to the invention. Thus, it has surprisingly been found that by using a catalyst according to the present invention, the service life of the catalyst to which the catalyst regeneration process must be stopped, at least with respect to the use of this catalyst charge over the prior art catalysts, is considerable can be increased. Thus, in accordance with the present invention, it is particularly preferred to choose for the implementation of the process for the conversion of oxygenates to olefins at one of the particular or preferred space velocities, as described in the present application, long service lives. Thus, lifetimes are preferred which are in the range of 15 to 400 h, more preferably in the range of 20 to 300 h, more preferably from 60 to 250 h, more preferably from 90 to 220 h, more preferably from 1 10 to 200 h, more preferably from 130 to 180 hours, more preferably from 150 to 170 hours and more preferably from 155 to 165 hours. In particular, based on the particular and preferred space velocities at which the erfindungsge- MAESSEN method is performed prior speeds of 15 to 400 hours at a space velocity in the range of 0.5 to 50 h ^-1 are preferred Thus, for example. Further preferred is a service life of 20 to 300 h at a space velocity of 1 to 30 hr ¹ , more preferably a service life of 60 to 250 h at a space velocity of 1 to 30 hr ¹ , more preferably a service life of 90 to 220 h at a Space velocity of 3 to 25 hr ¹ , more preferably a service life of 1 10 to 200 h at a space velocity in the range of 5 to 20 hr ¹ , more preferably a service life of 130 to 180 h at a space velocity in the range of 7 to 15 hr ¹ and more preferably from 150 to 170 h at a space velocity of 8 to 12 hl ^-1 . According to a particularly preferred embodiment of the inventive method, a life of the catalyst is selected during the continuous Liehe process is carried out without interruption, which is in the range of 155 to 165 H at a room rate of 9 to 1 1 hr. ¹

According to alternative embodiments of the present invention, and in particular according to preferred embodiments according to which in the catalyst the layer applied to the substrate further contains a binder, residence times are preferred which are in the range of 5 to 800 h, more preferably in the range of 10 to 600 h more preferably in the range of 30 to 550 hours, more preferably in the range of 50 to 500 hours, more preferably in the range of 70 to 450 hours, more preferably in the range of 80 to 420 hours, more preferably in the range from 90 to 400 hours, and more preferably in the range of 100 to 380 hours. In particular, based on the particular and preferred space velocities at which the method according to the invention is carried out according to alternative embodiments, and in particular according to preferred embodiments thereof In the catalyst, for example, if the layer applied to the substrate further contains a binder, service lives of, for example, 5 to 800 hours at a space velocity in the range from 0.1 to 20 hr.sup.- ^{1 are} preferred. Further preferred is a service life of 10 to 600 h at a space velocity of 0.5 to 15 hr ¹ , more preferably a service life of 30 to 550 h at a space velocity of 1 to 10 hr ¹ , more preferably a service life of 50 to 500 h at a space velocity of 1.5 to 8 hr ¹ , more preferably a service life of 70 to 450 h at a space velocity of 2 to 7 hr ¹ , more preferably a service life of 80 to 420 h at a space velocity of 2.5 to 6 hr ¹ , more preferably a service life of 90 to 400 h at a space velocity of 3 to 5 hr ¹ , and more preferably a service life of 100 to 380 h at a space velocity of 3.5 to 4.5 hr. ¹

According to the present invention, the particular and preferred embodiments, with regard to the selected service life and in particular the selected service lives in combination with certain space velocities, preferably relate to a minimum conversion of the one or more oxygenates contained in the gas stream according to (1) of the method according to the invention whose permanent drop below the regeneration of the catalyst is subsequently carried out. According to the present invention, there is no particular restriction on the selected minimum conversion, which preferably allows full conversion of the one or more oxygenates contained in the gas stream according to (1) of the process according to the invention during the service life of the catalyst. Thus, in accordance with preferred embodiments of the present invention, a minimum conversion of 60% of the one or more oxygenates contained in the gas stream according to (1) of the process according to the invention is selected, at whose permanent underrun the regeneration of the catalyst is carried out, preferably a minimum conversion of 70% or more, more preferably 80% or more, further preferably 85% or more, still more preferably 90% or more, still more preferably 95% or more, still more preferably 97% or more, still more preferably 98% or more, and more preferably 99% or more, of the one or more oxygenates contained in the gas stream according to (1) of the process of the invention.

