Electrochemical hydroxide systems and methods using metal oxidation

Abstract

There are provided methods and systems for an electrochemical cell including an anode and a cathode where the anode is contacted with a metal ion that converts the metal ion from a lower oxidation state to a higher oxidation state. The metal ion in the higher oxidation state is reacted with hydrogen gas, an unsaturated hydrocarbon, and/or a saturated hydrocarbon to form products.

1 - 31 . (canceled) 
     
     
         32 . A method comprising:
 contacting an anode with an anode electrolyte in an electrochemical cell wherein the anode electrolyte comprises metal halide or metal sulfate;   adding a ligand to the anode electrolyte;   contacting a cathode with a cathode electrolyte in the electrochemical cell;   applying a voltage to the anode and the cathode and oxidizing the metal halide or the metal sulfate from a lower oxidation state to a higher oxidation state at the anode; and   reacting an unsaturated hydrocarbon or a saturated hydrocarbon with the anode electrolyte comprising the metal halide or the metal sulfate in the higher oxidation state and the ligand wherein the ligand is of formula D, or an oxide thereof:   
       
         
           
           
               
               
           
         
         wherein R 1 , R 2 , and R 3  independently are H, alkyl, substituted alkyl, alkoxy, substituted alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, amine, substituted amine, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, and substituted heterocycloalkyl; and the metal halide or the metal sulfate in the lower oxidation state. 
       
     
     
         33 . The method of  claim 32 , wherein the unsaturated hydrocarbon is a C2-C10 alkene or the saturated hydrocarbon is C2-C10 alkane. 
     
     
         34 . The method of  claim 32 , wherein the unsaturated hydrocarbon is ethylene, propylene, or butylene which after the reaction results in ethylene dichloride, propylene dichloride or dichlorobutane, respectively. 
     
     
         35 . The method of  claim 34 , further comprising forming vinyl chloride monomer from the ethylene dichloride and forming poly(vinyl chloride) from the vinyl chloride monomer. 
     
     
         36 . The method of  claim 32 , wherein the reaction of the unsaturated hydrocarbon or the saturated hydrocarbon with the anode electrolyte comprising the metal halide or the metal sulfate in the higher oxidation state forms halohydrocarbon or sulfohydrocarbon. 
     
     
         37 . The method of  claim 36 , wherein the halohydrocarbon comprises ethylene dichloride, chloroethanol, chloral, chloral hydrate, 1,1-dichloroethene, trichloroethylene, tetrachloroethene, 1,1,2,2-tetrachloroethane, allyl chloride, or combinations thereof. 
     
     
         38 . The method of  claim 32 , wherein the saturated hydrocarbon is methane, ethane, or propane. 
     
     
         39 . The method of  claim 32 , wherein concentration of the metal ion of the metal halide or the metal sulfate in the higher oxidation state is between 4.5-7M, concentration of the metal ion of the metal halide or the metal sulfate in the lower oxidation state is between 0.25-1.5M, and concentration of the ligand is between 0.25-6M. 
     
     
         40 . The method of  claim 39 , further comprising sodium chloride in a concentration of between 1-3M. 
     
     
         41 . The method of  claim 32 , wherein the anode electrolyte further comprises saltwater. 
     
     
         42 . The method of  claim 41 , wherein the saltwater comprises more than 1 wt % chloride content. 
     
     
         43 . The method of  claim 41 , wherein the saltwater comprises more than 10 wt % NaCl. 
     
     
         44 . The method of  claim 32 , wherein the reaction is in an aqueous medium wherein the aqueous medium comprises more than 5 wt % water. 
     
     
         45 . The method of  claim 32 , further comprising forming an alkali, water, or hydrogen gas at the cathode. 
     
     
         46 . The method of  claim 32 , wherein the cathode electrolyte comprises water and the cathode is an oxygen depolarizing cathode that reduces oxygen and water to hydroxide ions; the cathode electrolyte comprises water and the cathode is a hydrogen gas producing cathode that reduces water to hydrogen gas and hydroxide ions; the cathode electrolyte comprises hydrochloric acid and the cathode is a hydrogen gas producing cathode that reduces hydrochloric acid to hydrogen gas; or the cathode electrolyte comprises hydrochloric acid and the cathode is an oxygen depolarizing cathode that reacts hydrochloric acid and oxygen gas to form water. 
     
     
         47 . The method of  claim 32 , wherein the metal ion of the metal halide or the metal sulfate is selected from the group consisting of iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium, and combination thereof. 
     
     
         48 . The method of  claim 32 , wherein the metal ion of the metal halide or the metal sulfate is selected from the group consisting of iron, chromium, copper, and tin. 
     
     
         49 . The method of  claim 32 , wherein the metal ion of the metal halide or the metal sulfate is copper. 
     
     
         50 . The method of  claim 32 , wherein the lower oxidation state of the metal ion of the metal halide or the metal sulfate is 1+, 2+, 3+, 4+, or 5+. 
     
     
         51 . The method of  claim 32 , wherein the higher oxidation state of the metal ion of the metal halide or the metal sulfate is 2+, 3+, 4+, 5+, or 6+. 
     
     
         52 . The method of  claim 32 , wherein the metal ion of the metal halide or the metal sulfate is copper that is converted from Cu +  to Cu 2+ , the metal ion of the metal halide or the metal sulfate is iron that is converted from Fe 2+  to Fe 3+ , the metal ion of the metal halide or the metal sulfate is tin that is converted from Sn 2+  to Sn 4+ , the metal ion of the metal halide or the metal sulfate is chromium that is converted from Cr 2+  to Cr 3+ , the metal ion of the metal halide or the metal sulfate is platinum that is converted from Pt 2+  to Pt 4+ , or combinations thereof. 
     
     
         53 . The method of  claim 32 , wherein the anode electrolyte comprising the metal halide or the metal sulfate in the higher oxidation state further comprises the metal halide or the metal sulfate in the lower oxidation state. 
     
     
         54 . The method of  claim 32 , wherein the R 1 , R 2 , and R 3  independently are H, amine, or substituted amine wherein the substituted amine is substituted with a group selected from alkyl and alkoxy. 
     
     
         55 . The method of  claim 32 , wherein the R 1 , R 2 , and R 3  independently are H, aryl or substituted aryl wherein the substituted aryl is substituted with group selected from alkyl, alkoxy, and amine. 
     
     
         56 . The method of  claim 32 , wherein the R 1 , R 2 , and R 3  independently are H, alkoxy, substituted alkoxy, amine, or substituted amine.