Catalyst for epoxidation reactions

Abstract

The present invention relates to the manufacture of solid materials or shaped bodies containing at least one zeolite and being at least partly crystalline. Furthermore, the present invention relates to the solid materials or shaped bodies as such and to the use of these materials for reactions of compounds having at least one C—C double bond with at least one hydroperoxide. Specifically, the present invention relates to a process for the manufacture of a solid material containing at least one zeolite and being at least partly crystalline, wherein the synthesis of the said solid material involves at least one partial step of contacting at least one transition metal oxide source with at least one epoxide or hydrolysate thereof prior to or during the at least partial crystallization of said solid material.

1 - 19 . (Canceled).  
     
     
         20 . A catalytic material for epoxidation reactions containing at least one zeolite and being at least partially crystalline, obtainable by a process comprising the steps 
 (I) at least partial crystallization of at least one solid material containing at least one zeolite out of a synthesis mixture, said mixture comprising at least a silicon source, a transition metal oxide source and a mineralizing and/or structure forming agent, resulting in a mixture (I) containing at least said solid material and a mother liquor, step (I) further comprising adding an epoxide or hydrolysate thereof to the transition metal oxide source;    (II) separating and/or concentrating of the solid material from mixture (I), wherein step (II) additionally includes drying of the solid material;    (C) calcining of the solid material at temperatures higher than 400° C.    
     
     
         21 . The catalytic material of  claim 20 , wherein the silicon source comprises at least one silicon oxide, the transition metal oxide source comprises at least one titanate, and the mineralizing and/or structure forming agent comprises at least one tetraalkylammonium hydroxide.  
     
     
         22 . The catalytic material of  claim 20 , wherein the silicon source comprises at least tetraethoxy silicate, the transition metal oxide source comprises at least tetrabutylorthotitanate, the mineralizing and/or structure forming agent comprises at least tetrapropylammonium hydroxide, and the epoxide or hydrolysate thereof comprises at least propylene oxide or propylene glycol.  
     
     
         23 . The catalytic material of  claim 20 , wherein the zeolite contains Ti.  
     
     
         24 . The catalytic material of  claim 20 , wherein the zeolite is a titanium silicalite.  
     
     
         25 . The catalytic material of  claim 20 , wherein in step (II), the solid material is separated from the mother liquor by filtration, ultrafiltration or diafiltration.  
     
     
         26 . The catalytic material of  claim 20 , wherein in step (II), the solid material is separated from the mother liquor by spray drying or spray granulation.  
     
     
         27 . The catalytic material of  claim 20 , said process further comprising (S) shaping of the solid material to produce a shaped body.  
     
     
         28 . The catalytic material of  claim 27 , said process further comprising drying the shaped body at a temperature of from about 30° C. to about 140° C. for a time from 1 to 20 h and subsequently calcining the dried shaped body at a temperature of from about 400° C. to about 800° C. for a time from about 3 h to about 10 h.  
     
     
         29 . The catalytic material of  claim 28 , said process further comprising 
 (W) bringing the dried and calcined shaped body in contact with a composition containing water.    
     
     
         30 . A catalytic material for epoxidation reactions containing at least one zeolite and being at least partially crystalline, obtainable by a process comprising a step (I), which step comprises at least partial crystallization of at least one solid material containing at least one zeolite out of a synthesis mixture, wherein said process comprises contacting at least one transition metal oxide source with at least one epoxide or hydrolysate thereof prior to or during the at least partial crystallization, wherein step (I) comprises 
 (Ia) mixing of at least one hydrolyzable silicon source with a mineralizing and/or structuring agent and water;    (Ib) mixing of at least one transition metal oxide source with an epoxide or a hydrolysate thereof;    (Ic) mixing of the mixtures from (Ia) and (Ib) so that at least a part of the hydrolyzable compounds hydrolyzes;    (Id) distilling at least parts of the alcohol that has been formed as a result of the at least partial hydrolysation of at least part of the hydrolyzable compounds;    (Ie) adding water to the bottom of (Id);    (If) reacting of the synthesis mixture resulting from (Ie) at a temperature elevated with respect to room temperature to obtain a mixture (I) of the solid material in its mother liquor,    said process further comprising    (II) separating and/or concentrating of the solid material in mixture (I), wherein (II) additionally includes drying of the solid material;    (C) calcining of the solid material at temperatures higher than 400° C.    
     
     
         31 . The catalytic material of  claim 30 , wherein the hydrolyzable silicon source comprises at least one silicon oxide, the mineralizing and/or structuring agent comprises at least one tetraalkylammonium hydroxide, and the transition metal oxide source comprises at least one titanate.  
     
