JP2015522408A - Catalyst coating and process for the conversion of oxygenates to olefins - Google Patents

Abstract

The present invention is a catalyst for the conversion of oxygenates to olefins comprising: a support substrate, and a layer applied to the substrate, wherein the layer is of MFI, MEL and / or MWW structure type A catalyst comprising one or more zeolites, wherein the one or more zeolites comprise one or more alkaline earth metals, methods of making and using the same, and methods of converting oxygenates to olefins using the catalysts About.

Description

  The present invention relates to a catalyst in the form of a coated support substrate for the conversion of oxygenates to olefins and a process for the production thereof. The invention further relates to a process for the conversion of oxygenates to olefins, in particular using the coated support substrate of the invention as a catalyst, and a process for using the catalyst according to the invention in a specific contacting process.

Introduction Given the increasing shortage of mineral oil reserves that are the starting materials for the production of lower hydrocarbons and their derivatives, alternative production methods for such generic chemicals are becoming increasingly important . In an alternative method for obtaining lower hydrocarbons and their derivatives, in particular to obtain lower hydrocarbons and their derivatives, such as unsaturated lower hydrocarbons, with the highest selectivity from other raw materials and / or chemicals The catalyst is frequently used. In this context, important methods include those where the starting chemical methanol is subjected to catalytic conversion, usually resulting in a mixture of olefins, paraffins and aromatics.

  In the case of such catalytic conversion, improve the catalyst used in the catalytic conversion and improve the process mode and its parameters so that a very small number of very specific products are produced with the highest selectivity in the catalytic conversion. Is a unique issue. These methods are therefore named mainly according to the product obtained. In the last few decades, a process that allows the conversion of methanol to olefins and is accordingly regarded as a process for producing olefins from methanol (MTO process for producing olefins from methanol) has gained particular significance. For this purpose, there has been developed a catalyst and a method for converting methanol, in particular, into a mixture based on ethene and propene via a dimethyl ether intermediate.

  Antia et al., Ind. Eng. Chem. Res. 1995, 34, 140-147, describes the coating of a support substrate with ZSM-5 and the use of it in a process for producing gasoline from methanol (MTG process).

  US Pat. No. 4,692,423 discloses a process for producing a supported zeolitic catalyst by applying a mixture of zeolites in a polymerizable solvent, for example tetrahydrofuran, to a porous support substrate which may be composed of an organic material or an inorganic material. About.

  Ivanova et al. Phys. Chem. C, 2007, 111, 4368-4374, are foam molded articles and extrudates composed of β-silicon carbide, each coated with a ZSM-5 coating, and such coated foams and extrusions. The present invention relates to a method for using a product in a method for producing olefin from methanol (MTO method). Compared to the method using powdered zeolite itself, in this case an improvement in catalytic activity / selectivity is observed, and the coated catalyst has increased stability against deactivation due to coking.

  Patcas, F.M. C. , Journal of Catalysis, 2005, Vol. 231, pages 194-200, describe ceramic foams coated with ZSM-5 zeolite and methods of using them in a process for producing olefins from methanol. More particularly, it is stated that such coated ceramic foams should show improvements in activity and selectivity compared to zeolitic pellets. However, it is stated that at relatively low temperatures and relatively high space velocities, the space-time yield is low compared to zeolitic pellets.

  WO 98/29519 A1 describes non-zeolitic molecular sieves, in particular SAPO supported on inorganic materials, and methods of using them in a process for producing olefins from methanol.

  WO 94/25151 A1 describes ZSM-5 supported on zeolites, in particular monoliths, and a method of using it as a molecular sieve in a separation process.

  Hammon et al., Applied Catalysis, 1988, 37, 155-174, describe methods for producing zeolite extrudates with little to no binder and methods for producing olefins from methanol using these zeolite extrudates. It is related to the method used. However, Hammon et al. Describe that the method of using an extrudate formed into a monolith as a catalyst is particularly disadvantageous due to rapid coking and correspondingly short service life.

  Li et al., Catal. Lett. 2009, 129, 408-415 relate to foamed ZSM-5 monoliths and methods of using them in a process for producing olefins from methanol.

  DD238733 A1 relates to, for example, a magnesium-doped zeolite and a method for use in the process of converting it from methanol to a lower olefin, specifically having a carbon number in the range of ≧ 3. McIntosh et al., Applied Catalysis, 1983, 6, 307-314, specifically describes a ZSM-5 catalyst, a method of using it in a process for producing olefins from methanol, various metals and non-metals such as magnesium. Or its doping with phosphorus and its effect on the yield and product distribution of catalytic conversion of methanol.

  US 4,049,573 for the selective conversion of lower alcohols and their ethers, in particular methanol and dimethyl ether, to hydrocarbon mixtures having a high proportion of C2-C3 olefins and monocyclic aromatics, in particular para-xylene. Wherein the catalyst used therein is doped with boron, magnesium and / or phosphorus.

  Goryanova et al., Petroleum Chemistry, 2011, 51, 3, 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 Cs. V. Amsterdam, 1988, pp. 239-246, discusses the influence of magnesium in the MTO process, particularly in combination with ZSM-5 zeolite as a catalyst.

  Okado et al., Applied Catalysis, 1988, 41, 121-135, relates to a process for producing olefins from methanol using a ZSM-5 catalyst, and various alkaline earth metals during the useful life of the catalyst. The effect on the catalyst deactivation has been studied.

  In the prior art, several advancements have been realized with regard to catalyst selectivity and / or activity by changing the composition and / or configuration of the catalyst, especially in the process of producing olefins from methanol, There remains a significant need for new catalysts and methods that not only have improved selectivity but also have better resistance to any deactivation in such methods. This is especially true for improvements that can lead to reduced catalyst coking and allow increased efficiency of existing and new processes.

US 4,692,423 WO98 / 29519 WO94 / 25151 DD238733 US 4,049,573

Antia et al., Ind. Eng. Chem. Res. 1995, 34, 140-147. Ivanova et al. Phys. Chem. C, 2007, 111, 4368-4374. Patcas, F.M. C. , Journal of Catalysis, 2005, 231, 194-200. Hammon et al., Applied Catalysis, 1988, 37, 155-174. Li et al., Catal. Lett. 2009, 129, 408-415. McIntosh et al., Applied Catalysis, 1983, 6, 307-314. Goryanova et al., Petroleum Chemistry, 2011, 51, 3, 169-173 Ciambelli et al., “Acid-base catalysis in the conversion of methanol to olefins over Mg-modified ZSM-5 zeolite, Successful Design of Cs. V. Company, Amsterdam, 1988, pp. 239-246 Okado et al., Applied Catalysis, 1988, 41, 121-135.

DETAILED DESCRIPTION Accordingly, it is an object of the present invention to improve the catalyst, particularly for the conversion of oxygenates to olefins, to extend the useful life of catalysts with comparable oxygenate space velocities and conversions. It is to provide a catalyst capable of In this context, a particular object of the present invention is that before the regeneration of the catalyst is required, for example in a process for producing olefins from methanol, in order to achieve the desired selectivity and / or sufficient space time yield. It was to bring about an improvement with respect to the coking of the catalyst which determines the service life of the catalyst.

Surprisingly, it comprises a support substrate and a layer applied to the substrate, the catalytically active layer comprising one or more zeolites of MFI, MEL and / or MWW structure type, each containing one or more alkaline earth metals, catalysts for the conversion of oxygenates to olefins, as well as service life is considerably improved, C 3 _- and C ₄ - selectivity to olefin Was surprisingly high. More particularly, unexpectedly, one or more zeolites of the MFI, MEL and / or MWW structure types, together with the configuration of the catalyst being a support substrate coated with one or more zeolites. The specific combination of doping with one or more alkaline earth metals unexpectedly improves the resistance to catalyst deactivation when using the catalyst in a catalytic process and uses a catalyst for the conversion of oxygenate It was also revealed that the olefin selectivity was surprisingly high.

Accordingly, the present invention is a catalyst for the conversion of oxygenate to olefin,
A support substrate;
A layer applied to a substrate, the layer comprising one or more zeolites of MFI, MEL and / or MWW structure type, the one or more zeolites comprising one or more alkaline earth metals Relates to the catalyst containing.

  With respect to the support substrate used in the catalyst of the present invention, there is in principle no limitation as to its shape. Accordingly, it is in principle possible to select any available form that can be considered for the support substrate. Provided that the support substrate is suitable to be at least partially coated with a layer of one or more zeolites of MFI, MEL and / or MWW structure type. However, according to the present invention, the shape of the support substrate is selected from the group consisting of granules, pellets, meshes, rings, spheres, cylinders, cylinders, and mixtures and / or combinations of two or more thereof. Is preferred. With regard to the preferred mixtures, these preferably relate to the shape of the support substrate commonly used for the production of floors, which is particularly selected from the group of granules, pellets, meshes, rings, spheres, cylinders and cylinders. It relates to a preferred shape of the substrate. On the other hand, for the support substrate shape combination according to the present invention, a combination of floor and monolith is preferred, and the bed consists of granules, pellets, mesh, rings, spheres, cylinders, cylinders, and mixtures of two or more thereof. It is preferred to include a support substrate selected from the group. More particularly, such floor and monolith combinations include a series of one or more monoliths and one or more beds, where the bed (s) and monolith (s) are catalytic. The preferred form of the catalyst forms the individual zones of the catalyst. However, also preferred are embodiments of the catalyst of the invention comprising a combination of monoliths in the form of a support substrate, in particular a combination of monoliths according to certain or preferred embodiments described in this application. In a particularly preferred embodiment of the invention, the support substrate consists of one or more monoliths, and if a plurality of monoliths are used, the individual monoliths or the plurality of monoliths arranged side by side at least in pairs It is preferred that a stretch and / or continuity is present in the catalyst.

  Thus, according to the present invention, the shape of the support substrate is selected from the group consisting of granules, pellets, meshes, rings, spheres, cylinders, cylinders, monoliths, and mixtures and / or combinations of two or more thereof, Preferred is an embodiment of the catalyst for the conversion of oxygenate to olefin, wherein the support substrate is preferably one or more monoliths.

  With respect to the monolith or monoliths that are preferably present as the support substrate of the catalyst of the present invention, there is in principle no limitation as to the form that the monolith or monoliths can take. According to the present invention, a monolith selected from the group consisting of honeycombs, braids, foams, and combinations of two or more thereof is preferred, wherein one or more monoliths comprise one or more honeycombs and / or braids. It is further preferable to include it. More preferably, according to the present invention, the monolith or monoliths that are preferably used as a support substrate are in the form of a honeycomb.

  Thus, according to the present invention, one or more monoliths that are preferred support substrates are further selected from the group consisting of honeycombs, braids, foams, and combinations of two or more thereof. Preferred is an embodiment of the catalyst for the conversion of oxygenate to olefin, wherein the monolith is preferably in the form of a honeycomb.

