Synthesis of High Caloric Fuels and Chemicals

Abstract

In one embodiment, the present application discloses methods to selectively synthesize higher alcohols and hydrocarbons useful as fuels and industrial chemicals from syngas and biomass. Ketene and ketonization chemistry along with hydrogenation reactions are used to synthesize fuels and chemicals. In another embodiment, ketene used to form fuels and chemicals may be manufactured from acetic acid which in turn can be synthesized from synthesis gas which is produced from coal, biomass, natural gas, etc.

What is claimed is: 
     
         1 .- 37 . (canceled) 
     
     
         38 . A method for the preparation of a high caloric fuel comprising a butanol, the method comprising:
 a) preparing a beta-butyro lactone; and   b) hydrogenating the beta-butyro lactone to form the butanol.   
     
     
         39 . The method of  claim 38  where the beta-butyro lactone is prepared by steps comprising:
 a) conversion of synthesis gas to methanol; 
 b) carbonylation of methanol to form acetic acid; 
 c) dehydration of acetic acid to form a ketene of the formula I; 
 
       
         
           
           
               
               
           
         
         where: 
         R 1  is H; and 
         R 2  is H; 
         d) dimerization of the ketene to form diketene; and 
         e) hydrogenation of the diketene using a catalyst to form beta-butyrolactone. 
       
     
     
         40 . The method of  claim 39 , where the acetic acid is obtained from a fermentation process. 
     
     
         41 . The method of  claim 38  where the beta-butyro lactone is prepared by the steps comprising:
 a) preparing propylene oxide from propylene; and 
 b) carbonylating the propylene oxide to form beta-butyro lactone. 
 
     
     
         42 . The method of  claim 38  where beta-butyrolactone is prepared by the reaction of ketene with acetaldehyde to form beta-butyro lactone. 
     
     
         43 . The method of  claim 38  where the catalyst used in the hydrogenation step comprises a transition metal catalyst. 
     
     
         44 . The method of  claim 43  where the transition metal catalyst comprises of two or more transition metals. 
     
     
         45 . The method of  claim 44  where the catalyst is a copper zinc catalyst. 
     
     
         46 . The method of  claim 43 , where the catalyst is a nickel catalyst. 
     
     
         47 . The method of  claim 43  where the catalyst is a ruthenium catalyst. 
     
     
         48 . The method of  claim 44  where the catalyst is a copper chromite catalyst. 
     
     
         49 . The method of  claim 38  where the butanol is 2-butanol. 
     
     
         50 . The method of  claim 38  where the butanol is 1-butanol. 
     
     
         51 . The method of  claim 38  where the butanol comprises of a mixture of 1-butanol and 2-butanol. 
     
     
         52 . The method of  claim 38  where the fuel further comprises butyl butyrate. 
     
     
         53 . The method of  claim 39  where the synthesis gas is produced from feed stock selected from the group consisting of biomass, natural gas, coal, trash and petroleum. 
     
     
         54 . The method of  claim 39  where the acetic acid is produced from a fermentation process. 
     
     
         55 . A high caloric fuel comprising the butanol prepared by the method of  claim 38 . 
     
     
         56 . A method for the preparation of a fuel comprising a heptanol comprising:
 a) preparing beta-butyro lactone using a feed stock;   b) hydrogenating the beta-butyro lactone with a catalyst to form butyric acid;   c) ketonizing the butyric acid to form 4-heptanone; and   d) hydrogenating the 4-heptanone with a catalyst to form the heptanol, where the heptanol is 4-heptanol.   
     
     
         57 . The method of  claim 56  where the beta-butyro lactone is prepared by the steps comprising:
 a) preparing propylene oxide from propylene; and 
 b) carbonylating the propylene oxide to form beta-butyro lactone. 
 
     
     
         58 . The method of  claim 56 , where the beta-butyrolactone is prepared by a reaction of ketene with acetaldehyde, where the ketene is of the formula I: 
       
         
           
           
               
               
           
         
         where: 
         R 1  is H; and 
         R 2  is H. 
       
     
     
         59 . The method of  claim 58  where the ketene is prepared from a pyrolysis reaction of acetic acid. 
     
     
         60 . The method of  claim 59  where the acetic acid is prepared by a fermentation process. 
     
     
         61 . The method of  claim 56  where the catalyst used in the hydrogenation reaction comprises a transition metal catalyst. 
     
     
         62 . The method of  claim 61  where the transition metal catalyst comprises of two or more catalysts. 
     
     
         63 . The method of  claim 62  where the catalyst is a copper zinc catalyst. 
     
     
         64 . The method of  claim 56  where the feed stock for the process is selected from the group of biomass, natural gas, coal, trash and petroleum. 
     
     
         65 . The method of  claim 56  where the heptanol is further converted to heptane by the steps of:
 a) dehydrating the heptanol to form heptene; and 
 b) hydrogenating the heptene to form heptane. 
 
     
     
         66 . A fuel composition comprising the heptanol prepared by the method of  claim 56 . 
     
     
         67 . A fuel composition comprising the heptane prepared by the method of  claim 65 .