Thus, according to the present invention, embodiments of the process for the conversion of oxygenates to olefins are further preferred in which the service life of the coated carrier substrate as a catalyst, during which the continuous process is carried out without interruption, in the range of 15 to 400 h, preferably from 20 to 300 h, more preferably from 60 to 250 h, more preferably from 90 to 220 h, more preferably from 110 to 200 h, more preferably from 130 to 180 h, more preferably from 150 to 170 h, and still more preferably from 155 up to 165 h.

Furthermore, the present invention also relates to the use of the catalyst according to the invention as described above, and in particular the use of the catalyst according to the invention according to the particular and preferred embodiments as described in the present application. According to the present invention, in principle, there is no Restriction on the use of the catalyst according to the invention, so that it can be used both for the conversion of oxygenates to olefins and in any conceivable catalytic process in which the catalyst exhibits a corresponding catalytic effect with respect to a chemical reaction. However, according to the present invention, the catalyst according to the invention is preferably used in a methanol-to-olefin process (MTO process) and furthermore preferably in a methanol-to-gasoline process (MTG process), in a methanol-to-methanol process. Hydrocarbon process, in a methanol-to-propylene process (MTP process), in a methanol-to-propylene / butylene process (MT3 / 4 process) and for the alkylation of aromatics or in a fluid catalytic - Cracking method (FCC method). However, in the present invention, the catalyst of the present invention is preferably used in a methanol-to-olefin (MTO) process, more preferably in a methanol-to-propylene / butylene process (MT3 / 4 process), especially in a process for the conversion of oxygenates to olefins according to one of the particular or preferred processes for the conversion of oxygenates to olefins according to the present invention.

EXAMPLES Comparative Example 1: Preparation of an extrudate containing H-ZSM-5

380 g of H-ZSM-5 (ZEO-cat PZ2-100 H from Zeochem) with Si / Al = 50 were mixed with 329 g of pseudoboehmite (Pural SB, Sasol), treated with 10 g of formic acid in 50 ml of water and processed with 300 ml of water in a kneader to a homogeneous mass. The initial weight was chosen such that the zeolite / binder ratio in the calcined extrudates corresponds to 60:40. This putty was pushed with the aid of an extruder at about 100 bar through a 2.5 mm die. The strands were anschießend 16 h at 120 ° C in a drying oven dried and calcined (after 4 h heating) for 4 h at 500 ° C in a muffle furnace. Thereafter, the strands were processed in a screening machine with 2 steel balls (diameter about 2 cm, 258 g / ball) to 1, 6- 2.0 mm grit.

Comparative Example 2 Preparation of H-ZSM-5 Coated Carrier (Load: 71 g / L)

An aqueous suspension having a solids concentration of 40% by weight of H-ZSM-5 zeolite (ZEO-cat PZ2-100 H from Zeochem) with Si / Al = 50 was prepared and homogenized in an ultrasound bath. Cordierite cylindrical honeycomb pieces (900 cpsi, diameter 0.9 cm, length = 1 1 cm) were immersed in this suspension and then blown out with compressed air. The coated supports were then dried for 1 h at 110 ° C and then calcined for 3 h at 550 ° C. The coating step was repeated until a loading of 0.5 g of zeolite per honeycomb body (0.071 g / cm ³ ) was achieved, with the amount of suspension applied being given in grams of dry matter per liter of total body volume. Example 1: Preparation of Mg-ZSM-5 Coated Carrier (Load: 71 g / L)

