Decarboxylation cell for production of coupled radical products

Abstract

A method that produces coupled radical products from biomass. The method involves obtaining a lipid or carboxylic acid material from the biomass. This material may be a carboxylic acid, an ester of a carboxylic acid, a triglyceride of a carboxylic acid, or a metal salt of a carboxylic acid, or any other fatty acid derivative. This lipid material or carboxylic acid material is converted into an alkali metal salt. The alkali metal salt is then used in an anolyte as part of an electrolytic cell. The electrolytic cell may include an alkali ion conducting membrane (such as a NaSICON membrane). When the cell is operated, the alkali metal salt of the carboxylic acid decarboxylates and forms radicals. Such radicals are then bonded to other radicals, thereby producing a coupled radical product such as a hydrocarbon. The produced hydrocarbon may be, for example, saturated, unsaturated, branched, or unbranched, depending upon the starting material.

1 . A cell comprising:
 an anolyte compartment capable of housing a quantity of anolyte, the anolyte comprising a quantity of an alkali metal salt of a carboxylic acid;   an anode in communication with the anolyte;   a catholyte compartment capable of housing a quantity of catholyte;   a cathode in communication with the catholyte;   an alkali ion conducting membrane; and   a voltage source and/or a photolysis device, wherein the voltage source and/or the photolysis device decarboxylates the alkali metal salt of the carboxylic acid into alkyl radicals that react to form a coupled radical product.   
     
     
         2 . A cell as in  claim 1 , wherein the alkali metal salt comprises sodium such that the alkali metal salt of the carboxylic acid comprises a sodium salt of the carboxylic acid and wherein the alkali ion conducting membrane comprises a NaSICON membrane, wherein the membrane separates the anolyte compartment from the catholyte compartment. 
     
     
         3 . A cell as in  claim 1 , wherein the cell is an undivided cell. 
     
     
         4 . A cell as in  claim 1 , wherein the catholyte compartment comprises an outlet that is used to collect hydrogen gas, and wherein the anolyte compartment comprises an outlet that is used to collect the coupled radical product. 
     
     
         5 . A cell as in  claim 1 , further comprising a conduit that transports a quantity of base from the catholyte compartment to the anolyte compartment. 
     
     
         6 . A cell as in  claim 1 , wherein the photolysis device is positioned to irradiate the anolyte compartment. 
     
     
         7 . A cell as in  claim 1 , wherein the cell is an electrolytic cell, wherein a voltage is applied to the electrolytic cell via the voltage source. 
     
     
         8 . A cell as in  claim 1 , wherein the anolyte further comprises a quantity of the carboxylic acid. 
     
     
         9 . A cell as in  claim 1 , wherein the anolyte comprises a first solvent or a first mixture of solvents. 
     
     
         10 . A cell as in  claim 9 , wherein the first solvent or first mixture of solvents comprises methanol. 
     
     
         11 . A cell as in  claim 9 , wherein the first mixture of solvents comprises at least one G-type solvent and at least one H-type solvent. 
     
     
         12 . A cell as in  claim 11 , wherein the G-type solvent comprises a solvent chosen from ehthylene glycol, glycerine, 1,2-dihydroxy-4-oxadodecane, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-amino-2-methyl-1,3-propanediol, 2,3-butanediol, 3-amino-1,2-propanediol, 1,2-octanediol, cis-1,2-cyclohexanediol, rans-1,2-cyclohexanediol, cis-1,2-cyclopentanediol, 1,2-pentanediol, and 1,2-hexanediol. 
     
     
         13 . A cell as in  claim 11 , wherein the H-type solvent comprises a solvent chosen from isopropanol, methanol, ethanol, butanol, amyl alcohol, octanol, hexane, trichloroethane, dichloroethane, methylene, dichloride, chloroform, carbon tetrachloride, tetralin, decalin, monoglyme, diglyme, tetraglyme, acetone, and acetaldehyde. 
     
     
         14 . A cell as in  claim 11 , wherein the H-type solvent comprises a product of the decarboxylation. 
     
     
         15 . A cell as in  claim 1 , wherein the anode comprises material chosen from platinum, stainless steel, and carbon-based material. 
     
     
         16 . A cell as in  claim 1 , wherein the alkyl radicals react to form a coupled radical product according to the formula: 2R—COONa→R—R+2CO 2 +2e − +2Na +  where R is an alkyl radical. 
     
     
         17 . A cell as in  claim 1 , wherein one or more of the anode and anolyte comprises palladium, rhodium, nickel, platinum, iridium, and ruthenium. 
     
