Process for the conversion of oxygenates to olefins

Abstract

The present invention relates to a process for converting oxygenates to olefins, comprising (1) providing a gas stream comprising one or more ethers; (2) contacting the gas stream provided in (1) with a catalyst, the catalyst comprising a support substrate and a layer applied to the substrate, the layer comprising one or more zeolites of the MFI, MEL and/or MWW structure type.

1 - 26 . (canceled) 
     
     
         27 . A catalyst for the conversion of oxygenates to olefins, wherein the catalyst comprises one or more zeolites of the MFI, MEL and/or MWW structure type and particles of one or more metal oxides, the one or more zeolites of the MFI, MEL and/or MWW structure type comprising one or more alkaline earth metals, and the particles of the one or more metal oxides comprising phosphorus, the phosphorus being present at least partly in oxidic form, and the one or more alkaline earth metals being selected from the group consisting of Mg, Ca, Sr, Ba and combinations of two or more thereof. 
     
     
         28 . The catalyst according to  claim 27 , wherein the one or more zeolites of the MFI, MEL and/or MWW structure type comprise phosphorus, the phosphorus being present at least partly in oxidic form. 
     
     
         29 . The catalyst according to  claim 27 , wherein the one or more zeolites are of the MFI structure type. 
     
     
         30 . The catalyst according to  claim 27 , wherein the alkaline earth metal is Mg. 
     
     
         31 . The catalyst according to  claim 27 , wherein the one or more zeolites of the MFI, MEL and/or MWW structure type comprise the one or more alkaline earth metals in a total amount in the range from 0.1 to 20% by weight, based on the total amount of the one or more zeolites of the MFI, MEL and/or MWW structure type and calculated as the metal. 
     
     
         32 . The catalyst according to  claim 27 , wherein the one or more metal oxides are selected from the group consisting of alumina, titania, zirconia, aluminum-titanium mixed oxides, aluminum-zirconium mixed oxides, aluminum-lanthanum mixed oxides, aluminum-zirconium-lanthanum mixed oxides, titanium-zirconium mixed oxides and mixtures of two or more thereof. 
     
     
         33 . The catalyst according to  claim 27 , wherein the zeolite:metal oxide weight ratio in the catalyst is in the range from 10:90 to 95:5. 
     
     
         34 . The catalyst according to  claim 27 , wherein the total amount of phosphorus, based on the sum of the total weight of zeolites of the MFI, MEL and/or MWW structure type and the total weight of the particles of the one or more metal oxides and calculated as the element, is in the range from 0.1 to 20% by weight. 
     
     
         35 . The catalyst according to  claim 27  in the form of a shaped body comprising a mixture of the one or more zeolites of the MFI, MEL and/or MWW structure type and of the particles of the one or more metal oxides. 
     
     
         36 . A process for preparing the catalyst according to  claim 35 , comprising
 (i) providing the one or more zeolites of the MFI, MEL and/or MWW structure type;   (ii) impregnating the one or more zeolites of the MFI, MEL and/or MWW structure type with a solution comprising the one or more alkaline earth metals;   (iii) optionally drying the one or more impregnated zeolites obtained in (ii);   (iv) optionally calcining the one or more impregnated zeolites obtained in (ii) or (iii);   (v) preparing a mixture comprising the one or more impregnated and optionally dried and/or calcined zeolites of the MFI, MEL and/or MWW structure type, one or more solvents and particles of the one or more metal oxides and/or precursor compounds of the one or more particles of the one or more metal oxides;   (vi) homogenizing the mixture obtained in (v);   (vii) extruding the homogenized mixture obtained in (vi);   (viii) optionally drying the extrudate obtained in (vii);   (ix) optionally calcining the extrudate obtained in (vii) or (viii);   (x) impregnating the optionally dried and/or calcined extrudate with a phosphorus-comprising solution;   (xi) optionally drying the impregnated extrudate obtained in (x);   (xii) optionally calcining the extrudate obtained in (x) or (xi).   
     