H-ZSM-5 (ZEO-cat PZ2-100H from Zeochem) with Si / Al = 50 powder was spray-impregnated with an amount of magnesium nitrate solution corresponding to 90% of its water-uptake capacity. The amount of Mg was weighed so that the powder after calcination contains 4% by weight of Mg. For impregnation, 58.7 g of zeolite powder were placed in a round bottom flask and placed in a rotary evaporator. 43.9 g of magnesium nitrate were dissolved in water with heating, and with dist. Water is made up to 54 ml of total fluid. The resulting magnesium nitrate solution was charged into a dropping funnel and slowly sprayed onto the powder while rotating through a glass spray nozzle flooded with 100 l / h of N 2. At regular intervals, the piston was suspended and shaken by hand to achieve an even distribution. After complete addition of the magnesium nitrate solution, the powder was 10 min. continues to rotate. The powder was then dried for 16 hours at 120 ° C. in a quartz rotary flask, then calcined for 5 hours at 500 ° C. under air (20 L / h), and then the calcined powder was ground to a small size by means of an analytical mill and through a sieve with a mesh size of Sieved 1 mm.

The BET surface area of the obtained magnesium-impregnated zeolite was 303 m ² / g.

elemental analysis:

Mg: 4g / 100g

The spray-impregnated Mg-ZSM-5 powder was applied to honeycomb pieces according to Comparative Example 2, wherein the solid concentration of the aqueous suspension of Mg-ZSM-5 used therefor was 20% by weight. The coating step was repeated according to Comparative Example 2 until a loading of 0.5 g of Mg-ZSM-5 per honeycomb body piece (0.071 g / cm ³ ) was achieved. [Example 2: Preparation of Mg-ZSM-5 coated carrier (load: -85 g / L)

Distilled water was placed in a container with a propeller mixer. With continuous stirring and speed adjustment, Mg-ZSM-5 powder prepared according to Example 1 was slowly added until a solids content of 33% by weight was reached. Subsequently, the grinding of the Mg-ZSM-5 starting suspension was carried out in a stirred ball mill to a particle size D90 of 10μηη. The temperature during grinding did not exceed 30 ° C. After milling, Ludox AS-40 was added as a binder. The solids content of the binder was in total 12% by weight, based on the total solids content of the final suspension.

To prepare the carrier substrate, the suspension was applied to a honeycomb body (cordierite honeycomb body with a cell density of 400 cpsi (62 cells / cm ² ) and a wall thickness of 6). 7 mil (152.4 μηι - 177.8 μηι)) applied. For this, the suspension was diluted to a solids content of 28%. The catalyst was immersed in the suspension over the full height so that all cells were completely filled. After waiting for 10 seconds, the substrate was withdrawn from the suspension, inverted, and freed of excess suspension with inlet side to outlet side compressed air.

Subsequently, the catalyst was dried in a dryer by means of hot air (140 ° C) alternately from both sides with a respective cycle time of 10 seconds for a total of 45 minutes. Thereafter, the catalyst was calcined in the continuous calciner at a maximum temperature of 590 ° C, during which process the catalyst underwent three warm-up, holding and cooling zones within three hours.

The loading of the carrier substrate was calculated by mass balance to 0.085 g / cm ³ . [Example 3: Preparation of Mg-ZSM-5 coated carrier (load: -150 g / L)

The preparation procedure according to Example 2 was repeated, wherein the carrier substrate was coated twice. For this purpose, the suspension was first diluted to a solids content of 26% with distilled water, and the catalyst was coated with this according to Example 2, and then thermally fixed the layer. The suspension was then further diluted to a solids content of 25%, and the process of coating and thermal fixation according to Example 2 was repeated with this suspension, whereby a loading of the carrier substrate of 0.15 g / cm ^{3 was} achieved. [Example 4: Preparation of Mg-ZSM-5 coated carrier (load: -190 g / L)

