Homogeneous Process for the Hydrogenation of Carboxylic Acids and Derivatives Thereof

Abstract

A homogenous process for the hydrogenation of the carboxylic acids and/or derivatives thereof in the presence of a catalyst comprising ruthenium, rhodium, iron, osmium or palladium, and an organic phosphine is described in which the hydrogenation is carried out in the presence of at least about 1% by weight water. A process for regenerating a catalyst comprising ruthenium, rhodium, iron, osmium or palladium and an organic phosphine is also described in which the regeneration is carried out in the presence of hydrogen and water.

1 . A homogeneous process for the hydrogenation of carboxylic acids and/or derivatives thereof in the presence of a catalyst comprising:
 (a) ruthenium, rhodium, iron, osmium or palladium; and   (b) an organic phosphine;   wherein the hydrogenation is carried out in the presence of more than 1% by weight water.   
   
   
       2 . A homogeneous process according to  claim 1  wherein the carboxylic acids and/or derivatives thereof are present as solvent. 
   
   
       3 . A homogeneous process according to  claim 1  wherein a solvent is present and the water is present as an additive therein. 
   
   
       4 . A homogeneous process according to  claim 3  wherein the water is present in an amount of more than 1% to the solubility limit of the water in the solvent. 
   
   
       5 . A homogeneous process according to  claim 3  wherein the water is present in an amount greater than the solubility limit of the water in the solvent and the excess water forms an aqueous phase. 
   
   
       6 . A homogeneous process according to  claim 1  wherein water is generated in situ. 
   
   
       7 . A homogeneous process according to  claim 2  wherein the product of the reaction forms the solvent. 
   
   
       8 . A homogeneous process according to  claim 1  wherein the water is a solvent for the reaction. 
   
   
       9 . A homogeneous process according to  claim 1  wherein the catalyst is a ruthenium/phosphine catalyst system 
   
   
       10 . A homogeneous process according to  claim 9  wherein the phosphine component of the catalyst system is a tridentate phosphine. 
   
   
       11 . A homogeneous process according to  claim 9  wherein the phosphine component of the catalyst system is tris-1,1,1-(diphenyl-phosphinomethyl)ethane. 
   
   
       12 . A homogeneous process according to  claim 1  wherein the reaction is carried out in the absence of a promotor for the catalyst. 
   
   
       13 . A homogeneous process according to  claim 1  wherein the reaction is carried out in the absence of halide. 
   
   
       14 . A homogeneous process according to  claim 1  wherein the reaction temperature is in the range of from about 150° C. to about 350° C. 
   
   
       15 . A homogeneous process according to  claim 1  wherein the reaction pressure is in the range of from about 250 psig to about 2000 psig. 
   
   
       16 . A homogeneous process according to  claim 10  wherein the pressure is from about 800 psig to about 1200 psig. 
   
   
       17 . A homogeneous process according to  claim 1  wherein the catalyst is regenerated in the presence of the water and hydrogen. 
   
   
       18 . A process for regenerating a catalyst comprising:
 (a) ruthenium, rhodium, iron, osmium or palladium; and   (b) an organic phosphine;   
     wherein the regeneration is carried out in the presence of hydrogen and water. 
   
   
       19 . A process according to  claim 18  wherein the regeneration is carried out at a temperature of from about 150° C. to about 350° C.