Electrochemical systems and methods using metal and ligand

• US 9,187,835 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:
  US13/474,599
• Publication Number:
  US 20120292197A1
• Time in Patent Office: 1,279 Days
• Field of Search: 205/444, 205/457, 205/459, 205/460, 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 in an electrochemical cell wherein the anode electrolyte comprises metal halide or metal sulfate;

adding a ligand to the anode electrolyte;

applying a voltage to the anode and cathode and oxidizing the metal halide or the metal sulfate from a lower oxidation state to a higher oxidation state at the anode;

contacting the cathode with a cathode electrolyte in the electrochemical cell; 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 A;

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 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.

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

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

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

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

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

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

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

12. The method of claim 1, 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.

13. The method of claim 1, wherein the unsaturated hydrocarbon is ethylene, propylene, or butylene resulting in ethylene dichloride, propylene dichloride or 1,4-dichlorobutane, respectively.

14. The method of claim 13, further comprising forming vinyl chloride monomer from the ethylene dichloride and forming poly(vinyl chloride) from the vinyl chloride monomer.

15. The method of claim 1, wherein the ligand results in one or more of the properties selected from enhanced reactivity of metal ion of the metal halide or the metal sulfate towards the unsaturated hydrocarbon or the saturated hydrocarbon, enhanced selectivity of metal ion of the metal halide or the metal sulfate towards halogenations of the unsaturated or the saturated hydrocarbon, enhanced transfer of halogen from metal ion of the metal halide or the metal sulfate to the unsaturated hydrocarbon or the saturated hydrocarbon, reduced redox potential of the electrochemical cell, enhanced solubility of metal ion of the metal halide or the metal sulfate in aqueous medium, reduced membrane cross-over of metal ion of the metal halide or the metal sulfate to the cathode electrolyte in the electrochemical cell, reduced corrosion of the electrochemical cell, enhanced separation of metal ion of the metal halide or the metal sulfate from halogenated hydrocarbon solution, and combination thereof.

16. The method of claim 1, wherein the substituted alkyl is alkyl substituted with one or more of a group selected from alkenyl, halogen, amine, and substituted amine.

17. The method of claim 1, 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.

18. The method of claim 17, wherein the anode electrolyte is sodium chloride.

19. The method of claim 18, wherein concentration of the sodium chloride is between 1-3M.

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

21. The method of claim 1, wherein the unsaturated hydrocarbon is ethylene and the metal halide is metal chloride.

22. The method of claim 21, wherein the metal chloride is copper chloride.

23. The method of claim 22, wherein the ethylene reacts with the copper chloride in the higher oxidation state and the ligand to form the halohydrocarbon comprising ethylene dichloride.

24. The method of claim 1, wherein the halohydrocarbon comprises ethylene dichloride, chloroethanol, chloral, chloral hydrate, 1,1-dichloroethene, trichloroethylene, tetrachloroethene, 1,1,2,2-tetrachloroethane, or combinations thereof.

25. The method of claim 1, wherein the reaction is in an aqueous medium wherein the aqueous medium comprises more than 5 wt% water.

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