     
         32 . The catalytic material of  claim 30 , wherein the epoxide is propylene oxide and the hydrolysate of the epoxide is propylene glycol.  
     
     
         33 . The catalytic material of  claim 32 , wherein the hydrolyzable silicon source comprises at least tetraethoxy silicate, the mineralizing and/or structuring agent comprises at least tetrapropylammonium hydroxide, the transition metal oxide source comprises at least tetrabutylorthotitanate.  
     
     
         34 . The catalytic material of  claim 33 , wherein in (Ib), the transition metal oxide source is mixed with propylene glycol.  
     
     
         35 . The catalytic material of  claim 30 , wherein the at least one zeolite contains Ti and belongs to at least one of the following structure classes consisting of the group of MFI, MEL, MWW, BEA and any mixed structures thereof.  
     
     
         36 . The catalytic material of  claim 30 , wherein the at least one zeolite is a titanium silicalite.  
     
     
         37 . The catalytic material of  claim 30 , wherein in step (II), the solid material is separated from the mother liquor.  
     
     
         38 . The catalytic material of  claim 37 , wherein in step (II), the solid material is separated from the mother liquor by filtration, ultrafiltration or diafiltration.  
     
     
         39 . The catalytic material of  claim 37 , wherein in step (II), the solid material is separated from the mother liquor by spray drying or spray granulation.  
     
     
         40 . The catalytic material of  claim 30 , said process further comprising 
 (S) shaping of the solid material to produce a shaped body.    
     
     
         41 . The catalytic material of  claim 40 , wherein (S) comprises adding a binding material to the solid material.  
     
     
         42 . The catalytic material of  claim 41 , wherein the binding material is selected from the group consisting of hydrated silica gel, silicic acid, tetraalkoxy silicates, tetraalkoxy titanates, tetraalkoxy zirconates and mixtures of two or thereof.  
     
     
         43 . The catalytic material of  claim 41 , wherein the binding material is selected from the group consisting of tetramethoxy silicate, tetraethoxy silicate and silica sols.  
     
     
         44 . The catalytic material of  claim 41 , wherein (S) comprises milling the solid material and mixing the milled solid material with silica sol, a dispersion of polystyrene, cellulose, polyethylene oxide and water, kneading the resulting mixture and molding the kneaded mixture.  
     
     
         45 . The catalytic material of  claim 44 , wherein molding is extrusion molding.  
     
     
         46 . The catalytic material of  claim 45 , the extrudates obtained having a diameter ranging from about 2 to about 5 mm.  
     
     
         47 . The catalytic material of  claim 40 , said process further comprising drying the shaped body at a temperature of from about 30° C. to about 140° C. for a time from 1 to 20 h and subsequently calcining the dried shaped body at a temperature of from about 400° C. to about 800° C. for a time from about 3 h to about 10 h.  
     
     
         48 . The catalytic material of  claim 47 , said process further comprising 
 (W) bringing the dried and calcined shaped body in contact with a composition containing water.    
     
     
         49 . The catalytic material of  claim 48 , wherein the composition containing water is water in its liquid phase or water steam.  
     
     
         50 . A shaped body for the use as catalyst for reactions of compounds having at least one C—C double bond with at least one hydroperoxide, said shaped body comprising at least one solid material containing at least one zeolite, said zeolite containing Ti and being selected from the group consisting of MFl, MEL, MWW, BEA and any mixed structures thereof, and said solid material being at least partially crystalline, wherein the shaped body is obtainable by a process comprising a step (I), which step comprises at least partial crystallization of the at least one solid material containing at least one zeolite out of a synthesis mixture, wherein said process comprises contacting at least one transition metal oxide source with at least one epoxide or hydrolysate thereof prior to or during the at least partial crystallization, wherein step (I) comprises 
 (Ia) mixing of at least one hydrolyzable silicon source with a mineralizing and/or structuring agent and water;    (Ib) mixing of at least one transition metal oxide source with an epoxide or a hydrolysate thereof;    (Ic) mixing of the mixtures from (Ia) and (Ib) so that at least a part of the hydrolyzable compounds hydrolyzes;    (Id) distilling at least parts of the alcohol that has been formed as a result of the at least partial hydrolysation of at least part of the hydrolyzable compounds;    (Ie) adding water to the bottom of (Id);    (If) reacting of the synthesis mixture resulting from (Ie) at a temperature elevated with respect to room temperature to obtain a mixture (I) of the solid material in its mother liquor,    said process further comprising    (II) separating and/or concentrating of the solid material in mixture (I), wherein (II) additionally includes drying of the solid material;    (C) calcining of the solid material at temperatures higher than 400° C.;    (S) shaping of the solid material to produce a shaped body.    
     
