Electrochemical hydroxide systems and methods using metal oxidation

• US 9,187,834 B2
• Filed: 05/17/2012
• Issued: 11/17/2015
• Est. Priority Date: 05/19/2011
• Status: Active Grant

• Current Assignee: Calera Corporation
• Original Assignee: Calera Corporation
• Inventors: Albrecht, Thomas A., Gilliam, Ryan J., Boggs, Bryan, Self, Kyle, Solas, Dennis W., Kostowskyj, Michael, Leclerc, Margarete K., Gorer, Alexander, Weiss, Michael Joseph
• Primary Examiner(s): Wong, Edna
• Application Number:
  US13/474,598
• Publication Number:
  US 20120292196A1
• Time in Patent Office: 1,279 Days
• Field of Search: 205/459, 205/497, 205/507, 205/545, 205/687, 570/101, 570/261, 568/18, 526/344
• US Class Current: 1/1
• CPC Class Codes: B01J 27/122 of copper
• CPC Class Codes: B01J 27/132 with chromium, molybdenum, tungsten or polonium
• CPC Class Codes: C07C 17/02 to unsaturated hydrocarbons
• CPC Class Codes: C07D 301/03 by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
• CPC Class Codes: C25B 1/00 Electrolytic production of inorganic compounds or non-metals
• CPC Class Codes: C25B 1/02 Hydrogen or oxygen
• CPC Class Codes: C25B 1/16 Hydroxides by simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine C25B1/34
• CPC Class Codes: C25B 1/18 Alkaline earth metal compounds or magnesium compounds
• CPC Class Codes: C25B 1/20 Hydroxides
• CPC Class Codes: C25B 1/26 Chlorine; Compounds thereof by simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine C25B1/34
• CPC Class Codes: C25B 1/46 in diaphragm cells
• CPC Class Codes: C25B 11/095 at least one of the compounds being organic
• CPC Class Codes: C25B 3/23 Oxidation halogenation C25B3/27
• CPC Class Codes: C25B 3/27 Halogenation
• CPC Class Codes: C25B 9/17 Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
• CPC Class Codes: C25B 9/19 with diaphragms
• CPC Class Codes: Y02E 60/36 Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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.

Claims

1. A method, comprising:

contacting an anode with an anode electrolyte wherein the anode electrolyte comprises saltwater and metal halide;

applying a voltage to the anode and cathode and oxidizing the metal halide from a lower oxidation state to a higher oxidation state at the anode wherein no gas is formed at the anode;

contacting the cathode with a cathode electrolyte; 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 wherein the aqueous medium comprises more than 25 wt % water to result in a halohydrocarbon and the metal halide in the lower oxidation state, wherein yield of the halohydrocarbon is more than 80% by weight.

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

3. 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.

4. 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.

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

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

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

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

9. The method of claim 1, wherein metal ion in the metal halide is copper that is converted from Cu⁺ to Cu²⁺, metal ion in the metal halide is iron that is converted from Fe²⁺ to Fe³⁺, metal ion in the metal halide is tin that is converted from Sn²⁺ to Sn⁴⁺, metal ion in the metal halide is chromium that is converted from Cr²⁺ to Cr³⁺, metal ion in the metal halide is platinum that is converted from Pt²⁺ to Pt⁴⁺, or combination thereof.

10. The method of claim 1, wherein no gas is used at the anode.

11. The method of claim 1, further comprising adding a ligand to the anode electrolyte wherein the ligand interacts with the metal halide.

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

13. 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.

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

15. 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.

16. The method of claim 15, further comprising forming vinyl chloride monomer from the ethylene dichloride and forming poly(vinyl chloride) from the vinyl chloride monomer.

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

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

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

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

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

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

23. 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.

24. The method of claim 1, wherein the yield of the halohydrocarbon is more than 90% by weight.

25. A method, comprising:

contacting an anode with an anode electrolyte wherein the anode electrolyte comprises saltwater and copper halide;

applying a voltage to the anode and cathode and oxidizing the copper halide from a lower oxidation state to a higher oxidation state at the anode wherein no gas is formed at the anode;

contacting the cathode with a cathode electrolyte; and

reacting ethylene with the anode electrolyte comprising the copper halide in the higher oxidation state, in an aqueous medium wherein the aqueous medium comprises more than 25 wt % water, to form ethylene dichloride wherein yield of the ethylene dichloride is more than 80% by weight.

26. The method of claim 25, wherein the reaction further forms chloroethanol, trichloroethane, chloral, chloral hydrate, 1,1-dichloroethene, trichloroethylene, tetrachloroethene, 1,1,2,2-tetrachloroethane, or combinations thereof.