     
         18 . A cell comprising:
 an anolyte compartment capable of housing a quantity of anolyte, the anolyte comprising a quantity of a sodium metal salt of a carboxylic acid and first solvent or mixture of solvents;   an anode in communication with the anolyte;   a catholyte compartment capable of housing a quantity of catholyte, the catholyte compartment comprising an outlet for collecting hydrogen gas;   a cathode in communication with the catholyte;   a NaSICON membrane, wherein the membrane separates the anolyte compartment from the catholyte compartment; and   a voltage source, wherein the voltage source decarboxylates the sodium metal salt of the carboxylic acid into alkyl radicals that react to form a coupled radical product comprising a hydrocarbon, and wherein the anolyte compartment comprises an outlet for collecting the hydrocarbon.   
     
     
         19 . A cell as in  claim 18 , further comprising a conduit that transports a quantity of base from the catholyte compartment to the anolyte compartment. 
     
     
         20 . A cell as in  claim 18 , wherein the first solvent or first mixture of solvents comprises methanol. 
     
     
         21 . A cell as in  claim 18 , wherein the first mixture of solvents comprises at least one G-type solvent and at least one H-type solvent. 
     
     
         22 . A cell as in  claim 21 , wherein the G-type solvent comprises a solvent chosen from ethylene glycol, glycerine, 1,2-dihydroxy-4-oxadodecane, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-amino-2-methyl-1,3-propanediol, 2,3-butanediol, 3-amino-1,2-propanediol, 1,2-octanediol, cis-1,2-cyclohexanediol, rans-1,2-cyclohexanediol, cis-1,2-cyclopentanediol, 1,2-pentanediol, and 1,2-hexanediol. 
     
     
         23 . A cell as in  claim 21 , wherein the H-type solvent comprises a solvent chosen from isopropanol, methanol, ethanol, butanol, amyl alcohol, octanol, hexane, trichloroethane, dichloroethane, methylene, dichloride, chloroform, carbon tetrachloride, tetralin, decalin, monoglyme, diglyme, tetraglyme, acetone, and acetaldehyde. 
     
     
         24 . A cell as in  claim 21 , wherein the H-type solvent comprises a product of the decarboxylation. 
     
     
         25 . A cell as in  claim 18 , wherein the anode comprises material chosen from platinum, stainless steel, and carbon-based material. 
     
     
         26 . A cell as in  claim 18 , wherein the alkyl radicals react to form a coupled radical product according to the formula: 2R—COONa→R—R+2CO 2 +2e − 2Na +  where R is an alkyl radical. 
     
     
         27 . A cell as in  claim 18 , wherein one or more of the anode and anolyte comprises palladium, rhodium, nickel, platinum, iridium, and ruthenium. 
     
     
         28 . A cell comprising:
 an anolyte compartment capable of housing a quantity of anolyte, the anolyte comprising a quantity of a sodium metal salt of a carboxylic acid and first solvent or mixture of solvents, wherein the first mixture of solvents comprises at least one G-type solvent and at least one H-type solvent;   an anode in communication with the anolyte, wherein the anode comprises material chosen from platinum, stainless steel, and carbon-based material, and wherein one or more of the anode and anolyte comprises palladium, rhodium, nickel, platinum, iridium, and ruthenium;   a catholyte compartment capable of housing a quantity of catholyte, the catholyte compartment comprising an outlet for collecting hydrogen gas;   a cathode in communication with the catholyte;   a NaSICON membrane, wherein the membrane separates the anolyte compartment from the catholyte compartment; and   a voltage source, wherein the voltage source decarboxylates the sodium metal salt of the carboxylic acid into alkyl radicals that react to form a coupled radical product comprising a hydrocarbon according to the formula: 2R—COONa→R—R+2CO 2 +2e − +2Na +  where R is an alkyl radical, and wherein the anolyte compartment comprises an outlet for collecting the hydrocarbon.   
     
     
         29 . A cell as in  claim 28 , wherein the G-type solvent comprises a solvent chosen from ethylene glycol, glycerine, 1,2-dihydroxy-4-oxadodecane, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-amino-2-methyl-1,3-propanediol, 2,3-butanediol, 3-amino-1,2-propanediol, 1,2-octanediol, cis-1,2-cyclohexanediol, rans-1,2-cyclohexanediol, cis-1,2-cyclopentanediol, 1,2-pentanediol, and 1,2-hexanediol. 
     
     
         30 . A cell as in  claim 29 , wherein the H-type solvent comprises a solvent chosen from isopropanol, methanol, ethanol, butanol, amyl alcohol, octanol, hexane, trichloroethane, dichloroethane, methylene, dichloride, chloroform, carbon tetrachloride, tetralin, decalin, monoglyme, diglyme, tetraglyme, acetone, and acetaldehyde. 
     
     
         31 . A cell as in  claim 30 , wherein the H-type solvent comprises a product of the decarboxylation.