  In a preferred embodiment comprising one or more monoliths in the form of a honeycomb, the honeycomb form is suitable for being at least partially coated with one or more zeolites of the MFI, MEL and / or MWW structure types. Subject to no specific restrictions. In a particularly preferred embodiment, the honeycomb consists of a number of channels parallel to each other and separated from each other by monolith walls, the shape of the channels and / or the thickness of the monolith walls preferably separating the channels from each other to a certain tolerance. Are preferably the same both in terms of channel shape and in terms of wall thickness, the wall thickness typically being caused by the material used to produce the monolith or the mode of production of the honeycomb or the shape of the honeycomb . For example, a channel having an angular shape, preferably a regular polyhedron shape having 3 or more vertices, preferably 3, 4 or 6 vertices, and more preferably 4 vertices is preferred. With regard to the dimensions of the channels in the preferred embodiment of the monolith in the form of a honeycomb, depending on the selected dimensions, the monolith in the form of a honeycomb which is the support substrate for the catalyst of the present invention is converted to a MFI, MEL and / or MWW structure type 1 In principle there is no restriction, provided that it is possible to at least partially coat with one or more zeolites.

  Thus, according to the present invention, it is possible to use a monolith in the form of a honeycomb, for example having 62 to 186 channels per square centimeter (400 to 1200 cpsi = cells per square inch) Monoliths in the form of honeycombs with 171 channels (500-1100 cpsi) are preferred, those with 93-163 channels per square centimeter (600-1050 cpsi) are more preferred, and 109-155 channels (700-1000 cpsi) per square centimeter. More preferred are those having 124 to 147 channels per square centimeter (800 to 950 cpsi), more preferably 1 per square centimeter. More preferably those having from 2 to 144 channels (850~930cpsi). In a particularly preferred embodiment of the invention, according to the invention, the support substrate comprises a monolith in the form of one or more honeycombs and has 136 to 141 channels per square centimeter (880 to 910 cpsi). Is done. In an alternative embodiment of the invention, in particular a preferred embodiment in which the layer applied to the substrate of the catalyst of the invention further comprises a binder, a monolith with a honeycomb having 8-124 channels per square centimeter (50-800 cpsi) Are preferred, monoliths in the form of honeycombs having 23 to 109 channels per square centimeter (150 to 700 cpsi), more preferably having 31 to 93 channels per square centimeter (200 to 600 cpsi), more preferably 39 per square centimeter. Those having ˜85 channels (250-550 cpsi) are more preferred, and those having 47-78 channels (300-500 cpsi) per square centimeter are more preferred. In an alternative embodiment of the present invention, an embodiment in which the monolith in the form of one or more honeycombs has 54 to 70 channels per square centimeter (350 to 450 cpsi) is particularly preferred.

  In an alternative embodiment of the invention using one or more monoliths as the support substrate for the catalyst, the substrate foam is not present there. Accordingly, preferred are catalyst embodiments in which the support substrate does not contain any foam, and more particularly no foam as a monolith.

  With regard to the material constituting the support substrate, in particular the floors and / or monoliths present therein, according to the invention, the material is at least partly composed of one or more zeolites of the MFI, MEL and / or MWW structure type. There is no restriction in this respect provided that it is suitable for coating. It is therefore possible in principle to use any material and / or any material composite as a material for the support substrate, if appropriate, with high thermal stability and / or chemical reactivity. Are preferably highly inert materials. Accordingly, ceramic and / or metallic materials and ceramic and / or metallic material composites are preferably used as the support substrate of the catalyst of the present invention, and ceramic materials are preferably used as the support substrate. . Regarding preferred ceramic materials, these selected from the group consisting of alumina, silica, silicate, aluminosilicate, silicon carbide, cordierite, mullite, zirconium, spinel, magnesia, titania and mixtures of two or more thereof. It is preferred to use one or more of the substances. In a particularly preferred embodiment of the invention, the ceramic material that is preferably used for the support substrate is selected from the group consisting of α-alumina, silicon carbide, cordierite and mixtures of two or more thereof. In particularly preferred embodiments, the support substrate comprises cordierite, more preferably a cordierite substrate.

  Thus, according to the present invention, the support substrate is a ceramic and / or metallic material, preferably a ceramic material, more preferably alumina, silica, silicate, aluminosilicate, silicon carbide, cordierite, mullite, zirconium, One or more substances selected from the group consisting of crystallite, magnesia, titania and mixtures of two or more thereof, preferably α-alumina, silicon carbide, cordierite and mixtures of two or more thereof Preferred is an embodiment of a catalyst for the conversion of oxygenate to olefin, which is more preferably a cordierite substrate.

  With respect to one or more zeolites present in the catalyst, according to the invention, as used herein, provided that the zeolite is one or more zeolites of MFI, MEL and MWW structure types. There are no restrictions on the type or number of zeolites that can be made. If one or more of the zeolites present in the catalyst are of the MWW structure type, there is also no limitation as to the type and / or number of MWW zeolites that can be used according to the present invention. Thus, these include, for example, MCM-22, MCM-36, [Ga-Si-O] -MWW, [Ti-Si-O] -MWW, ERB-1, ITQ-1, PSH-3, SSZ-25 and MWW structure type zeolites consisting of a mixture of two or more thereof can be selected, and MWW structure types suitable for the conversion of oxygenates to olefins, in particular MCM-22 and / or MCM-36 zeolites. It is preferable to use it.

  The same applies equally to zeolites of the MEL structure type that can be used according to the invention in the catalyst, which are for example ZSM-11, [Si—B—O] -MEL, boron-D (MFI / MEL Mixed crystal), Boralite D, SSZ-46, Silicalite 2, TS-2 and mixtures of two or more thereof. In this case as well, it is preferable to use a MEL structure type suitable for the conversion of oxygenate to olefin, in particular [Si—B—O] -MEL zeolite.

  However, according to the invention, in particular zeolites of the MFI structure type are used in the catalyst of the invention for the conversion of oxygenates to olefins. With respect to these preferred embodiments of the present invention, there is likewise no limitation as to the type and / or number of zeolites of this structure type used, one or more zeolites of the MFI structure type used in the catalyst of the present invention. Are preferably ZSM-5, ZBM-10, [As-Si-O] -MFI, [Fe-Si-O] -MFI, [Ga-Si-O] -MFI, AMS-1B, AZ-1, Boron-C, Boralite C, Ensilite, FZ-1, LZ-105, Monoclinic H-ZSM-5, Mutinaite, NU-4, NU-5, Silicalite, TS-1, TSZ, TSZ-III , TZ-01, USC-4, USI-108, ZBH, ZKQ-1B, ZMQ-TB and mixtures of two or more thereof. More preferably, according to the invention, it is preferred that the catalyst comprises ZSM-5 and / or ZBM-10 as zeolite of MFI structure type, in particular ZSM-5 is used as zeolite. The zeolitic material ZBM-10 and its production process are described, for example, in EP 0 007 081 A1 and EP 0 034 727 A2, the contents of which are particularly relevant to the process for the production and characterization of the material. Incorporated.

  Thus, according to the present invention, one or more zeolites are of MFI structure type, preferably ZSM-5, ZBM-10, [As-Si-O] -MFI, [Fe-Si-O] -MFI. , [Ga-Si-O] -MFI, AMS-1B, AZ-1, Boron-C, Boralite C, Ensilite, FZ-1, LZ-105, Monoclinic H-ZSM-5, Mutinaite, NU -4, NU-5, silicalite, TS-1, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B, ZMQ-TB and mixtures of two or more thereof Oxygen, more preferably selected from the group consisting of ZSM-5, ZBM-10 and mixtures thereof, wherein the MFI structure type zeolite is preferably ZSM-5 Embodiment of the catalyst for the conversion of bets to olefins are preferred.

  In a preferred embodiment of the present invention, the catalyst does not contain a significant amount of one or more non-zeolitic materials, and in particular does not contain a significant amount of one or more alumino silicophosphates (SAPO). In the context of the present invention, the specific material is less than 0.1% by weight, preferably 0.05% by weight, based on 100% by weight of the total amount of one or more zeolites of MFI, MEL and / or MWW structure type. Or less, more preferably 0.001% by weight or less, more preferably 0.0005% by weight or less, more preferably 0.0001% by weight or less when present in the catalyst, the catalyst essentially contains this particular material. Does not contain or does not contain a significant amount of this particular material. A particular material in the context of the present invention also particularly represents a particular element or a particular combination of elements, a particular substance or a particular substance mixture, and combinations and / or mixtures of two or more thereof.

  In the context of the present invention, as alumino silicophosphate (SAPO), particularly the SAPO materials SAPO-11, 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 zeolites of MFI, MEL and / or MWW structure type comprise one or more alkaline earth metals. In general, in accordance with the present invention, no limitation is imposed on the type and / or number of alkaline earth metals present in one or more zeolites or the manner in which alkaline earth metals are present in one or more zeolites. Nor. Thus, the one or more zeolites can include one or more alkaline earth metals selected from the group consisting of, for example, magnesium, calcium, strontium, barium, and combinations of two or more thereof. However, according to 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, particularly preferred for the catalyst of the present invention. In an embodiment, the alkaline earth metal is magnesium. In a preferred alternative embodiment of the invention, the catalyst does not contain calcium and / or strontium or does not contain significant amounts of calcium and / or strontium.

  Thus, according to the invention, the alkaline earth metal present in one or more zeolites of MFI, MEL and / or MWW structure type is composed of Mg, Ca, Sr, Ba and combinations of two or more thereof. Embodiments of catalysts for the conversion of oxygenates to olefins, preferably selected from the group consisting of Mg, Ca, Sr and combinations of two or more thereof, wherein the alkaline earth metal is more preferably Mg Is preferred.

  With respect to the manner in which one or more alkaline earth metals are present in one or more zeolites in the catalyst, these one or more alkaline earth metals are in principle the micropores of one or more zeolites. And / or in particular at least partly present as an element of the zeolitic framework by isomorphous substitution of elements of the zeolitic framework, preferably silicon and / or aluminum, more preferably aluminum of the zeolitic framework be able to. With respect to the presence of one or more alkaline earth metals in the micropores of one or more zeolites, these one or more alkaline earth metals can contain separate compounds such as salts and / or Alternatively, it can exist as an oxide and / or as a positive counter ion to the zeolite framework. According to the present invention, one or more of the zeolites already produced and / or as may occur in the course of the production of one or more zeolites in the presence of one or more alkaline earth metals, for example. As provided by performing ion exchange with the alkaline earth metal, the one or more alkaline earth metals are at least partially present in one or more zeolite pores, preferably micropores, more preferably The one or more alkaline earth metals are present at least in part as counterions of the zeolite framework.

  With respect to the amount of one or more alkaline earth metals, as already indicated above, according to the present invention, there are no specific restrictions regarding the amount present in one or more zeolites. Thus, any conceivable amount of one or more alkaline earth metals in one or more zeolites, for example one total of one or more alkaline earth metals relative to the total amount of one or more zeolites. It is possible in principle to be present at 1 to 20% by weight. However, according to the present invention, the total amount of the one or more alkaline earth metals is 0.5 to 15% by mass, more preferably 1 to 10% by mass, based on 100% by mass of the total amount of the one or more zeolites. More preferably, it is 2-7 mass%, More preferably, it is 3-5 mass%, More preferably, it exists in the range of 3.5-4.5 mass%. In a particularly preferred embodiment of the invention, the one or more alkaline earth metals are present in the one or more zeolites in a total amount of 3.8-4.2% by weight. For all the above mass percentages relating to alkaline earth metals in one or more zeolites, these are calculated from one or more alkaline earth metals as the metal.

