Electrochemical hydroxide systems and methods using metal oxidation

Patent metadata

Field	Value
Publication number	US-2016108529-A1
Application number	US-201514879525-A
Country	US
Kind code	A1
Filing date	Oct 9, 2015
Priority date	May 19, 2011
Publication date	Apr 21, 2016
Grant date	—

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.

First claim

1 - 28 . (canceled)

29 . A method, comprising:
contacting an anode with an anode electrolyte in an electrochemical cell wherein the anode electrolyte comprises saltwater and metal halide; 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 from a lower oxidation state to a higher oxidation state at the anode; and halogenating an unsaturated hydrocarbon or a saturated hydrocarbon with the anode electrolyte comprising the metal halide in the higher oxidation state in an aqueous medium to result in a halohydrocarbon and the metal halide in the lower oxidation state.

30 . The method of claim 1 , further comprising forming an alkali, water, or hydrogen gas at the cathode.

31 . The method of claim 1 , 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.

32 . The method of claim 1 , wherein metal ion in the metal halide 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.

33 . The method of claim 1 , wherein metal ion in the metal halide is selected from the group consisting of iron, chromium, copper, and tin.

34 . The method of claim 1 , wherein metal ion in the metal halide is copper.

35 . The method of claim 1 , wherein the lower oxidation state of metal ion in the metal halide is 1+, 2+, 3+, 4+, or 5+ and the higher oxidation state of metal ion in the metal halide is 2+, 3+, 4+, 5+, or 6+.

36 . The method of claim 1 , wherein metal ion in the metal halide is copper that is converted from Cu + to Cu 2+ , metal ion in the metal halide is iron that is converted from Fe 2+ to Fe 3+ , metal ion in the metal halide is tin that is converted from Sn 2+ to Sn 4+ , metal ion in the metal halide is chromium that is converted from Cr 2+ to Cr 3+ , metal ion in the metal halide is platinum that is converted from Pt 2+ to Pt 4+ , or combination thereof.

37 . The method of claim 1 , wherein no gas is used or formed at the anode.

38 . The method of claim 1 , further comprising adding a ligand to the anode electrolyte.

39 . The method of claim 1 , wherein the metal halide in the lower oxidation state is re-circulated back to the anode electrolyte.

40 . The method of claim 1 , wherein the anode electrolyte comprising the metal halide in the higher oxidation state further comprises the metal halide in the lower oxidation state.

41 . The method of claim 1 , wherein the unsaturated hydrocarbon is compound of formula I resulting in compound of formula II after halogenation:

wherein, n is 2-10; m is 0-5; and q is 1-5;
R is independently selected from hydrogen, halogen, —COOR′, —OH, and —NR′(R″), where R′ and R″ are independently selected from hydrogen, alkyl, and substituted alkyl; and
X is a halogen selected from chloro, bromo, and iodo.

42 . The method of claim 1 , wherein the unsaturated hydrocarbon is ethylene, propylene, or butylene which reacts with the anode electrolyte comprising the metal halide in the higher oxidation state to form ethylene dichloride, propylene dichloride or 1,4-dichlorobutane, respectively.

43 . The method of claim 42 , further comprising forming vinyl chloride monomer from the ethylene dichloride and forming poly(vinyl chloride) from the vinyl chloride monomer.

44 . The method of claim 1 , wherein the saturated hydrocarbon is compound of formula III resulting in compound of formula IV after halogenation:

wherein, n is 2-10; k is 0-5; and s is 1-5;
R is independently selected from hydrogen, halogen, —COOR′, —OH, and —NR′(R″), where R′ and R″ are independently selected from hydrogen, alkyl, and substituted alkyl; and
X is a halogen selected from chloro, bromo, and iodo.

45 . The method of claim 1 , wherein the saturated hydrocarbon is methane, ethane, or propane.

46 . The method of claim 1 , wherein the unsaturated hydrocarbon is a C2-C10 alkene or the saturated hydrocarbon is C2-C10 alkane.

47 . The method of claim 1 , wherein the saltwater comprises water comprising more than 1% chloride content.

48 . The method of claim 1 , wherein the saltwater comprises sodium chloride.

49 . The method of claim 1 , wherein total amount of the metal halide in the anode electrolyte is between 6-12M.

50 . The method of claim 1 , wherein the anode electrolyte comprises metal ion of the metal halide in the higher oxidation state in range of 4-7M, metal ion of the metal halide in the lower oxidation state in range of 0.1-2M and sodium chloride in range of 1-3M.

51 . A method, comprising:
contacting an anode with an anode electrolyte wherein the anode electrolyte comprises saltwater and copper halide; contacting a cathode with a cathode electrolyte; applying a voltage to the anode and the cathode and oxidizing the copper halide from a lower oxidation state to a higher oxidation state at the anode; and reacting ethylene with the anode electrolyte comprising the copper halide in the higher oxidation state, in an aqueous medium to form ethylene dichloride.

52 . The method of claim 51 , wherein the reaction further forms chloroethanol, trichloroethane, chloral, chloral hydrate, 1,1-dichloroethene, trichloroethylene, tetrachloroethene, 1,1,2,2-tetrachloroethane, or combinations thereof.

Assignees

• Calera Corp

Inventors

• Albrecht Thomas A
• Gilliam Ryan J
• Boggs Bryan
• Self Kyle
• Solas Dennis W
• Kostowskyj Michael
• Leclerc Margarete K
• Gorer Alexander
• Weiss Michael Joseph

Classifications

• C25B1/46 Primary

  in diaphragm cells · CPC title

• C07C17/02

  to unsaturated hydrocarbons · CPC title

• C25B1/16

  Hydroxides (by simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine C25B1/34) · CPC title

• C25B1/00

  Electrolytic production of inorganic compounds or non-metals · CPC title

• C25B1/18

  Alkaline earth metal compounds or magnesium compounds · CPC title