Reaction and use of a solid mixed oxide composition as redox system in the said reaction

Abstract

Solid mixed oxides composition of formula (I): Mo 12 V a Sr b W c Cu d Si e O x   (I) 2≦a≦14, 0.1≦B≦6, 0≦c≦12, 0≦d≦6, 0≦e≦15; x is the quantity of oxygen bonded to the other elements and depends on their oxidation states, are used in the manufacture of acrylic acid by oxidation of acrolein, the said solid composition reacting with acrolein according to the redox reaction (1): SOLID oxidized +ACROLEIN→SOLID reduced +ACRYLIC ACID   (1). To manufacture acrylic acid, a gaseous mixture of acrolein and of water vapor and, if appropriate, of an inert gas is passed over a solid composition of formula (I), to conduct the redox reaction (1) by operating at a temperature of 200 to 500° C., at a pressure of 1.01×10 4 to 1.01×10 6 Pa (0.1 to 10 atmospheres), and with a residence time of 0.01 second to 90 seconds, in the absence of molecular oxygen.

1 . A process for the manufacture of acrylic acid from acrolein, according to the redox reaction (1):  
       SOLID oxidized +ACROLEIN→SOLID reduced +ARCYLIC ACID  (1), 
       said process comprising passing a gaseous mixture of acrolein and of water vapour and optionally of an inert gas over a solid composition of formula (I):  
       Mo 12 V a Sr b W c Cu d Si e O x   (I) 
       in which: 
 a is between 1 and 14, limits included,  
 b is between 0.1 and 6, limits included,  
 c is between 0 and 12, limits included,  
 d is between 0 and 6, limits included,  
 e is between 0 and 15, limits included, and  
 x is the quantity of oxygen bonded to the other elements and depends on their oxidation state,  
 the said solid composition reacting with the acrolein at a temperature of 200 to 500° C., at a pressure of 1.01×10 4  to 1.01×10 6  Pa (0.1 to 10 atmospheres) and with a residence time of 0.01 second to 90 seconds, in the substantial absence of molecular oxygen.  
 
     
     
         2 . A process according to    claim 1   , wherein the redox reaction (1) is conducted at a temperature of 250 to 450° C.  
     
     
         3 . A process according to    claim 1   , wherein the redox reaction (1) is conducted at a pressure of 5.05×10 4 -5.05× 10 5  Pa (0.5-5 atmospheres).  
     
     
         4 . A process according to    claim 3   , wherein the redox reaction (1) is conducted at a pressure of 5.05×10 4 -5.05× 10 5  Pa (0.5-5 atmospheres).  
     
     
         5 . A process according to    claim 1   , wherein the redox reaction (1) is conducted with a residence time of 0.1 second to 30 seconds.  
     
     
         6 . A process according to    claim 4   , wherein the redox reaction (1) is conducted with a residence time of 0.1 second to 30 seconds.  
     
     
         7 . A process according to    claim 1   , wherein once the solid composition is converted to the reduced state, said solid composition is regenerated according to the reaction (2):  
       SOLID reduced+O 2→ Solid oxidized   (2) 
       by heating in the presence of an excess of oxygen or of an oxygen-containing gas at a temperature of 250 to 500° C., for the time needed for the reoxidation of the solid composition.  
     
     
         8 . A process according to    claim 7   , wherein the redox reaction (1) and the regeneration are conducted in a two-stage device comprising a reactor and a regenerator which operate simultaneously and in which two charges of solid composition alternate periodically.  
     
     
         9 . A process according to    claim 7   , wherein the redox reaction (1) and the regeneration are conducted in the same reactor by alternating the reaction and regeneration periods.  
     
     
         10 . A process according to    claim 1    further comprising prior to the reaction, introducing the solid composition into a reactor and flushing the resultant reactor with a continuous flow of an inert gas to remove molecular oxygen.  
     
     
         11 . A process according to    claim 10   , wherein the reaction is conducted in the absence of molecular oxygen.  
     
     
         12 . A process according to    claim 1    further comprising heating the solid composition to 200-500° C. and introducing an aqueous solution of acrolein over the solid composition to initiate the reaction.  
     
     
         13 . A process according to    claim 10    further comprising heating the solid composition to 200-500° C. and introducing an aqueous solution of acrolein over the solid composition to initiate the reaction.  
     
     
         14 . A process according to    claim 1   , wherein the solid composition is of the formula  
       Mo 12 V 4.8 Sr 0.5 W 2.4 Cu 2.2 Ox. 
     
     
         15 . A solid mixed oxide composition of the formula  
       Mo 12 V 4.8 Sr 0.5 W 2.4 Cu 2.2 Ox, 
        x being the quantity of oxygen bonded to the other elements and depending on their oxidation states.