  Thus, according to the present invention, one or more zeolites of the MFI, MEL and / or MWW structure type comprise one or more alkaline earth metals, in each case the MFI, MEL and / or MWW structure. Based on the total amount of one or more types of zeolite, the total amount calculated as metal is 0.1-20% by weight, preferably 0.5-15% by weight, more preferably 1-10% by weight, more preferably 2 to 7% by mass, more preferably 3 to 5% by mass, more preferably 3.5 to 4.5% by mass, and even more preferably 3.8 to 4.2% by mass. Preferred is a catalyst embodiment for conversion to olefin.

With respect to the components that can be present in the layer applied to the substrate of the catalyst of the present invention, there is no limitation provided that 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 can consist of one or more zeolites of MFI, MEL and / or MWW structure types comprising one or more alkaline earth metals. In another embodiment of the catalyst of the invention, the layer applied to the substrate comprises one or more other components for the described zeolite. There are no restrictions regarding the additional components to one or more zeolites of the MFI, MEL and / or MWW structure types, so that the layer applied to the substrate can be, for example, another catalytically active component, cocatalyst, filler. , Support materials and / or binders, and combinations of two or more thereof. In a preferred embodiment, the layer applied to the substrate further comprises a binder. In these preferred embodiments, any suitable binder can be present in the layer and thus one or more additional components that can be present in the applied layer act as a binder, in particular Improve the adhesion of another component, especially one or more zeolites. Thus, one or more components for _example, present in the layer as a binding agent selected from the group consisting of _{SiO 2, Al 2 O 3,} TiO 2, ZrO 2, MgO, clay minerals, and mixtures of two or more thereof The layer in a particularly preferred embodiment comprises SiO ₂ as binder in addition to one or more zeolites of MFI, MEL and / or MWW structure type.

With respect to the amount of one or more zeolites of MFI, MEL and / or MWW structure type applied to the support substrate of the catalyst according to the invention, a layer comprising one or more zeolites on the support substrate. In principle, there is no restriction on the condition that at least partial formation is possible. Thus, the catalyst of the present invention comprises, for example, one or more zeolites of MFI, MEL and / or MWW structure type with a total load of 0.005 to 1 g / cm ³ . According to the present invention, the term “loading amount” represents the amount of applied component of the layer in units of grams of dry matter per unit total volume of the support substrate. The volume here relates to the volume of the coated support substrate, and in the case of objects and forms comprising hollow bodies and / or recesses, the volume also includes cavities and recesses. In an alternative definition according to the invention, in an embodiment comprising a floor, the volume in the case of support substrate loading is based on the respective volume of the floor, including the intermediate regions and cavities present therein. In a preferred embodiment of the present invention, the catalyst comprises one or more zeolites of MFI, MEL and / or MWW structure type relative to the volume of the coated support substrate, in particular its volume according to the specific preferred definitions above. The total load amount is 0.01 to 0.5 g / cm ³ , more preferably 0.02 to 0.2 g / cm ³ , still more preferably 0.04 to 0.1 g / cm ³ , further preferably 0.055. 0.08 g / cm ^3, even more preferably at 0.065~0.075g / cm ^3. In a particularly preferred embodiment of the invention, the catalyst has a total load of one or more zeolites of MFI, MEL and / or MWW structure type relative to the volume of the coated support substrate according to certain preferred definitions of the present application. In a quantity of 0.07 to 0.072 g / cm ³ .

Thus, according to the present invention, the catalyst comprises one or more zeolites of MFI, MEL and / or MWW structure type with a total loading of 0.005 to 1 g / cm relative to the volume of the coated support substrate. ³ , preferably 0.01 to 0.5 g / cm ³ , more preferably 0.02 to 0.2 g / cm ³ , more preferably 0.04 to 0.1 g / cm ³ , more preferably 0.055 0.08 g / cm ^3, more preferably 0.065~0.075g / cm ^3, even more preferably at 0.07~0.072g / cm ^3, the catalyst for the conversion of oxygenates to olefins Embodiments are preferred.

In a further preferred alternative embodiment of the invention, in particular a preferred embodiment in which the layer applied to the substrate of the catalyst of the invention further comprises a binder, the catalyst for the conversion of oxygenate to olefin is MFI, MEL and One or more zeolites of the MWW structure type with a total loading of 0.01 to 0.8 g / cm ³ , preferably 0.05 to 0.5 g / cm ^3, more preferably 0.08~0.3g / cm ^3, more preferably 0.12~0.25g / cm ^3, more preferably 0.15~0.23g / cm ^3, more preferably 0. 17 to 0.21 g / cm ³ , more preferably 0.18 to 0.2 g / cm ³ .

  The catalyst according to the invention is of the MFI, MEL and / or MWW structure type present in a layer applied to a support substrate according to the invention, in particular one of the particularly preferred embodiments of the invention described in this application. It can be produced in any suitable manner, provided that it contains one or more zeolites.

Accordingly, the present invention also provides a process for producing a catalyst according to the invention, in particular a catalyst according to one of its specific or preferred embodiments,
(I) providing a support substrate and one or more zeolites of MFI, MEL and / or MWW structure type;
(Ii) impregnating one or more zeolites of MFI, MEL and / or MWW structure type with a solution comprising one or more alkaline earth metals, preferably by spray impregnation;
(Iii) optionally drying one or more impregnated zeolites obtained in (ii);
(Iv) optionally calcining one or more impregnated zeolites obtained in (ii) or (iii);
(V) producing an impregnated, optionally dried, and / or calcined mixture comprising one or more zeolites of MFI, MEL and / or MWW structure type and one or more solvents; ,
(Vi) homogenizing the mixture obtained in (v);
(Vii) coating the support substrate with the homogenized mixture obtained in (vi);
(Viii) optionally drying the coated support substrate obtained in (vii);
And (ix) a method comprising optionally calcining the coated support substrate obtained in (vii) or (viii).

  With regard to the impregnation method in step (ii) of the method according to the invention, the impregnation can be carried out by any suitable method, for example by immersion, spray impregnation and / or capillary impregnation. However, in a particularly preferred embodiment of the process according to the invention, the impregnation in step (ii) is realized by spray impregnation.

One or more of the MFI, MEL and / or MWW structure types prepared in step (i) in the process according to the invention for producing the catalyst of the invention, especially in certain preferred embodiments described in this application. In principle there are no restrictions on the properties of the zeolite, in particular the particle size and / or morphology. However, depending on the particle size of the zeolite prepared in step (i), one or more steps are preferably carried out in the process according to the invention in order to bring one or more zeolites to the preferred particle size. ) After impregnation or after the preparation of the mixture in step (v). In this context, the particle size of one or more zeolites is initially specified provided that the particle size is suitable for carrying out another step in the present invention, in particular the method according to certain preferred embodiments of the present invention. The particle size is more particularly dependent on the nature and form of the support substrate used according to the present invention, in particular the specific or preferred embodiments of the support substrate described in this application, It should be particularly suitable for performing the coating in step (vii). Thus, in a particular embodiment of the method according to the invention, one or more zeolites of MFI, MEL and / or MWW structure type impregnated, optionally dried and / or calcined are from 0.01 to In order to obtain a particle size D ₅₀ in the range of 200 μm, one or more steps are carried out after impregnation in step (ii) or after preparation of the mixture in step (v), preferably of the mixture in step (v) After production, it is more preferably carried out in step (vi) of homogenizing the mixture obtained in (v). In a further preferred embodiment of the method according to the invention, after one or more of the above steps, the one or more zeolites are 0.03 to 150 μm, more preferably 0.05 to 100 μm, in one or more steps. More preferably, the particle diameter D ₅₀ is in the range of 0.1 to ₅₀ μm, more preferably 0.3 to 30 μm, and still more preferably 0.4 to 20 μm. In yet another preferred embodiment of the process according to the invention, after the preparation of the mixture in step (v), preferably in the step (vi) of homogenizing the mixture obtained in (v), impregnation and optionally The dried and / or calcined one or more zeolites are brought to a particle size D ₅₀ in the range of 0.5-15 μm in one or more steps.

In another preferred embodiment of the process according to the invention, in particular in a preferred embodiment in which a binder is used in the process according to the invention, the MFI, MEL and / or impregnated, optionally dried and / or calcined In order to bring one or more zeolites of MWW structure type to a particle size D ₉₀ in the range of 0.5-50 μm, one or more steps are carried out after impregnation in step (ii) or in step (v) After the preparation of the mixture, preferably after the preparation of the mixture in step (v), more preferably in the step (vi) of homogenizing the mixture obtained in step (v). In a further preferred embodiment of the method according to the invention, after one or more of the above steps, the one or more zeolites are 1-30 μm, more preferably 3-20 μm, more preferably in one or more steps. The particle size D ₉₀ is in the range of 5-15 μm, more preferably 9-11 μm. In yet another preferred embodiment of the process according to the invention, after the preparation of the mixture in step (v), preferably in the step (vi) of homogenizing the mixture obtained in (v), impregnation and optionally The dried and / or calcined one or more zeolites are brought to a particle size D ₉₀ in the range of 7-13 μm in one or more steps.

In accordance with the present invention, there is no limitation on the number and manner of steps to bring one or more zeolites to a specific or preferred particle size D ₅₀ and / or D ₉₀ , and thus any method suitable for this purpose. But in principle it can be used. However, according to the present invention, it is preferred that the one or more zeolites are subjected to one or more grinding steps after one or more of steps (ii) and (v). In particular, it is more preferred to achieve one of the specific or preferred particle sizes D ₅₀ by the homogenization operation in step (vi), in particular according to certain preferred embodiments of the present invention.

Thus, according to the invention, after impregnation in step (ii) or preparation of the mixture in step (v), preferably after preparation of the mixture in step (v), more preferably the mixture obtained in (v) In the step (vi) of homogenizing one or more impregnated zeolites of MFI, MEL and / or MWW structure type from 0.01 to 200 μm, more preferably from 0.03 to 150 μm, more preferably from 0.05 to 100 [mu] m, more preferably 0.1 to 50 [mu] m, more preferably 0.3～30Myuemu, more preferably 0.4～20Myuemu, even more preferably the particle size _{D 50} in the range of 0.5 to 15 m, the present invention Preferred is an embodiment of the process according to the invention, in particular a process according to one of its specific or preferred embodiments. Thus, according to the invention, after impregnation in step (ii) or after preparation of the mixture in step (v), preferably after preparation of the mixture in step (v), more preferably the mixture obtained in (v) In the step (vi) of homogenizing 0.5 to 50 μm, more preferably 1 to 30 μm, more preferably 3 to 20 μm, more preferably one or more impregnated zeolites of MFI, MEL and / or MWW structure type Carrying out the process for producing a catalyst, in particular a catalyst according to one of its specific or preferred embodiments, having a particle size D ₉₀ in the range of 5-15 μm, more preferably 9-11 μm, even more preferably 7-13 μm The form is likewise preferred.