The preparation procedure according to Example 2 was repeated, wherein the carrier substrate was repeatedly coated as in Example 3. For this purpose, the suspension was first diluted to a solids content of 28% with distilled water, and the catalyst was coated with this according to Example 2, and then thermally fixed the layer. The suspension was then further diluted to a solids content of 25% and the process of coating and thermal fixation according to Example 2 was repeated with this suspension, whereby a loading of the carrier substrate of 0.19 g / cm ^{3 was} achieved. Example 5 Comparative Experiments in the Methanol-to-Propylene / Butylene Process (MT3 / 4 Process)

2 g of the catalyst prepared according to Comparative Example 1 were mixed with 24 g of silicon carbide and installed in a continuously operated, electrically heated tubular reactor, so that the bed in the reactor has a length of 30 cm and a diameter of 12 mm. For the experiments using the catalysts prepared according to Comparative Example 2 and Examples 1 to 4, two of the coated honeycomb bodies were respectively installed in the reactor and sealed at the pipe wall with glass fiber cord. Before the test reactor methanol vapor was generated to a gas stream containing 75 vol .-% of methanol and 25 vol .-% N2 which loaded by a 34 ml_ alumina grit loaded prereactor at 275 ° C and an (absolute) pressure of 1 -2 bar Dimethyl ether was reacted. The dimethyl ether-containing stream was then passed into the tube reactor, and there at a temperature of 450 to 500 ° C, a load (WHSV = weight hourly space yelocity) depending on the sample in the range of 3.6 to 10 r ¹ based on methanol and reacted at an (absolute) pressure of 1 to 2 bar, the reaction parameters were kept throughout the term. After the tube reactor, the gaseous product mixture was analyzed on-line chromatographically.

The selectivity results obtained in the MT3 / 4 method for the catalysts according to Comparative Examples 1 and 2 and Examples 1 to 4 are shown in Table 1, these representing the average selectivities during the lifetime of the catalyst, in which the conversion of methanol 95% or more.

Table 1: Average selectivities of one cycle (methanol conversion of> 95%).

As can be seen from the values in Table 1, it has surprisingly been found that the specific use of an alkaline earth metal-containing zeolite which has been applied to a carrier substrate in an MT3 / 4 process not only leads to very high selectivities with respect to propylene and butylene in the product stream but it can be maintained for a surprisingly long time, as can be determined by the unexpectedly long service life of the catalyst, in which a conversion of methanol over 95% can be maintained. As can be seen from the results of Comparative Examples 1 and 2 and Example 1 in Table 1, it was found that prolonging the life or unexpected increase in MeOH load per cycle achieved by the application of the zeolite to a substrate unexpectedly can be further increased by the additional use of an alkaline earth metal-containing zeolite. All the more surprising, however, is the fact that this simultaneously causes an unexpected and above all constant selectivity of the catalyst according to Example 1 towards the C3 and C4 olefins propylene and butylene. Thus, a catalyst for the conversion of oxygenates an unexpectedly high selectivity to C3 and _C4 olefins is by the present invention provided to olefins which, as was shown in Example 5 on the basis of the test results in MT3 / 4 method, which comprises using surprisingly long service life is associated, in particular in comparison to a catalyst which is present as an extrudate (see Comparative Example 1) or which was applied to a carrier substrate, but no alkaline earth metal has (see Comparative Example 2).

As can be seen from the results for the catalysts of Examples 2, 3 and 4, which contain a binder compared to Example 1, the substantial improvement in the life was observed despite the use of a binder. In particular, by a constantly higher loading of the catalyst in Examples 3 and 4, a further significant increase in the service life could be achieved, although the methanol load per cycle observed in Example 1 could not be fully achieved. However, the use of a binder leads to a catalyst which has a much higher resistance due to the better adhesion of the layer.

