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 hydrocarbon having a carbon number C n , where n≧2, comprising: 
 forming a halogenated hydrocarbon by allowing a reactant hydrocarbon having a carbon number C m , where m<n, to react with a halogenating agent;    forming a product hydrocarbon having a carbon number C n , where n≧2, by allowing the halogenated hydrocarbon to contact a metal-oxygen cataloreactant;    recovering the product hydrocarbon; and    regenerating the cataloreactant.    
     
     
         2 . A method as recited in  claim 1 , wherein the reactant hydrocarbon comprises methane.  
     
     
         3 . A method as recited in  claim 1 , wherein the metal-oxygen cataloreactant is selected from the group consisting of zeolites, doped zeolites, metal oxides, mixed metal oxides, metal oxide-impregnated zeolites, and mixtures thereof.  
     
     
         4 . A method as recited in  claim 1 , wherein the cataloreactant is regenerated with air or oxygen.  
     
     
         5 . A method as recited in  claim 1 , wherein synthesis of the product hydrocarbon is carried out in a zone reactor.  
     
     
         6 . A method as recited in  claim 1 , wherein the halogenating agent comprises molecular halogen.  
     
     
         7 . A method as recited in  claim 1 , wherein the molecular halogen comprises bromine.  
     
     
         8 . A method as recited in  claim 1 , wherein the halogenating agent comprises an alkyl halide.  
     
     
         9 . A method as recited in  claim 1 , wherein the halogenating agent comprises a solid halide.  
     
     
         10 . A method as recited in  claim 1 , wherein the halogenating agent comprises a hydrogen halide.  
     
     
         11 . A method of making a hydrocarbon having a carbon number C n , where n≧2, comprising: 
 forming a brominated hydrocarbon by allowing a reactant hydrocarbon having a carbon number C m , where m<n, to react with a brominating agent;    forming a product hydrocarbon having a carbon number C n , where n≧2, by allowing the brominated hydrocarbon to contact a metal-oxygen cataloreactant;    recovering the product hydrocarbon; and    regenerating the cataloreactant.    
     
     
         12 . A method as recited in  claim 11 , wherein the reactant hydrocarbon comprises methane.  
     
     
         13 . A method as recited in  claim 11 , wherein the metal-oxygen cataloreactant is selected from the group consisting of zeolites, doped zeolites, metal oxides, mixed metal oxides, metal oxide-impregnated zeolites, and mixtures thereof.  
     
     
         14 . A method as recited in  claim 1 , wherein the cataloreactant is regenerated with air or oxygen.  
     
     
         15 . A method as recited in  claim 1 , wherein synthesis of the product hydrocarbon is carried out in a zone reactor.  
     
     
         16 . A method as recited in  claim 1 , wherein the halogenating agent is selected from the group consisting of bromine, alkyl bromides, solid bromides, and hydrogen bromide.  
     
     
         17 . A method of making a hydrocarbon having a carbon number C n , where n≧2, comprising: 
 (i) forming an alkyl halide by allowing a reactant alkane having a carbon number C m , where m<n, to react with molecular halogen;    (ii) forming a product hydrocarbon having a carbon number C n , where n≧2, by allowing the alkyl halide to contact a metal-oxygen cataloreactant;    (iii) recovering the product hydrocarbon; and    (iv) regenerating the cataloreactant with air or oxygen.    
     
     
         18 . A method as recited in  claim 17 , wherein the reactant hydrocarbon comprises methane.  
     
     
         19 . A method as recited in  claim 17 , wherein the molecular halogen comprises bromine.  
     
     
         20 . A method as recited in  claim 17 , wherein step (i) occurs at an alkane-to-halogen ratio of from 1:10 to 1:100 by volume.  
     
     
         21 . A method as recited in  claim 19 , wherein step (i) occurs at a temperature of from 20 to 900° C. and a pressure of from 0.1 to 200 atm.  
     
     
         22 . A method as recited in  claim 17 , wherein the metal-oxygen cataloreactant is selected from the group consisting of zeolites, doped zeolites, metal oxides, mixed metal oxides, metal oxide-impregnated zeolites, and mixtures thereof.  
     
     
         23 . A method as recited in  claim 17 , wherein the cataloreactant is regenerated with air or oxygen.  
     
     
         24 . A method as recited in  claim 17 , wherein steps (i)-(iv) take place in a zone reactor.  
     
     
         25 . A method of making a hydrocarbon having a carbon number C n , where n≧2, comprising: 
 (i) forming an alkyl halide by allowing methane to react with molecular bromine, at a temperature of from 20 to 900° C., a pressure of from 0.1 to 200 atm, and a methane-to-bromine ratio of from 1:10 to 1:100 by volume;    (ii) forming a product hydrocarbon having a carbon number C n , where n≧2, by allowing the alkyl bromide to contact a doped zeolite;    (iii) recovering the product hydrocarbon; and    (iv) regenerating the doped zeolite with air or oxygen; wherein steps (i)-(iv) occur in a zone reactor.