  According to the invention, in the process according to the invention, the drying step is carried out according to steps (iii) and / or (viii). There is in principle no limitation on the manner in which optional drying is achieved in one or more of these steps, so that drying can be carried out at any suitable temperature and in any suitable atmosphere. Accordingly, optional drying can be performed in a protective gas atmosphere or in air, and optional drying is preferably performed in air. With respect to the temperature at which drying is performed, for example, a temperature in the range of 50 to 220 ° C. can be selected. According to the present invention, the optional drying according to steps (iii) and / or (viii) is 70-180 ° C., more preferably 80-150 ° C., more preferably 90-130 ° C., more preferably 100-125 ° C. Done in a range of temperatures. In a particularly preferred embodiment of the process according to the invention, the drying according to steps (iii) and / or (viii) is carried out at a temperature in the range from 110 to 120 ° C. In particular with regard to the time of the one or more optional drying steps in certain preferred embodiments of the method according to the invention, provided that drying suitable for further process steps can be achieved after, for example, a drying step of 1 to 50 hours. There is no limit. In a particular embodiment of the process according to the invention, the optional drying is 5 to 40 hours, more preferably 8 to 30 hours, more preferably 10 to 25 hours, more preferably 12 to 20 hours, even more preferably 14 to It takes 18 hours.

  Therefore, according to the present invention, the drying in (iii) and / or (viii) is 50-220 ° C, preferably 70-180 ° C, more preferably 80-150 ° C, more preferably 90-130 ° C, more preferably Preferred is an embodiment of the process for producing a catalyst according to the invention, in particular a catalyst according to one particular or preferred embodiment thereof, carried out at a temperature in the range from 100 to 125 ° C., more preferably from 110 to 120 ° C.

  With regard to the optional calcination process according to the invention, the same applies in principle as with the optional drying process, so that in terms of the temperature or atmosphere at which the calcination according to certain preferred embodiments of the invention takes place, the final In particular with regard to the time of calcination, there are also certain restrictions, provided that the product of calcination is processed in a further step of the process according to the invention and is a suitable intermediate for providing the catalyst according to the invention. Absent. Thus, for example, with respect to the optional calcination temperature in steps (iv) and / or (ix), a temperature in the range of 300-850 ° C. can be selected, preferably 350-750 ° C., more preferably 400-700 ° C., More preferably, it is preferable to select a temperature in the range of 450 to 650 ° C, even more preferably 480 to 600 ° C. In yet another preferred embodiment of the invention, the optional calcination in steps (iv) and / or (ix) is performed at a temperature of 500-550 ° C. The atmosphere in which the optional calcination according to one or more of the above-mentioned steps of the method according to the invention is carried out can be an inert atmosphere or air, and the optional calcination in steps (iv) and / or (ix) is It is preferably performed in air. Finally, also regarding the time of the calcination step in optional steps (iv) and / or (ix), the product of the calcination produces a catalyst, in particular a catalyst according to one of the specific or preferred embodiments of the present application. In the process according to the invention, there is no restriction provided that it is suitable for further use as an intermediate according to optional step (iv). Thus, the calcination time according to one or more of the optional calcination steps in (iv) and / or (ix) can be, for example, 0.5 to 20 hours, preferably 1 to 15 hours, more preferably 2 -10 hours, more preferably 3 to 7 hours, and particularly preferably 4 to 5 hours.

  Thus, according to the present invention, the calcination in (iv) and / or (ix) is 300-850 ° C, preferably 350-750 ° C, more preferably 400-700 ° C, more preferably 450-650 ° C, Preferred is an embodiment of the process for producing a catalyst according to the invention, in particular a catalyst according to one particular or preferred embodiment thereof, which is preferably carried out at a temperature in the range from 480 to 600 ° C., more preferably from 500 to 550 ° C.

In step (ii) of the method according to the invention, one or more zeolites of MFI, MEL and / or MWW structure type are first impregnated with a solution comprising one or more alkaline earth metals. According to the present invention, there is no limitation regarding the type and / or number of solvents used for this purpose in step (ii). Thus, it is in principle possible to use any solvent or solvent mixture as appropriate in step (ii). Provided that the solvent or solvent mixture is particularly suitable for providing a corresponding impregnation of the material defined in step (ii), in accordance with one of the particularly preferred embodiments of the invention. This applies equally to the solvent or solvents used in step (v) for producing the mixture defined in step (v). Provided that the solvent or solvents used for this purpose are suitable to allow homogenization in step (vi) and coating in step (vii). For example, one or more solvents selected from the group consisting of alcohol, water, a mixture of two or more alcohols, and a mixture of water and one or more alcohols in steps (ii) and / or (v) Can be used. In a preferred embodiment of the invention, the solvent or solvents used in (ii) and / or (v) are (C ₁ -C ₆ ) -alcohol, water, two or more (C ₁ -C ₆₎ - a mixture of alcohol and water with one or more _(C 1 -C ₆₎ - is selected from the group consisting of an alcohol, more preferably _(C 1 -C ₄₎ - alcohol, water, 2 one or more _(C 1 _{~C 4)} - a mixture of alcohol and water with one or more _(C 1 _{~C 4)} - is selected from the group consisting of an alcohol. In a further preferred embodiment, 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 selected from the group consisting of methanol, ethanol, water, and mixtures of two or more thereof, even more preferably the solvent is water, preferably distilled water.

Thus, according to the present invention, the solution used in (ii) and / or the mixture prepared in (v) comprises alcohol, water, a mixture of two or more alcohols, and water and one or more alcohols. Preferably from (C ₁ -C ₆ ) alcohol, water, a mixture of two or more (C ₁ -C ₆ ) alcohols, and water and one or more (C ₁ -C _6). A) a mixture of alcohols, more preferably (C ₁ -C ₄ ) alcohol, water, a mixture of two or more (C ₁ -C ₄ ) alcohols, and water and one or more (C ₁ -C ₄₎ from the group consisting of an alcohol, more preferably methanol, ethanol, n- propanol, isopropanol, from the group consisting of water and mixtures of two or more thereof More preferably, it comprises one or more solvents selected from the group consisting of methanol, ethanol, water and mixtures of two or more thereof, more preferably the solvent is water, preferably distilled water. Preferred is an embodiment of the process according to the invention, in particular a process according to one of its specific or preferred embodiments.

  Regarding the solids concentration of the mixture prepared in (v), according to the invention, the homogenization of the mixture in step (vi) and the coating in (vii) of the homogenized mixture obtained in (vi) There are no specific restrictions, provided that the use of is possible. Therefore, the solid concentration of the mixture prepared in (v) can be, for example, in the range of 5 to 50% by mass, and the solid concentration according to the present invention is preferably in the range of 10 to 30% by mass, Preferably it is the range of 15-25 mass%. In a particularly preferred embodiment of the process according to the invention for producing a catalyst, the solids concentration of the mixture prepared in (v) is in the range from 18 to 22% by weight.

  Therefore, according to the present invention, the solid concentration of the mixture produced in (v) is 5 to 50% by mass, preferably 10 to 30% by mass, more preferably 15 to 25% by mass, and still more preferably 18 to 22%. Preferred is an embodiment of the process for producing a catalyst according to the invention, in particular a catalyst according to one of its specific or preferred embodiments, in the mass% range.

  In alternative preferred embodiments, in particular preferred embodiments in which a binder is used in the process according to the invention, the solids concentration of the mixture prepared in (v) is in the range of 10 to 70% by weight, and the present invention The solids concentration by is preferably in the range of 20-50% by weight, more preferably in the range of 30-40% by weight. In a particularly preferred embodiment of the process according to the invention for producing a catalyst, the solids concentration of the mixture prepared in (v) is in the range of 32 to 36% by weight.

  According to the present invention, there is no specific limitation with respect to the homogenization in step (vi), and therefore any possible procedure can be selected to obtain a homogeneous mixture of the mixture produced in step (v). It is possible to use, for example, one or more processes selected from the group consisting of stirring, kneading, agitation, vibration, or combinations of two or more thereof. According to the invention, the mixture produced in step (v) is preferably homogenized by stirring and / or vibration in step (vi), more preferably the homogenization in step (vi) is vibration, preferably ultrasonic. By introducing, for example, a mixture to be homogenized using an ultrasonic cleaner.

  Thus, according to the present invention, the homogenization in (vi) is by stirring, kneading, agitation, vibration or a combination of two or more thereof, preferably stirring and / or vibration, more preferably vibration, more preferably ultrasonic. Preferred is an embodiment of the process for producing a catalyst according to the invention, in particular a catalyst according to one particular or preferred embodiment thereof.

  With regard to the components that can be present in the mixture produced in (v) and homogenized in (vi), in principle any coating, provided that the coated support substrate is obtained in (vi) There is no limit. Thus, in certain embodiments, the mixture produced in (v) and / or homogenized in (vi) is impregnated, optionally dried and / or calcined, MFI, MEL and / or Alternatively, it may consist of one or more zeolites of MWW structure type and one or more solvents. In another embodiment of the catalyst of the invention, the mixture produced in (v) and / or homogenized in (vi) comprises one or more other components for the zeolite and the solvent. With regard to the additional components that can be present in the mixture produced in (v) and / or homogenized in (vi), in principle there is no limitation and therefore (v) and / or (vi) The mixture in can include, for example, other catalyst components, cocatalysts, fillers, auxiliaries, support materials, binders, and combinations of two or more thereof. In particularly preferred embodiments, the mixture in (v) and / or (vi) comprises a binder, in which case the binder may comprise one or more substances. In principle, the binder can be added to the mixture in (v), the mixture in (vi), or both the mixture in (v) and the mixture in (vi), but in a preferred embodiment (vi ) Is added to the mixture.

In a preferred embodiment in which the binder is added at (vi), this binder is essentially prior to or homogenization of the mixture, provided that a homogenized mixture is obtained at (vi). Can be added at any time. Embodiments in which one or more additional components are added to the zeolite and solvent, particularly for preferred embodiments in which one or more zeolites are made specific D ₅₀ and / or D ₉₀ particle sizes in step (vi), in particular An embodiment in which the auxiliary is added only after the particle size is established is particularly preferred.

There is no limitation on the binder that is optionally added in the method, so the use of any suitable material and any suitable mixture for this is the adhesion of the coated substrate substrate layer. In principle, it is possible, provided that is increased as desired. Thus, according to the present invention, for example, SiO ₂ , Al ₂ O ₃ , TiO ₂ , ZrO ₂ , MgO, clay minerals, and mixtures of two or more thereof, and their respective precursor compounds and two of them. Mixtures of the above, and also mixtures of two or more of the former and two or more of their precursor compounds can be used as binders in the method of the present invention.