     
         51 . The shaped body of  claim 50 , wherein the hydrolyzable silicon source comprises at least one silicon oxide, the mineralizing and/or structuring agent comprises at least one tetraalkylammonium hydroxide, and the transition metal oxide source comprises at least one titanate.  
     
     
         52 . The shaped body of  claim 50 , wherein the hydrolyzable silicon source comprises at least tetraethoxy silicate, the mineralizing and/or structuring agent comprises at least tetrapropylammonium hydroxide, the transition metal oxide source comprises at least tetrabutylorthotitanate, wherein the epoxide is propylene oxide and the hydrolysate of the epoxide is propylene glycol.  
     
     
         53 . The shaped body of  claim 50 , wherein the at least one zeolite is a titanium silicalite.  
     
     
         54 . The shaped body of  claim 50 , wherein (S) comprises adding a binding material to the solid material, the binding material being selected from the group consisting of tetramethoxy silicate, tetraethoxy silicate and silica sols.  
     
     
         55 . The shaped body of  claim 50 , wherein (S) comprises milling the solid material and mixing the milled solid material with silica sol, a dispersion of polystyrene, cellulose, polyethylene oxide and water, kneading the resulting mixture and molding the kneaded mixture by extrusion molding, wherein extrudates are obtained having a diameter ranging from about 2 to about 5 mm.  
     
     
         56 . The shaped body of  claim 50 , said process further comprising drying the shaped body at a temperature of from about 30° C. to about 140° C. for a time from 1 to 20 h and subsequently calcining the dried shaped body at a temperature of from about 400° C. to about 800° C. for a time from about 3 h to about 10 h.  
     
     
         57 . The shaped body of  claim 56 , said process further comprising 
 (W) bringing the dried and calcined shaped body in contact with a composition containing water.    
     
     
         58 . The shaped body of  claim 57 , wherein the composition containing water is water in its liquid phase or water steam.  
     
     
         59 . The shaped body of  claim 50 , wherein in step (II), the solid material is separated from the mother liquor by filtration, ultrafiltration or diafiltration.  
     
     
         60 . The shaped body of  claim 50 , wherein in step (II), the solid material is separated from the mother liquor by spray drying or spray granulation.  
     
     
         61 . A shaped body for the use as catalyst for the epoxidation of propene with hydrogen peroxide, said shaped body comprising at least one solid material containing a titanium silicalite zeolite and being at least partially crystalline, wherein the shaped body is obtainable by a process comprising a step (I), which step comprises at least partial crystallization of the at least one solid material containing the zeolite out of a synthesis mixture, wherein said process comprises contacting tetrabutylorthotitanate with propylene oxide or propylene glycol prior to or during the at least partial crystallization, wherein step (I) comprises 
 (Ia) mixing of tetraethoxy silicate with tetrapropylammonium hydroxide and water;    (Ib) mixing of tetrabutylorthotitanate with propylene oxide or propylene glycol;    (Ic) mixing of the mixtures from (Ia) and (Ib) so that at least a part of the hydrolyzable compounds hydrolyzes;    (Id) distilling at least parts of the alcohol that has been formed as a result of the at least partial hydrolysation of at least part of the hydrolyzable compounds;    (Ie) adding water to the bottom of (Id);    (If) reacting of the synthesis mixture resulting from (Ie) at a temperature elevated with respect to room temperature to obtain a mixture (I),    said process further comprising    (II) separating of the solid material in mixture (I) by filtration, ultrafiltration, diafiltration, spray-drying or spray-granulation, wherein (II) additionally includes drying of the solid material;    (C) calcining of the separated solid material at temperatures higher than 400° C.;    (S) shaping of the solid material to produce a shaped body comprising milling the solid material and mixing the milled solid material with silica sol, a dispersion of polystyrene, cellulose, polyethylene oxide and water, kneading the resulting mixture and molding the kneaded mixture by extrusion molding, wherein extrudates are obtained having a diameter ranging from about 2 to about 5 mm; said process further comprising drying the extrudates at a temperature of from about 30° C. to about 140° C. for a time from 1 to 20 h and subsequently calcining the dried shaped body at a temperature of from about 400° C. to about 800° C. for a time from about 3 h to about 10 h.    
     
     
         62 . The shaped body of  claim 61 , wherein separation in (II) is filtration, ultrafiltration or diafiltration.  
     
     
         63 . The shaped. body of  claim 61 , said process further comprising 
 (W) bringing the dried and calcined extrudates in contact with a composition containing water, wherein the composition containing water is water in its liquid phase or water steam.