     
         37 . A process for preparing the catalyst according to  claim 35 , comprising
 (i) providing the one or more zeolites of the MFI, MEL and/or MWW structure type;   (ii) impregnating the one or more zeolites of the MFI, MEL and/or MWW structure type with a solution comprising the one or more alkaline earth metals;   (iii) optionally drying the one or more impregnated zeolites obtained in (ii);   (iv) optionally calcining the one or more impregnated zeolites obtained in (ii) or (iii);   (v.1) preparing a mixture comprising the one or more impregnated and optionally dried and/or calcined zeolites of the MFI, MEL and/or MWW structure type and particles of the one or more metal oxides and/or precursor compounds of the one or more particles of the one or more metal oxides;   (v.2) admixing the mixture obtained in (v.1) with a phosphorus-comprising solution;   (v.3) mixing the mixture obtained in (v.2) with one or more solvents;   (vi) homogenizing the mixture obtained in (v.3);   (vii) extruding the homogenized mixture obtained in (vi);   (viii) optionally drying the extrudate obtained in (vii);   (ix) optionally calcining the extrudate obtained in (vii) or (viii).   
     
     
         38 . The process according to  claim 36 , wherein the impregnating in (ii) or the drying in (iii) or the calcining in (iv) is followed by bringing the one or more impregnated zeolites of the MFI, MEL and/or MWW structure type to a particle size D50 in the range from 5 to 1000 μm. 
     
     
         39 . The process according to  claim 36 , wherein the drying in (iii), (viii) and/or (xi) is effected at a temperature in the range from 50 to 220° C. 
     
     
         40 . The process according to  claim 36 , wherein the calcining in (iv), (ix) and/or (xii) is effected at a temperature in the range from 300 to 850° C. 
     
     
         41 . The process according to  claim 36 , wherein the solution used in (ii) and/or (x) and/or the mixture prepared in (v) comprises one or more solvents selected from the group consisting of
 a. alcohols,   b. water,   c. mixtures of two or more alcohols, and   d. mixtures of water and one or more alcohols.   
     
     
         42 . A catalyst for the conversion of oxygenates to olefins, obtained by the process according to  claim 36 . 
     
     
         43 . A process for converting oxygenates to olefins, comprising:
 (1) providing a gas stream comprising one or more oxygenates;   (2) contacting the gas stream with a catalyst according to  claim 27 .   
     
     
         44 . The process according to  claim 43 , 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. 
     
     
         45 . The process according to  claim 43 , wherein the content of oxygenates in the gas stream according to (1) is in the range from 30 to 100% by volume based on the total volume. 
     
     
         46 . The process according to  claim 43 , wherein the water content in the gas stream according to (1) is in the range from 5 to 60% by volume based on the total volume. 
     
     
         47 . The process according to  claim 43 , wherein the contacting according to (2) is effected at a temperature in the range from 200 to 700° C. 
     
     
         48 . The process according to  claim 43 , wherein the contacting according to (2) is effected at a pressure in the range from 0.1 to 10 bar. 
     
     
         49 . The process according to  claim 43 , wherein the process is a continuous process. 
     
     
         50 . The process according to  claim 49 , in which the space velocity in the contacting according to (2) is in the range from 0.5 to 50 h-1. 
     
     
         51 . The process according to  claim 50 , in which the service life of the catalyst during which the continuous process is performed without interruption is in the range from 40 to 300 h. 
     
     
         52 . A method which comprises utilizing the catalyst according to  claim 27  in a process wherein the process is a methanol-to-olefin process (MTO process), a methanol-to-gasoline process (MTG process), a methanol-to-hydrocarbon process, a methanol-to-propylene process (MTP process), a methanol-to-propylene/butylene process (MT¾ process), an alkylation of aromatics or in fluid catalytic cracking process (FCC process).