Al ₂ O ₃ binders and their precursor compounds that can be used are, for example, clay minerals; natural such as α-, β-, γ-, δ-, η-, κ-, χ- or θ-alumina. Or synthetic aluminas and their inorganic and / or organometallic precursor compounds such as gibbsite, bayerite, boehmite, pseudoboehmite, or trialkoxyaluminates such as aluminum triisopropoxide.

  Another binder that can be used in the present method is montmorillonite, kaolin, bentonite, halloysite, dickite or nacrite.

Preferred binders include one or more of SiO ₂ and / or its precursor compounds, more preferably SiO ₂ , preferably using colloidal SiO ₂ . In a further preferred embodiment, colloidal SiO ₂ is added as a binder in (v) and / or (vi), preferably (vi).

  There is no restriction on the concentration of binder in the homogenized mixture obtained in (vi), provided that the resulting catalyst can be used for the conversion of at least one oxygenate to at least one olefin. As a rule, it is possible in principle to use any suitable amount of binder. Thus, the binder is (v) and / or (vi), preferably (vi), for example in an amount of 0.1 to 50% by weight, based on the total solid content of the homogenized mixture obtained in (vi). Can be obtained in In a more preferred embodiment, 0.5 to 35% by weight, more preferably 1 to 30% by weight, more preferably 5 to 25% by weight, based on the total solid content of the homogenized mixture obtained in (vi). More preferably 7 to 20% by weight, still more preferably 9 to 17% by weight, still more preferably 10 to 15% by weight, still more preferably 11 to 13% by weight of binder (v) and / or (vi). , Preferably added in (vi).

  As regards the coating of the support substrate in step (vii) of the method according to the invention, there is in principle no limitation with regard to its performance, provided that the corresponding layer is at least partly formed on the support substrate. . Thus, any suitable form of coating or layer formation can be used in the process according to the invention for producing the catalyst of the invention, the coating in step (vii) being performed by spray coating and / or wash coating. Is preferred. In a particularly preferred embodiment of the method according to the invention, it is preferred that the coating in step (vii) is carried out by wash coating and the wash coating is carried out by dip coating. Such a preferred dip coating operation is performed, for example, by immersing the support substrate one or more times in the mixture produced in step (v) and homogenized in step (vi). Therefore, it is preferable to carry out a treatment for removing the excess mixture from the support substrate following the dip coating. In a preferred embodiment of dip coating in which the substrate is repeatedly immersed in the mixture produced in step (v) and homogenized in step (vi), a further preferred removal treatment of excess mixture is essentially immersion. After repeated and / or between two or more dipping steps, it is preferred to remove excess mixture by appropriate treatment of the coated substrate substrate following each dipping step. More preferably, however, according to the invention, the immersion process is performed once in the mixture produced in step (v) and homogenized in step (vi), followed by a corresponding removal treatment of excess mixture. Do. With regard to the particularly preferred removal of excess mixture according to certain embodiments of the method in which dip coating is carried out in step (vii), there are in principle no restrictions on the manner in which the excess mixture is removed. Thus, removal can be achieved, for example, by properly suspending and / or leaving the coated support substrate upright and / or directly or indirectly by mechanical or other action, for example It can be achieved by mechanical stripping and / or by removal with a suitable gas blower and / or by appropriate application of centripetal forces, for example by appropriately directed centrifugal forces. However, according to the invention, it is particularly preferred to remove the excess mixture by means of a gas blower, more preferably by means of suitable extraction blowing of the excess mixture using compressed air.

  Thus, according to the present invention, the coating in (vii) is performed by spray coating and / or wash coating, preferably wash coating, which is preferably performed by dip coating, preferably followed by removal of excess mixture. Preferred is an embodiment of the process for producing a catalyst according to the invention, in particular a catalyst according to one particular or preferred embodiment thereof, wherein the removal of excess mixture is preferably carried out at least in part with compressed air.

  In the process according to the invention, according to the invention, a support substrate is provided comprising a plurality of layers having the same and / or different compositions, in particular with respect to one or more zeolites of MFI, MEL and / or MWW structure type. In principle it is possible to do. Accordingly, step (vii) is repeated one or more times, during which step (viii) and / or step (ix), preferably both step (viii) and step (ix) are performed. Preferred is an embodiment of the process according to the invention for producing a catalyst according to the invention. In such a preferred embodiment of the process according to the invention, in particular where two or more layers of different composition with respect to one or more zeolites are applied to the support substrate, in the production of a mixture of different compositions in step (v) In some cases, steps (v) and (vi) are repeated as well, which is not only the chemical composition, but also other properties of the mixture, for example the average particle size of one or more zeolites of the MFI, MEL and / or MWW structure types And / or optional drying and / or optional calcination. In these preferred embodiments, the difference in the mixture produced in step (v) for producing the different layers on the support substrate is due to the MFI, MEL and / or MWW structure type in step (ii) of the method according to the invention. Of impregnation and / or optional drying and / or optional calcination of one or more zeolites, as well as impregnation in step (ii) and / or drying in step (iii) and / or calcination in step (iv) If also related to the mode, in these embodiments step (ii) and optionally (iii) and / or (iv) are repeated as well. In a particularly preferred embodiment of the process according to the invention, in order to achieve a multiple coating of the support substrate with the mixture produced in step (v) and homogenized in step (vi), steps (vii) and (viii) ) And / or (ix), preferably steps (vii) to (ix) are repeated one or more times.

  There is in principle no limit as to the number of iterations carried out in the preferred embodiment of the process according to the invention for producing the catalyst according to the invention, and the steps in the repetition of a particular preferred embodiment of the process according to the invention are preferably one time. -5 times, more preferably 1 to 4 times, more preferably 1 to 3 times, more preferably 1 or 2 times.

  Therefore, according to the present invention, step (vii), preferably steps (vii) and (viii), more preferably steps (vii) to (ix) are repeated one or more times, and the step is preferably performed once. ~ 5 times, more preferably 1 to 4 times, more preferably 1 to 3 times, more preferably 1 or 2 times, more preferably 2 times, the catalyst according to the invention, especially its specific or preferred Embodiments of the method for producing a catalyst according to one of the embodiments are preferred.

  In principle, there is no limitation with respect to the temperature and drying time for drying the coated support substrate obtained in (vii) in (viii). For example, the optional drying in (viii) can be performed at a temperature in the range of 50-220 ° C., and the drying is preferably in the range of 80-200 ° C., more preferably in the range of 100-180 ° C., more preferably 110-110 ° C. It is performed at a temperature in the range of 170 ° C, more preferably in the range of 120 to 160 ° C, more preferably in the range of 130 to 150 ° C, and still more preferably in the range of 135 to 145 ° C. There is no limitation on the drying time as well, so that the drying can be performed, for example, for 0.1 to 5 hours, and the drying in step (viii) is preferably 0.2 to 2 hours, more preferably 0.3 to 1 hour. .5 hours, more preferably 0.4 to 1.2 hours, more preferably 0.5 to 1 hour, more preferably 0.6 to 0.9 hours, more preferably 0.7 to 0.8 hours. Is called.

  In principle there are no restrictions regarding the temperature and calcination time for calcining the coated support substrate obtained in (vii) or (viii) with (ix). For example, the optional calcination in (ix) can be carried out at a temperature in the range of 250-1100 ° C., the calcination preferably in the range of 350-900 ° C., more preferably in the range of 400-800 ° C., more preferably The reaction is performed at a temperature 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 still more preferably in the range of 580 to 600 ° C. There is no limitation on the calcination time as well, so the calcination can be carried out, for example, for 0.5 to 20 hours, and the calcination in step (ix) is preferably 0.75 to 15 hours, more preferably 1 to It is performed for 10 hours, more preferably 1.5 to 5 hours, more preferably 2 to 4 hours, further preferably 2.5 to 3.5 hours, and more preferably 2.8 to 3.2 hours.

  In a particularly preferred embodiment of the process according to the invention, the coated substrate obtained in (vii) is dried and then calcined.

  In addition to the invention described in this application, in particular the catalyst for the conversion of oxygenates to olefins according to certain preferred embodiments thereof, the present invention likewise relates to oxygenates obtained with the process according to the invention. The catalyst for the conversion of olefins to olefins, ie the catalyst itself obtainable by the production process according to the invention, which does not necessarily have to be produced in this way, is included. Thus, in more detail, the present invention is a catalyst for the conversion of oxygenates to olefins and can be produced by the process according to the present invention, in particular its preferred embodiments described in this application. However, it relates to a catalyst which can or can be produced in a suitable alternative for this purpose.

  Thus, according to the invention, a catalyst, in particular a catalyst according to one particular or preferred embodiment of the invention, produces a catalyst according to the invention, preferably one of the particular or preferred embodiments of the method according to the invention. Preferred is an embodiment of the catalyst for the conversion of oxygenate to olefin obtained in one.

In addition to catalysts for the conversion of oxygenates to olefins and methods for making such catalysts, the present invention also relates to a method for converting oxygenates to olefins. More particularly, the present invention is such a method,
(1) providing a gas stream comprising one or more oxygenates;
(2) relates to a process comprising the step of contacting a gas stream with a catalyst according to the invention.

  With regard to the catalyst which can be used in the process according to the invention for converting oxygenates to olefins, it is for example provided that it is a catalyst according to the invention which is also obtained in the process according to the invention, and at least from one oxygenate. There are in principle no restrictions, provided that they are suitable for conversion to one olefin. This is especially true for the catalyst embodiments of the present invention according to certain preferred embodiments of the present invention.

The same applies to one or more oxygenate (s) present in the gas stream according to (1), and thus one or more oxygenates present in the gas stream according to (1). Is contacted in accordance with (2) in principle in this respect in the process according to the invention, provided that it can be converted into at least one olefin by one of the catalysts according to the invention, in particular its preferred embodiments. Nor. However, according to the present invention, the one or more oxygenates present in the gas stream according to (1) are selected from the group consisting of aliphatic alcohols, ethers, carbonyl compounds and mixtures of two or more thereof. preferable. More preferably, the one or more oxygenates are (C ₁ -C ₆ ) -alcohol, di (C ₁ -C ₃ ) alkyl ether, (C ₁ -C ₆ ) -aldehyde, (C ₂ -C _6). ) - ketones and the group consisting of a mixture of two or more thereof, more preferably _(C 1 -C ₄₎ - alcohol, di _(C 1 -C ₂₎ alkyl _{ether, (C} 1 -C ₄₎ - aldehyde, ( C ₂ -C ₄ ) -ketone and a mixture of two or more thereof. In yet another preferred embodiment of the invention, the gas stream according to (1) is methanol, ethanol, n-propanol, isopropanol, butanol, dimethyl ether, diethyl ether, ethyl methyl ether, diisopropyl ether, di-n-propyl ether, One or more oxygenates selected from the group consisting of formaldehyde, dimethyl ketone and mixtures of two or more thereof, wherein the one or more oxygenates are methanol, ethanol, dimethyl ether, diethyl ether, ethyl methyl More preferably, it is selected from the group consisting of ethers and mixtures of two or more thereof. In a particularly preferred embodiment of the process according to the invention for the conversion of oxygenates to olefins, the gas stream according to (1) comprises methanol and / or dimethyl ether as one or more oxygenates, the dimethyl ether being (1 More preferred are oxygenates present in the gas stream.