Quite surprisingly been found, however, that the use of a binder results in a further increase in the selectivity of the catalyst toward the C 3 and C ₄ olefins. In particular, a significant discontinuity is observed in the selectivity to C3 olefins in Example 2 compared to Example 1 observed that already shows a significant increase compared to the selectivities towards C3 and _C4 olefins of the comparative examples. This is done, above all, without compromising the selectivities towards C ₄ olefins, which corresponds to the results of Example 1. With a respective increase in the loading in Examples 3 and 4, a likewise very high selectivity towards C 3 -olefins can be observed in comparison to Example 1 and in particular to the comparative examples. Surprisingly, however, the selectivity to C ₄ olefins in Examples 3 and 4 increases, with the highest selectivity for Example 3 being observed.

Thus, the present invention also provides a catalyst for the conversion of oxygenates to olefins which, through the use of a binder, not only increases the resistance of the catalyst, but also its service life by the possibility of using higher loadings of the catalyst on the carrier substrate. In particular, but surprisingly found that the special use of a Binders could cause in the catalyst of the invention to a further improvement in the selectivity toward C ₄ olefins and in particular also towards C3 olefins. Accordingly, a much improved catalyst for the conversion of oxygenates to olefins is provided by the present invention, which has particularly long service life at the same time high selectivities towards C3 and _C4 olefins.

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- US 4,049,573

- Goryainova et al. in Petroleum Chemistry 201 1, Vol. 51, No. 3, pp. 169-173

Ciambelli et al "Acid-base catalysis in the conversion of methanol to olefins over Mg-modified ZSM-5 zeolite", Successful Design of Catalysts, Elsevier Science Publishers B.V., Amsterdam, 1988, pp. 239-246

- Okado et al. in Applied Catalysis 1988, 41, pp. 121-135

Claims

Claims:

1 . Catalyst for the conversion of oxygenates to olefins comprising

a carrier substrate and

a layer applied to the substrate,

wherein the layer contains one or more zeolites of the MFI, MEL and / or MWW structure type, the one or more zeolites containing one or more alkaline earth metals.

2. A catalyst according to claim 1, wherein the shape of the carrier substrate is selected from the group consisting of granules, pellets, nets, rings, spheres, cylinders, hollow cylinders, monoliths and mixtures and / or combinations of two or more thereof.

The catalyst of claim 2, wherein the one or more monoliths are selected from the group consisting of honeycombs, braids, foams, and combinations of two or more thereof.

4. Catalyst according to one of claims 1 to 3, wherein the carrier substrate contains ceramic and / or metallic substances.

5. A catalyst according to any one of claims 1 to 4, wherein the one or more zeolites are of the MFI structure type.

6. Catalyst according to one of claims 1 to 5, wherein the alkaline earth metal is Mg.

7. Catalyst according to one of claims 1 to 6, wherein the one or more zeolites of the MFI, MEL and / or the MWW structure type, the one or more alkaline earth metals in a total amount in the range of 0.1 to 20 wt .-% in each case based on the total amount of the one or more zeolites of the MFI, MEL and / or of the MWW structure type and calculated as metal.

8. A catalyst according to any one of claims 1 to 7, containing the one or more zeolites of MFI, MEL and / or MWW structure type in a total loading of 0.005 to 1 g / cm ³ based on the volume of the coated carrier substrate.

9. A process for preparing a catalyst according to any one of claims 1 to 8 comprising (i) providing the carrier substrate and the one or more zeolites of MFI, MEL and / or MWW structure type;

(ii) impregnating the one or more MFI, MEL and / or MWW-type zeolites with a solution containing the one or more alkaline earth metals, preferably by spray impregnation;

(iii) optionally drying the one or more impregnated zeolites obtained in (ii);

(iv) optionally calcining the one or more impregnated zeolites obtained in (ii) or (iii);

(vi) homogenizing the mixture obtained in (v) and optionally adding a binder;

(vii) coating the carrier substrate with the homogenized one obtained in (vi)

Mixture;

(viii) optionally drying the coated support substrate obtained in (vii);

(ix) optionally calcining the coated carrier substrate obtained in (vii) or (viii).

