Hydrocarbon synthesis

Abstract

A method of synthesizing hydrocarbons from smaller hydrocarbons includes the steps of hydrocarbon halogenation, simultaneous oligomerization and hydrogen halide neutralization, and product recovery, with a metal-oxygen cataloreactant used to facilitate carbon-carbon coupling. Treatment with air or oxygen liberates halogen and regenerates the cataloreactant.

1 . A method of making a plurality of hydrocarbons, comprising: 
 allowing methyl bromide to contact a zeolite doped with an alkaline-earth metal, at a temperature and pressure sufficient to yield a plurality of hydrocarbons.    
     
     
         2 . A method as recited in  claim 1 , wherein the alkaline-earth metal is selected from the group consisting of calcium, magnesium, and mixtures thereof.  
     
     
         3 . A method as recited in  claim 1 , wherein the zeolite has an Si:Al ratio of at least 5:1.  
     
     
         4 . A method as recited in  claim 1 , wherein the zeolite has an Si:Al ratio of between about 20:1 and about 1500:1.  
     
     
         5 . A method as recited in  claim 1 , wherein the zeolite has an Si:Al ratio of between about 80:1 and about 280:1.  
     
     
         6 . A method as recited in  claim 1 , wherein the zeolite doped with an alkaline-earth metal has an alkaline earth metal:silicon ratio of at least 4:1.  
     
     
         7 . A method as recited in  claim 1 , wherein the plurality of hydrocarbons includes at least one aromatic hydrocarbon.  
     
     
         8 . A method as recited in  claim 7 , wherein the at least one aromatic hydrocarbon comprises at least one hydrocarbon selected from the group consisting of benzene, toluene, xylene, ethylbenzene, mesitylene, and ethylmethylbenzene.  
     
     
         9 . A method as recited in  claim 1 , wherein the plurality of hydrocarbons includes at least one branched alkane.  
     
     
         10 . A method as recited in  claim 1 , wherein the plurality of hydrocarbons includes at least one olefin.  
     
     
         11 . A method as recited in  claim 1 , wherein the plurality of hydrocarbons includes at least one alkane, at least one olefin, and at least one aromatic hydrocarbon.  
     
     
         12 . A method as recited in  claim 1 , wherein the plurality of hydrocarbons comprises a gasoline grade mixture of hydrocarbons.  
     
     
         13 . A method as recited in  claim 1 , further comprising allowing any C 1  to C 3  hydrocarbons that are formed to contact a zeolite doped with an alkaline-earth metal to form one or more C 4  or higher hydrocarbons.  
     
     
         14 . A method as recited in  claim 1 , wherein the methyl bromide is formed by brominating methane.  
     
     
         15 . A method as recited in  claim 14 , wherein Br 2  is used to brominate methane.  
     
     
         16 . A method of making a plurality of hydrocarbons, comprising: 
 allowing methyl bromide to contact a zeolite doped with an alkaline-earth metal, at a temperature and pressure sufficient to yield a plurality of hydrocarbons, at least 50% of which are C 6  or higher hydrocarbons.    
     
     
         17 . A method of making a plurality of hydrocarbons, comprising: 
 allowing methyl bromide to contact a zeolite doped with an alkaline-earth metal, at a temperature and pressure sufficient to yield a plurality of hydrocarbons, at least 70% of which are C 5  or higher hydrocarbons.    
     
     
         18 . A method of making a plurality of hydrocarbons, comprising: 
 allowing methyl bromide to contact a zeolite doped with an alkaline-earth metal, at a temperature and pressure sufficient to yield a plurality of hydrocarbons, at least 50% of which are C 6  higher hydrocarbons, and at least 70% of which are C 5  or higher hydrocarbons.    
     
     
         19 . A method as recited in  claim 18 , wherein the temperature is 225° C. to 350 ° C., and the pressure is 1 to 5 bar.  
     
     
         20 . A method as recited in  claim 18 , wherein the doped zeolite is a ZSM-5-type zeolite doped with calcium to a Ca:Si ratio of at least 4:1.