Thus, according to the invention, the gas stream according to (1) is a group consisting of aliphatic alcohols, ethers, carbonyl compounds and mixtures of two or more thereof, preferably (C ₁ -C ₆ ) alcohols, di (C ₁ -C ₃₎ alkyl _{ether, (C} 1 ~C _{6) aldehyde, (C} 2 -C ₆₎ ketone and the group consisting of a mixture of two or more thereof, more preferably _(C 1 ~C ₄₎ alcohol, di _(C 1 -C ₂₎ alkyl _{ether, (C} 1 _{~C 4) aldehyde, (C} 2 -C ₄₎ ketones and their two or more of the group consisting of a mixture, more preferably methanol, ethanol, n- propanol, Isopropanol, butanol, dimethyl ether, diethyl ether, ethyl methyl ether, diisopropyl ether, di-n-propyl One selected from the group consisting of ether, formaldehyde, dimethyl ketone and a mixture of two or more thereof, more preferably methanol, ethanol, dimethyl ether, diethyl ether, ethyl methyl ether and a mixture of two or more thereof. Preferred is an embodiment of a process for converting oxygenate to olefin comprising a plurality of oxygenates, wherein the gas stream further preferably comprises methanol and / or dimethyl ether, more preferably dimethyl ether.

  On the other hand, regarding the oxygenate content in the gas stream according to (1) in the process according to the invention for converting oxygenates to olefins, according to the invention, according to the invention, the gas stream contacts the catalyst according to the invention in (2). There is also no limitation in this respect, provided that at least one oxygenate can be converted to at least one olefin. In a preferred embodiment, the oxygenate content in the gas stream according to (1) is in the range from 30 to 100% by volume with respect to the total volume, the content being in particular in the range from 200 to 700 ° C. temperature and pressure. 101.3 kPa, preferably 250-650 ° C, more preferably 300-600 ° C, more preferably 350-560 ° C, more preferably 400-540 ° C, more preferably 430-520 ° C, more preferably For gas flows in the range of 450-500 ° C. and pressure 101.3 kPa. According to the invention, the oxygenate content in the gas stream according to (1) is 30-99% by volume, more preferably 30-95% by volume, more preferably 30-90% by volume, more preferably 30-90%. More preferably, it is 80 volume%, More preferably, it is 30-70 volume%, More preferably, it is 30-60 volume%, More preferably, it is 30-50 volume%. In a particularly preferred embodiment of the process according to the invention for converting oxygenates to olefins, the oxygenate content in the gas stream according to (1) is in the range from 30 to 45% by volume.

  Therefore, according to the present invention, the oxygenate content in the gas stream according to (1) is 30 to 100% by volume, preferably 30 to 99% by volume, more preferably 30 to 95% by volume, based on the total volume. More preferably, it is 30-90 volume%, More preferably, it is 30-80 volume%, More preferably, it is 30-70 volume%, More preferably, it is 30-60 volume%, More preferably, it is 30-50 volume%, More preferably, it is 30 Preferred is an embodiment of the process for converting oxygenate to olefin in the range of ~ 45% by volume.

  With regard to the other components in the gas stream according to (1) in the process according to the invention, the conversion of at least one oxygenate to at least one olefin in step (2) when the gas stream comes into contact with the catalyst according to the invention. In principle, there are no restrictions, provided that they are comprehensively suitable. Furthermore, in addition to one or more oxygenates in the gas stream, for example according to (1), one or more inert gases, for example one or more noble gases, nitrogen, water and two or more thereof May also be present therein. In a particular embodiment of the invention, the gas stream according to (1) of the process according to the invention comprises water in addition to one or more oxygenates.

  For preferred embodiments in which water is present in addition to one or more oxygenates in the gas stream according to (1), from at least one oxygenate in the gas stream in step (2) of contacting the gas stream There is in principle no limit as to the water content that can be present therein, provided that the conversion to at least one olefin can be carried out with the catalyst according to the invention. However, in these preferred embodiments, the water content of the gas stream is preferably in the range of 5-60% by volume with respect to the total volume, the water content is more preferably 10-55% by volume, even more preferably 20- It is 50 volume%, More preferably, it is the range of 30-45 volume%.

  Thus, according to the present invention, water is preferably 5-60% by volume, preferably 10-55% by volume, more preferably 20-50% by volume, more preferably 20% by volume, based on the total volume in the gas stream according to (1). Preferred is an embodiment of the process for converting oxygenate to olefin present in the range of 30-45% by volume.

In a particularly preferred embodiment of the process according to the invention for converting oxygenates to olefins, the gas stream prepared in (1) is pre-reacted, preferably the conversion of one or more alcohols to one or more ethers. In particular one selected 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 Or derived from conversion from a plurality of alcohols, more preferably from a pre-reaction of methanol and / or ethanol, more preferably methanol is one or more di (C ₁ -C ₂ ) alkyl ethers, preferably dimethyl ether , Diethyl ether, ethyl methyl ether At least partially converted to one or more di (C ₁ -C ₂ ) alkyl ethers selected from the group consisting of ter and mixtures of two or more thereof. For example, the gas stream provided in (1) is derived from a pre-reaction for the conversion of methanol to dimethyl ether in a particularly preferred embodiment.

  In a particularly preferred embodiment of the process according to the invention in which the gas stream provided in (1) is derived from a pre-reaction of one or more alcohols, in principle with respect to the reaction of the conversion of one or more alcohols and thus to the reaction product There are no specific restrictions. However, this conversion results in a gas stream comprising one or more oxygenates, and in (2) the conversion of oxygenates from at least one to at least one olefin upon contact with the catalyst according to the invention. On condition that it is possible. In these particular embodiments, the pre-reaction leads to the conversion of at least one alcohol to at least one ether, in particular at least one dialkyl ether, more preferably a dehydration reaction, a by-product for one or more dialkyl ethers. More preferably, water is obtained. In certain preferred embodiments of the invention in which the gas stream prepared in (1) is derived from a pre-reaction, such a gas stream from the pre-reaction is directly applied to the process according to the invention without work-up (1 In the process according to the invention.

  With regard to the mode of contacting the gas stream with the catalyst according to the invention in step (2) of the process according to the invention for converting oxygenates to olefins, it is provided that the conversion from at least one oxygenate to at least one olefin can be carried out As a rule, there are no restrictions. This applies, for example, to the temperature at which contact (2) takes place. Thus, for example, the contact in step (2) of the method according to the invention can be carried out at a temperature in the range of 200 to 700 ° C., 250 to 650 ° C., more preferably 300 to 600 ° C., more preferably 350 to 560 ° C., More preferably, it is preferable to select a temperature in the range of 400 to 540 ° C, more preferably 430 to 520 ° C. In a particularly preferred embodiment of the invention, the contact according to (2) of the process according to the invention is carried out at a temperature in the range from 450 to 500 ° C.

  Therefore, according to the present invention, the contact according to (2) is 200-700 ° C, preferably 250-650 ° C, more preferably 300-600 ° C, more preferably 350-560 ° C, more preferably 400-540 ° C, More preferred is an embodiment of the process for converting oxygenate to olefin, carried out at a temperature in the range of preferably 430-520 ° C, more preferably 450-500 ° C.

  The same applies to the pressure at which the gas stream is brought into contact with the catalyst according to the invention in step (2) of the process according to the invention. Thus, in principle, contact can be made at any desired pressure. Provided that this pressure allows the conversion of at least one oxygenate to at least one olefin by contact of the gas stream with the catalyst. Thus, for example, the pressure at the contact in step (2) can be in the range of 0.1 to 10 bar, and the pressure according to the present application is such that a pressure of 1 bar at the contact thus corresponds to a standard pressure of 1.03 kPa. Indicates absolute pressure. According to the present invention, the contact in step (2) is preferably 0.3-7 bar, more preferably 0.5-5 bar, more preferably 0.7-3 bar, more preferably 0.8-2. It is carried out at a pressure of .5 bar, more preferably 0.9 to 2.2 bar. In a particularly preferred embodiment of the process according to the invention for converting oxygenates to olefins, the contacting in step (2) is carried out at a pressure of 1 to 2 bar.

  Thus, according to the invention, the contact according to (2) is 0.1-10 bar, preferably 0.3-7 bar, more preferably 0.5-5 bar, more preferably 0.7-3 bar, Implementation of a process for converting oxygenates to olefins, more preferably carried out at a pressure in the range from 0.8 to 2.5 bar, more preferably from 0.9 to 2.2 bar, more preferably from 1 to 2 bar. Form is preferred.

  Furthermore, there are no particular restrictions on the manner of carrying out the process according to the invention for converting oxygenates to olefins, so it is possible to use continuous or discontinuous processes, such as for example batch processes. Can be implemented in the form. According to the invention, it is preferred to carry out the process according to the invention for the conversion of oxygenates in a continuous process. Therefore, according to the present invention, an embodiment of a method for converting oxygenate to olefin, which is a continuous method, is preferred.

With respect to these preferred embodiments of the continuous process, there are no restrictions on the selected space velocity provided that the conversion of oxygenate to olefin can be performed. Thus, for example, in the range of 0.5～50H ^-1, it is possible to select a space velocity in the contact in step (2), 1~30h ^-1, more preferably 3～25H ^-1, further preferably 5~20h ^-1, more preferably 7~15h ^-1, more preferably a space velocity (WHSV = weight hourly space velocity of 8～12H ^-1 is oxygenate reactant stream (kg / hr) and the reactor Is preferably selected as a ratio of the amount (kg) of zeolite. In a particularly preferred embodiment of the process according to the invention for converting oxygenates, a range of 9-11 h ⁻¹ is selected as the space velocity for contacting the gas stream in step (2). In an alternative embodiment of the continuous process, in particular a preferred embodiment in which the layer applied to the catalyst substrate further comprises a binder, the space velocity in the course of contact in step (2) is in the range of 0.1-20 h ⁻¹ . 0.5 to 15 h ⁻¹ , more preferably ¹ to 10 h ⁻¹ , more preferably 1.5 to 8 h ⁻¹ , more preferably 2 to 7 h ⁻¹ , more preferably 2.5 to It is preferable to select a space velocity of 6 h ⁻¹ , more preferably 3 to 5 h ⁻¹ , more preferably 3.5 to 4.5 h ⁻¹ .

Therefore, according to the present invention, the space velocity in the contact process according to (2) is 0.5 to 50 h ⁻¹ , preferably ¹ to 30 h ⁻¹ , more preferably 3 to 25 h ⁻¹ , more preferably 5 to 20 h. ^-1, more preferably 7～15H ^-1, more preferably in the range of 8～12H ^-1, more preferably 9～11H ^-1, embodiments of the method for converting oxygenates to olefins are preferred. Thus, in accordance with the present invention, step (2) a space velocity in the course of the contact in the 0.1 to 20 ^-1, preferably 0.5～15H ^-1, more preferably 1～10H ^-1, more preferably 1. 5 to 8 h ⁻¹ , more preferably 2 to 7 h ⁻¹ , more preferably 2.5 to 6 h ⁻¹ , more preferably 3 to 5 h ⁻¹ , and still more preferably 3.5 to 4.5 h ⁻¹ . Certain embodiments of the process for converting oxygenates to olefins are likewise preferred.

