Apparatus and method for production of formate from carbon dioxide

Abstract

An apparatus is adapted for the production of formate from carbon dioxide. The apparatus includes a reactor including a reduction cell and a production cell and a formate dehydrogenase catalyst immobilized in the production cell. A cathode solution circulates through the reduction cell and the production cell. The cathode solution includes a charge carrier. An anode solution circulates through the anode compartment. The charge carrier is reduced in the reduction cell and reoxidized in the production cell. The carbon dioxide is converted to formate in the production cell.

What is claimed: 
     
         1 . An apparatus adapted for production of formate from carbon dioxide, comprising:
 a reactor including a reduction cell and a production cell;   a proton exchange membrane partitioning the reduction cell into an anode compartment and a cathode compartment;   an anode in the anode compartment;   a cathode in the cathode compartment;   a voltage source connected across the anode and the cathode;   a formate dehydrogenase catalyst immobilized in the production cell;   a cathode solution circulating through the cathode compartment and the production cell, the cathode solution including a charge carrier; and   an anode solution circulating through the anode compartment whereby (a) the charge carrier is reduced in the cathode compartment and reoxidized in the production cell and (b) carbon dioxide is converted to formate in the production cell.   
     
     
         2 . The apparatus of  claim 1 , wherein the formate dehydrogenase catalyst is formate dehydrogenase 1 from  Methylobacterium extorquens  AM1. 
     
     
         3 . The apparatus of  claim 2 , wherein the formate dehydrogenase 1 from  Methylobacterium extorquens  AM1 is immobilized on agarose beads. 
     
     
         4 . The apparatus of  claim 1 , wherein the charge carrier is selected from a group consisting of ethyl viologen, methyl viologen dibromide, 1,1′-diheptyl-4,4′-bipyridinium dibromide, 1,1′-di-n-octyl-4,4′-bipyridinium dibromide, 1,1′-dibenzyl-4,4′-bipyridinium dichloride, 1,1′-bis(2,4-dinitrophenyl)-4,4′-bipyridinium dichloride, 1,1′-diphenyl-4,4′-bipyridinium dichloride, propyl viologen, butyl viologen, benzyl viologen, ethanol viologen, propanol viologen, methyl acetate viologen, acetate viologen, ethylamine viologen, propylamine viologen, and methyl ethylamine viologen, chloride salts thereof, bromide salts thereof and combinations thereof. 
     
     
         5 . The apparatus of  claim 1 , further including an oxygen scavenger in the cathode solution. 
     
     
         6 . The apparatus of  claim 5 , wherein the oxygen scavenger is selected from a group consisting of sodium thiosulfate, ascorbic acid, ferrous carbonate, sodium sulphite, sodium bisulphite, sodium metabisulphite, tannin, sodium erythorbate, hydrazine/carbohydrazine, N,N-diethylhydroxylamine and combinations thereof. 
     
     
         7 . The apparatus of  claim 1 , further including a pH buffer in the cathode solution. 
     
     
         8 . The apparatus of  claim 7 , wherein the pH buffer is selected from a group consisting of Tris buffer, Tris-Bis buffer, BES, buffer, MOPS buffer, TES buffer, HEPES buffer, MOPSO buffer, Imidazole (glyoxaline)-HCl buffer, potassium hydroxide, sodium hydroxide, potassium carbonate, potassium phosphate and mixtures thereof, adapted to maintain a pH of the cathode solution between pH 6 and pH 8. 
     
     
         9 . The apparatus of  claim 1 , wherein the anode is selected from a group consisting of a platinum wire mesh electrode, a platinum oxide coated carbon electrode, an iridium oxide coated carbon electrode, a cobalt oxide coated carbon electrode, a lead oxide/titanium alloy iridium-platinum coated carbon electrode, an iridium-ruthenium coated carbon electrode, and an iridium-tantalum coated carbon electrode. 
     
     
         10 . The apparatus of  claim 1 , wherein the cathode is selected from a group consisting of a copper electrode, a tin-coated copper electrode, a bismuth-coated copper electrode, a lead-coated copper electrode, a bismuth-tin-lead alloys coated copper electrode, and bismuth-tin-lead alloys coated on porous carbon, carbon felt, carbon cloth, woven carbon, or carbon nanotube electrodes. 
     
     
         11 . An apparatus adapted for production of formate from carbon dioxide, comprising:
 a reactor including a reduction cell and a production cell;   a formate dehydrogenase catalyst immobilized in the production cell;   a cathode solution circulating through the reduction cell and the production cell, the cathode solution including a charge carrier; and   an anode solution circulating through the anode compartment whereby (a) the charge carrier is reduced in the reduction cell and reoxidized in the production cell and (b) carbon dioxide is converted to formate in the production cell.   
     
     
         12 . The apparatus of  claim 11 , wherein the formate dehydrogenase catalyst is formate dehydrogenase 1 from  Methylobacterium extorquens  AM1. 
     
     
         13 . The apparatus of  claim 12 , wherein the formate dehydrogenase 1 from  Methylobacterium extorquens  AM1 is immobilized on agarose beads. 
     
     
         14 . The apparatus of  claim 13 , further including an oxygen scavenger and a pH buffer in the cathode solution. 
     
     
         15 . A method of producing formate from carbon dioxide in a dual cell reactor, comprising:
 circulating a charge carrier solution between a reduction cell and a production cell;   reducing a charge carrier in the charge carrier solution in the reduction cell;   reoxidizing the charge carrier in the production cell; and   converting carbon dioxide and protons to formate in presence of a formate dehydrogenase catalyst in the production cell.   
     
     
         16 . The method of  claim 15 , further comprising:
 partitioning the reduction cell into an anode compartment and a cathode compartment with a proton exchange membrane;   locating an anode in the anode compartment;   locating a cathode in the cathode compartment; and   applying a voltage across the anode and the cathode.   
     
     
         17 . The method of  claim 15 , further comprising circulating an oxygen scavenger with the charge carrier in the charge carrier solution. 
     
     
         18 . The method of  claim 17 , further comprising circulating a pH buffer with the charge carrier in the charge carrier solution. 
     
     
         19 . The method of  claim 18 , further comprising maintaining the charge carrier solution at a temperature between 20° C. and 40° C. and a pH of between pH 6 and pH 8. 
     
     
         20 . The method of  claim 19 , including maintaining the applied voltage between −0.75 V to −0.95 V vs. Ag/AgCl. 
     
     
         21 . A method of producing formate from carbon dioxide in a dual cell reactor including a reduction cell and a production cell, the method comprising:
 partitioning the reduction cell into an anode compartment and a cathode compartment with a proton exchange membrane;   locating an anode in the anode compartment;   locating a cathode in the cathode compartment;   applying a voltage across the anode and the cathode;   immobilizing a formate dehydrogenase catalyst in the production cell;   circulating a cathode solution, including a charge carrier, through the cathode compartment and the production cell; and   circulating an anode solution through the anode compartment whereby (a) the charge carrier is reduced in the cathode compartment and reoxidized in the production cell and (b) carbon dioxide is converted to formate in the production cell.