10. The method according to claim 9, wherein after impregnation in step (ii) or after the preparation of the mixture in step (v), preferably after preparing the mixture in step (v) and particularly preferably in step (vi) of homogenizing the in (v) obtained mixture, the one or more impregnated zeolites of MFI, MEL and / or MWW structure type are brought to a particle size D ₅ o in the range of 0.01 to 200 μηη.

1 1. A process according to claim 9 or 10, wherein after the impregnation in step (ii) or after the preparation of the mixture in step (v), preferably after the preparation of the mixture in step (v) and particularly preferably in step (vi) of homogenizing the in (v) the mixture obtained, the one or more impregnated zeolites of MFI, MEL and / or MWW structure type are brought to a particle size D ₉ o in the range of 0.5 to 50 μηη.

A process according to any one of claims 9 to 11, wherein the drying in (iii) and / or (viii) is carried out at a temperature in the range of 50 to 220 ° C.

A process according to any one of claims 9 to 12, wherein the calcining in (iv) and / or (ix) is carried out at a temperature in the range of from 300 to 850 ° C.

14. The method according to any one of claims 9 to 13, wherein the solution used in (ii) and / or the mixture prepared in (v) contains one or more solvents selected from the group consisting of alcohols, water, mixtures of two or more Alcohols, and mixtures of water and one or more alcohols.

15. The method according to any one of claims 9 to 14, wherein the solids concentration of the mixture prepared in (v) is in the range of 5 to 50 wt .-%.

16. The method according to any one of claims 9 to 15, wherein the homogenization in (vi) is carried out by stirring, kneading, shaking, vibration or combinations of two or more thereof.

17. The method according to any one of claims 9 to 16, wherein the coating in (vii) is carried out by spray coating and / or wash coating.

18. The method according to any one of claims 9 to 17, wherein step (vii) is repeated one or more times.

19. A catalyst for the conversion of oxygenates to olefins, obtainable by a process according to any one of claims 9 to 18.

20. A process for converting oxygenates to olefins comprising

(1) providing a gas stream containing one or more oxygenates;

(2) contacting the gas stream with a catalyst according to any one of claims 1 to 8 or 19.

21. The process of claim 20, wherein the gas stream of (1) contains one or more oxygenates selected from the group consisting of aliphatic alcohols, ethers, carbonyl compounds and mixtures of two or more thereof.

22. The method according to claim 19 or 21, wherein the content of oxygenates in the

Gas flow according to (1) in the range of 30 to 100 vol .-% based on the total volume.

23. The method according to any one of claims 19 to 22, wherein the content of water in the gas stream according to (1) in the range of 5 to 60 vol .-% based on the total volume.

24. The method according to any one of claims 19 to 23, wherein the contacting according to (2) takes place at a temperature in the range of 200 to 700 ° C.

25. The method according to any one of claims 19 to 24, wherein the contacting according to (2) takes place at a pressure in the range of 0.1 to 10 bar.

26. The method according to any one of claims 19 to 25, wherein the method is a continuous process.

27. The method of claim 26, wherein the space velocity in contacting according to (2) is in the range of 0.5 to 50 r ¹ .

28. The method of claim 27, wherein the service life of the coated carrier substrate as a catalyst, during which the continuous process is carried out without interruption, in the range of 15 to 400 h.

29. Use of the catalyst according to one of claims 1 to 8 and 19 in a methanol-to-olefin process (MTO process), in a methanol-to-gasoline process (MTG process), in a methanol to hydrocarbon processes, in a methanol-to-propylene process (MTP process), in a methanol-to-propylene / butylene process (MT3 / 4 process), for the alkylation of aromatics or in fluid Catalytic cracking process (FCC process).