  As described above and shown in the examples of the present application, the catalyst of the present invention has a particularly long service life, particularly in the process for converting oxygenates described in this application, particularly with respect to certain preferred embodiments of the process according to the present invention. Can be realized. Surprisingly, therefore, the process using the catalyst according to the invention must interrupt the process for regeneration of the catalyst, at least with respect to the process using this catalyst batch compared to the process using the prior art catalyst. It has become clear that the useful life of the catalyst can be significantly extended before it runs out. Therefore, according to the present invention, it is particularly preferred to select a long service life to carry out the process of converting oxygenates to olefins as described in this application at one of the specific or preferred space velocities.

Therefore, 15 to 400 hours, more preferably 20 to 300 hours, more preferably 60 to 250 hours, more preferably 90 to 220 hours, more preferably 110 to 200 hours, still more preferably 130 to 180 hours, more preferably A practical lifetime in the range of 150 to 170 hours, more preferably 155 to 165 hours is preferred. More particularly, therefore, a working life of 15 to 400 hours is preferred, for example at a space velocity in the range of 0.5 to 50 h ⁻¹ , based on the specific preferred space velocity at which the process according to the invention is carried out. More preferably service life of 20 to 300 hours at a space velocity 1~30h ^-1, more preferably service life of 60 to 250 hours at a space velocity 1~30h ^-1, 90~220 hours at a space velocity of 3～25H ^-1 service life more preferably, still more preferably a service life of 110 to 200 hours at a space velocity in the range of 5～20H ^-1, more preferably useful life of 130 to 180 hours at a space velocity of 7～5H ^-1, space More preferably, the speed is 8 to 12 h ⁻¹ and 150 to 170 hours. In a particularly preferred embodiment of the process according to the invention, the range of 155 to 165 hours at a space velocity of 9 to 11 h ⁻¹ is selected as the practical life of the catalyst in which the continuous process is carried out without interruption.

In an alternative embodiment of the invention, in particular a preferred embodiment in which the layer applied to the catalyst substrate further comprises a binder, it is in the range of 5 to 800 hours, more preferably in the range of 10 to 600 hours, more preferably 30 to 550 hours, more preferably 50-500 hours, more preferably 70-450 hours, more preferably 80-420 hours, more preferably 90-400 hours, more preferably 100- A practical lifetime in the range of 380 hours is preferred. More particularly, therefore, on the basis of certain preferred space velocities, for example 0. Practical lifetimes of 5 to 800 hours with a space velocity in the range of ¹ to 20 h ⁻¹ are preferred. More preferably service life of 10 to 600 hours at a space velocity 0.5~15h ^-1, more preferably service life of 30 to 550 hours at a space velocity 1~10h ^-1, at a space velocity of 1.5～8H ^-1 A practical life of 50 to 500 hours is more preferred, a practical life of 70 to 450 hours at a space velocity of 2 to 7 h ⁻¹ is further preferred, and a practical life of 80 to 420 hours at a space velocity of 2.5 to 6 h ⁻¹ is more preferred. Further, a practical life of 90 to 400 hours at a space velocity of 3 to 5 h ⁻¹ is more preferable, and a practical life of 100 to 380 hours at a space velocity of 3.5 to 4.5 h ⁻¹ is further preferable.

  According to the invention, certain preferred embodiments relating to a selected service life, in particular a service life selected in combination with a specific space velocity, are preferably present in the gas stream according to (1) of the method according to the invention. With regard to the minimum conversion of one or more oxygenates, a sustained conversion below this value will subsequently lead to the performance of catalyst regeneration. According to the present invention, there is no particular limitation on the selected minimum conversion, whereby one or more oxygenates present in the gas stream according to (1) of the process according to the invention during the practical life of the catalyst. It is preferred that complete conversion of the nate is possible. Thus, in a preferred embodiment of the present invention, a minimum conversion of 60% of one or more oxygenates present in the gas stream according to (1) of the process according to the present invention is selected, and a sustained conversion below this value is The minimum conversion of one or more oxygenates present in the gas stream according to (1) of the process according to the invention leading to the performance of the catalyst regeneration is preferably 70% or more, more preferably 80% or more, more preferably 85% or more, more preferably 90% or more, more preferably 95% or more, more preferably 97% or more, further preferably 98% or more, and more preferably 99% or more is selected.

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

  The invention further relates to a method of using the inventive catalyst described above, in particular a method of using the inventive catalyst according to certain preferred embodiments described in this application. According to the present invention, there is in principle no limitation with respect to the process using the catalyst of the present invention, so that the catalyst corresponds to the conversion of oxygenates to olefins, or the catalyst corresponds to chemical conversion. Any conceivable contact method that exhibits catalysis can be used. However, according to the present invention, the catalyst of the present invention is preferably a method for producing olefins from methanol (MTO method), more preferably a method for producing gasoline from methanol (MTG method), and a hydrocarbon from methanol. Used in the process, the process for producing propylene from methanol (MTP process), the process for producing propylene / butylene from methanol (MT3 / 4 process), and the alkylation of aromatic compounds, or the fluid catalytic cracking process (FCC process). The However, according to the present invention, the catalyst of the present invention is preferably a process for producing olefins from methanol (MTO process), more preferably a process for producing propylene / butylene from methanol (MT3 / 4 process), especially the present invention. Is used in a process for converting oxygenate to olefin in one particular or preferred method for converting oxygenate to olefin.

Examples Comparative Example 1
Preparation of Extrudates Containing H-ZSM-5 380 g of Si / Al = 50 H-ZSM-5 (Zeochem ZEO-cat PZ2-100 H) was mixed with 329 g of pseudo-boehmite (Pural SB; Sasol) 10 g of formic acid in 50 ml of water was added and the mixture was treated with 300 ml of water in a kneader to obtain a homogeneous material. The starting mass was chosen so that the zeolite / binder ratio of the calcined extrudate corresponded to 60:40. The kneaded material was passed through a 2.5 mm die at about 100 bar using an extrusion press. Subsequently, the extrudates were dried in a drying cabinet at 120 ° C. for 16 hours (after a heating time of 4 hours) and calcined in a muffle furnace at 500 ° C. for 4 hours. Thereafter, the extrudate was treated with two steel balls (diameter about 2 cm, 258 g / sphere) in a sieving machine to obtain 1.6-2.0 mm pieces.

Comparative Example 2
Production of a substrate coated with H-ZSM-5 (load amount: 71 g / l)
An aqueous suspension (solid concentration 40% by mass) of H / ZSM-5 zeolite (Zeochem ZEO-cat PZ2-100H) with Si / Al = 50 was prepared and homogenized with an ultrasonic cleaner. A cylindrical honeycomb piece body of cordierite (900 cpsi, diameter 0.9 cm, length = 11 cm) was immersed in this suspension, and then dried by blowing compressed air. The coated support was then dried at 110 ° C. for 1 hour followed by calcination at 550 ° C. for 3 hours. The coating process is repeated until a loading of 0.5 g of zeolite per honeycomb piece body (0.071 g / cm ³ ) is achieved and the amount of suspension applied is reduced to the amount of dry material per liter of honeycomb total volume. Reported in grams.

Production of a support coated with Mg-ZSM-5 (load amount: 71 g / l)
Si / Al = 50 H-ZSM-5 (Zeochem ZEO-cat PZ2-100 H) powder was spray impregnated with an amount of magnesium nitrate solution corresponding to 90% of its water absorption capacity. The amount of Mg weighed was such that the powder after calcination contained 4% by weight of Mg. For impregnation, 58.7 g of zeolite powder was introduced into a round bottom flask and attached to a rotary evaporator. While heating, 43.9 g of magnesium nitrate was dissolved in water, and distilled water was added to make the total liquid volume 54 ml. The obtained magnesium nitrate solution was introduced into a dropping funnel, and while rotating, the powder was gradually sprayed through a glass spray nozzle in which 100 l / hour of N ₂ was flowed. During this time, the flask was removed at regular intervals and shaken by hand to achieve a uniform distribution. When the addition of the magnesium nitrate solution was complete, the powder was spun for another 10 minutes. Subsequently, the powder was dried in a quartz rotary sphere flask at 120 ° C. for 16 hours, then calcined at 500 ° C. for 5 hours under air (20 l / hour), and the calcined powder was subsequently analyzed by an analytical mill. Was crushed to a small size using a sieve and sieved with a sieve having a mesh size of 1 mm.

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

Elemental analysis:
Mg: 4g / 100g
The Mg-ZSM-5 powder produced by spray impregnation was applied to the honeycomb piece body according to Comparative Example 2, and the solid concentration of Mg-ZSM-5 in the aqueous suspension used for this was 20% by mass. there were. According to Comparative Example 2, the coating process was repeated until a load of 0.5 g (0.071 g / cm ³ ) of Mg-ZSM-5 per honeycomb piece body was achieved.

Production of a support coated with Mg-ZSM-5 (load amount: about 85 g / l)
First, distilled water was added to a vessel equipped with a propeller stirrer. While continuously stirring and adjusting the speed, the Mg-ZSM-5 powder prepared according to Example 1 was gradually added until a solid content of 33% by weight was achieved. After this, the Mg-ZSM-5 starting suspension was pulverized to a particle size D ₉₀ of 10 μm with a stirring ball mill. During grinding, the temperature did not exceed 30 ° C. After grinding, Ludox AS-40 was added as a binder. The total solid content of the binder was 12% by mass relative to the total solid content of the final suspension.

To produce a support substrate, the suspension was applied to a honeycomb (cell density 400 cpsi (62 cells / cm ² ) and wall thickness 6-7 mil (152.4 μm to 177.8 μm cordierite honeycomb)). did. For this, the suspension was diluted to 28% solids. The catalyst was immersed in the suspension over the entire height so that all cells were completely filled. After waiting 10 seconds, the substrate was removed from the suspension, turned over, and excess suspension was removed from the inlet to the outlet side with compressed air.

  Subsequently, the catalyst was dried in the dryer by hot air (140 ° C.) alternately from both sides with a cycle time of 10 seconds for a total of 45 minutes. Thereafter, the catalyst was calcined at a maximum temperature of 590 ° C. in a fluid calciner and the operating catalyst passed through 3 heating zones, 1 constant temperature zone and 1 cooling zone within 3 hours.

The load amount of the carrier substrate was calculated to be 0.085 g / cm ³ based on the mass balance.

Production of a support coated with Mg-ZSM-5 (load amount: about 150 g / l)
The production method according to Example 2 was repeated except that the support substrate was coated twice. For this purpose, the suspension was first diluted with distilled water to 26% solids, the catalyst was coated with the diluent according to Example 2, and then the layers were heat-fixed. The suspension was then further diluted to 25% solids and the coating and heat fixing operations according to Example 2 were repeated with this suspension to achieve a support substrate loading of 0.15 g / cm ³ .

Production of support coated with Mg-ZSM-5 (load amount: about 190 g / l)
The production method according to Example 2 was repeated except that the support substrate was repeatedly coated in the same manner as in Example 3. For this purpose, the suspension was first diluted with distilled water to a solid content of 28%, the catalyst was coated with the diluent according to Example 2 and then the layers were heat-fixed. The suspension was then further diluted to 25% solids and the coating and heat fixing operations according to Example 2 were repeated with this suspension to achieve a support substrate loading of 0.19 g / cm ³ .

Comparative test in a method for producing propylene / butylene from methanol (MT3 / 4 method) 2 g of the catalyst produced according to Comparative Example 1 was mixed with 24 g of silicon carbide, and the reactor bed was 30 cm long in a continuous electric heating tubular reactor. And a diameter of 12 mm. In tests using catalysts prepared according to Comparative Example 2 and Examples 1-4, two coated honeycomb bodies in each case were placed in the reactor and sealed with glass fiber cords on the tube wall.

Upstream of the test reactor, methanol vapor is generated to give a gas stream containing 75% by volume methanol and 25% by volume N ₂ , 275 ° C. and (absolute) by a pre-reactor charged with 34 ml of alumina pieces. Conversion to dimethyl ether at a pressure of 1-2 bar. The stream containing dimethyl ether is then passed through a tubular reactor in which a temperature of 450-500 ° C., WHSV (= mass space velocity) ranging from 3.6 to 10 h ⁻¹ on a methanol basis, depending on the sample, and The (absolute) pressure was converted at 1-2 bar and the reaction parameters were maintained throughout the run time. Downstream of the tubular reactor, the gaseous product mixture was analyzed by on-line chromatography.

  The results obtained for the selectivity of the catalysts according to Comparative Examples 1 and 2 and Examples 1 to 4 in the MT3 / 4 method are shown in Table 1, which are in the run time of the catalyst where the methanol conversion was 95% or more. The average selectivity is reproduced.

  As can be inferred from the values in Table 1, it is surprising that the specific use of the alkaline earth metal-containing zeolite applied to the support substrate by the MT3 / 4 method has a very high selectivity. In addition to being directed against propylene and butylene in the product stream, these are surprisingly long, as can be seen from the unexpectedly long service life of the catalyst capable of maintaining greater than 95% methanol conversion. Maintained over time.

As can be seen from the results of Comparative Examples 1 and 2 in Table 1 and Example 1, the increase in service life achieved by applying zeolite to the substrate or the unexpected increase in MeOH loading per cycle is expected. In addition, it has become clear that it can be increased several times by the additional use of alkaline earth metal zeolites. More surprisingly, however, this simultaneously leads to a selectivity which is even more unexpected and particularly constant for the catalyst according to Example 1 extending to the C ₃ and C ₄ olefins propylene and butylene. The present invention is therefore a catalyst for the conversion of oxygenates to olefins, which is present in particular in the form of extrudates, as evidenced by the test results obtained with the MT3 / 4 method according to Example 5. Associated with a surprisingly long service life compared to a catalyst (see Comparative Example 1) or a catalyst applied to a support substrate but not containing an alkaline earth metal (see Comparative Example 2). It provides a catalyst with unexpectedly high selectivity for C ₃ and C ₄ olefins.

  As can be seen from the results of the catalysts according to Examples 2, 3 and 4 containing the binder compared to Example 1, a significant improvement in the service life was observed despite the method of using the binder. More specifically, it was not always possible to achieve the methanol loading per cycle observed in Example 1 with the constantly higher loadings of the catalyst in Examples 3 and 4, but more substantial in service life. Increase realized. On the other hand, however, the method of using a binder results in a much more durable catalyst due to the improved adhesion of the layer.

Very surprisingly, however, it has been found that the process using binders further increases the selectivity of the catalyst for C ₃ -and C ₄ -olefins. More specifically, the selectivity for C ₃ -olefin of Example 2 is considerably higher than that of Example 1, which has already shown a significant increase compared to the selectivity for the comparative C ₃ -and C ₄ -olefins. Is allowed to jump. This occurs in particular without any trade-off with respect to the selectivity for C ₄ -olefins and corresponds to the results of Example 1. When the loading is increased in each of Examples 3 and 4, a very high selectivity for C ₃ -olefins is observed compared to Example 1, especially the comparative example. Surprisingly, however, the selectivity for C ₄ -olefins is increased in Examples 3 and 4, with the highest selectivity being observed in Example 3.

Thus, the present invention is a catalyst for the conversion of oxygenates to olefins, which not only increases the durability of the catalyst by the method using a binder, but also provides a higher load on the support substrate. Also provided is a catalyst that increases the useful life of the catalyst by the ability to use an amount of catalyst. More particularly, however, surprisingly, the specific use of the binder in the catalyst of the present invention could further improve the selectivity for C ₄ -olefins, and more particularly for C ₃ -olefins. It became clear. Thus, the present invention is a greatly improved catalyst for the conversion of oxygenates to olefins, particularly with high selectivity and long service life, especially for C ₃ -and C ₄ -olefins. A catalyst is provided.

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Claims (29)

A catalyst for the conversion of oxygenates to olefins,
A support substrate;
-A layer applied to the substrate,
The catalyst comprises one or more zeolites of MFI, MEL and / or MWW structure type, the one or more zeolites comprising one or more alkaline earth metals.   The catalyst according to claim 1, wherein the shape of the support substrate is selected from the group consisting of granules, pellets, meshes, rings, spheres, cylinders, cylinders, monoliths, and mixtures and / or combinations of two or more thereof. .   The catalyst of claim 2, wherein the one or more zeolites are selected from the group consisting of honeycombs, braids, foams, and combinations of two or more thereof.   The catalyst according to any one of claims 1 to 3, wherein the support substrate comprises a ceramic and / or metallic material.   The catalyst according to any one of claims 1 to 4, wherein the one or more zeolites are of the MFI structure type.   The catalyst according to any one of claims 1 to 5, wherein the alkaline earth metal is Mg.   The one or more zeolites are of MFI, MEL and / or MWW structure type and one or more alkaline earth metals, in each case one or more of MFI, MEL and / or MWW structure type The catalyst according to any one of claims 1 to 6, wherein the catalyst is contained as a metal in a range of 0.1 to 20% by mass with respect to the total amount of zeolite. 8. One or more zeolites of MFI, MEL and / or MWW structure type comprising a total load of 0.005 to 1 g / cm ³ relative to the volume of the coated support substrate. The catalyst as described in any one. A method for producing the catalyst according to any one of claims 1 to 8, comprising:
(I) providing a support substrate and one or more zeolites of MFI, MEL and / or MWW structure type;
(Ii) impregnating one or more zeolites of MFI, MEL and / or MWW structure type with a solution comprising one or more alkaline earth metals, preferably by spray impregnation;
(Iii) optionally drying one or more impregnated zeolites obtained in (ii);
(Iv) optionally calcining one or more impregnated zeolites obtained in (ii) or (iii);
(V) producing an impregnated, optionally dried, and / or calcined mixture comprising one or more zeolites of MFI, MEL and / or MWW structure type and one or more solvents; ,
(Vi) homogenizing the mixture obtained in (v) and optionally adding a binder;
(Vii) coating the support substrate with the homogenized mixture obtained in (vi);
(Viii) optionally drying the coated support substrate obtained in (vii);
(Ix) optionally calcining the coated support substrate obtained in (vii) or (viii). After the impregnation in step (ii) or the preparation of the mixture in step (v), preferably after the preparation of the mixture in step (v), more preferably homogenizing the mixture obtained in (v) (vi) in, MFI, the MEL and / or one or more impregnation zeolite MWW structure type particle size _{D 50} in the range of 0.01～200Myuemu, the method of claim 9. After the impregnation in step (ii) or the preparation of the mixture in step (v), preferably after the preparation of the mixture in step (v), more preferably homogenizing the mixture obtained in (v) (vi) in, MFI, the MEL and / or one or more impregnation zeolite MWW structure type particle size _{D 90} in the range of 0.5 to 50 [mu] m, method according to claim 9 or 10.   The method according to any one of claims 9 to 11, wherein the drying in (iii) and / or (viii) is performed at a temperature in the range of 50-220 ° C.   The method according to any one of claims 9 to 12, wherein the calcination in (iv) and / or (ix) is performed at a temperature in the range of 300-850 ° C.   The solution used in (ii) and / or the mixture prepared in (v) is selected from the group consisting of alcohol, water, a mixture of two or more alcohols, and a mixture of water and one or more alcohols. 14. A method according to any one of claims 9 to 13, comprising one or more solvents to be prepared.   15. The method according to any one of claims 9 to 14, wherein the solids concentration of the mixture produced in (v) is in the range of 5 to 50% by weight.   The method according to any one of claims 9 to 15, wherein the homogenization in (vi) is carried out by stirring, kneading, agitation, vibration or a combination of two or more thereof.   The method according to any one of claims 9 to 16, wherein the coating in (vii) is performed by spray coating and / or wash coating.   18. A method according to any one of claims 9 to 17, wherein step (vii) is repeated one or more times.   A catalyst for the conversion of oxygenates to olefins obtained by the process according to any one of claims 9 to 18. A method for converting oxygenate to olefin comprising:
(1) providing a gas stream comprising one or more oxygenates;
(2) A method comprising contacting a gas stream with the catalyst according to any one of claims 1 to 8 or 19.   21. The method of claim 20, wherein the gas stream according to (1) comprises one or more oxygenates selected from the group consisting of aliphatic alcohols, ethers, carbonyl compounds and mixtures of two or more thereof.   The method according to claim 19 or 21, wherein the oxygenate content in the gas stream according to (1) is in the range of 30 to 100% by volume with respect to the total volume.   The method according to any one of claims 19 to 22, wherein the water content in the gas stream according to (1) is in the range of 5 to 60% by volume with respect to the total volume.   24. The method according to any one of claims 19 to 23, wherein the contact according to (2) is performed at a temperature in the range of 200 to 700 <0> C.   25. A method according to any one of claims 19 to 24, wherein the contact according to (2) is performed at a pressure in the range of 0.1 to 10 bar.   26. A method according to any one of claims 19 to 25 which is a continuous method. 27. The method of claim 26, wherein the space velocity in contact at (2) is in the range of 0.5-50 h- ¹ .   28. A process according to claim 27, wherein the service life of the coated support substrate as a catalyst, wherein the continuous process is carried out without interruption, ranges from 15 to 400 hours.   A method for producing an olefin from methanol (MTO method), a method for producing gasoline from methanol (MTG method), and a method for producing hydrocarbons from methanol. , A method for producing propylene from methanol (MTP method), a method for producing propylene / butylene from methanol (MT3 / 4 method), for alkylation of aromatic compounds, or by fluid catalytic cracking method (FCC method) How to use.