Electrochemical systems and methods using metal halide to form products

• US 9,957,621 B2
• Filed: 09/15/2015
• Issued: 05/01/2018
• Est. Priority Date: 09/15/2014
• Status: Active Grant

• Current Assignee: Calera Corporation
• Original Assignee: Calera Corporation
• Inventors: Albrecht, Thomas A., Solas, Dennis, Leclerc, Margarete K., Weiss, Michael Joseph, Gilliam, Ryan J., Self, Kyle
• Primary Examiner(s): Abraham, Ibrahime A
• Assistant Examiner(s): Jain, Salil
• Application Number:
  US14/855,262
• Publication Number:
  US 20160076156A1
• Time in Patent Office: 959 Days
• CPC Class Codes: C25B 1/02 Hydrogen or oxygen
• CPC Class Codes: C25B 11/00 Electrodes; Manufacture thereof not otherwise provided for
• CPC Class Codes: C25B 11/036 Bipolar electrodes
• CPC Class Codes: C25B 11/051 Electrodes formed of electrocatalysts on a substrate or carrier
• CPC Class Codes: C25B 11/091 consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
• CPC Class Codes: C25B 11/095 at least one of the compounds being organic
• CPC Class Codes: C25B 15/08 Supplying or removing reactants or electrolytes; Regeneration of electrolytes
• 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 9/75 having bipolar electrodes

Abstract

There are provided electrochemical methods and systems to form one or more organic compounds or enantiomers thereof selected from the group consisting of substituted or unsubstituted dioxane, substituted or unsubstituted dioxolane, dichloroethylether, dichloromethyl methyl ether, dichloroethyl methyl ether, chloroform, carbon tetrachloride, phosgene, and combinations thereof.

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;

contacting the cathode with a cathode electrolyte; and

halogenating ethylene or ethane with the anode electrolyte comprising the saltwater and the metal halide in the higher oxidation state, in an aqueous medium wherein the aqueous medium comprises more than 5 wt % water to form one or more organic compounds or enantiomers thereof and the metal halide in the lower oxidation state,

wherein the one or more organic compounds or enantiomers thereof are selected from the group consisting of substituted or unsubstituted dioxane, substituted or unsubstituted dioxolane, dichloroethylether, dichloromethyl methyl ether, dichloroethyl methyl ether, chloroform, carbon tetrachloride, phosgene, and combinations thereof.

2. The method of claim 1, wherein the saltwater comprises water comprising alkali metal ions or alkaline earth metal ions.

3. The method of claim 1, further comprising forming chloroethanol in more than 20 wt % yield from the halogenation of ethylene or ethane under one or more reaction conditions selected from temperature of halogenation mixture between about 120-160°

C.;

incubation time of between about 10 min-2 hour;

total halide concentration in the halogenation mixture between about 7-12M, catalysis with noble metal, and combinations thereof, and

using the chloroethanol to form the one or more organic compounds or enantiomers thereof selected from substituted or unsubstituted dioxane, substituted or unsubstituted dioxolane, dichloroethylether, dichloromethyl methyl ether, dichloroethyl methyl ether, chloroform, carbon tetrachloride, phosgene, and combinations thereof.

4. The method of claim 3, wherein the chloroethanol is formed in more than 40 wt % yield.

5. The method of claim 1, further comprising forming trichloroacetaldehyde (TCA) in more than 20 wt % yield from the halogenation of ethylene or ethane under one or more reaction conditions selected from temperature of halogenation mixture between about 160-200°

C.;

incubation time of between about 15 min-2 hour;

concentration of the metal halide in the higher oxidation state at more than 4.5M, and combinations thereof, and

using the TCA to form the one or more organic compounds or enantiomers thereof selected from the group consisting of substituted or unsubstituted dioxane, substituted or unsubstituted dioxolane, dichloroethylether, dichloromethyl methyl ether, dichloroethyl methyl ether, chloroform, carbon tetrachloride, phosgene, and combinations thereof.

6. The method of claim 5, wherein TCA is formed in more than 40 wt % yield.

7. The method of claim 1, wherein total amount of chloride content in the anode electrolyte is between 6-15M.

8. The method of claim 1, wherein saltwater comprises sodium chloride and the anode electrolyte comprises metal halide in the higher oxidation state in range of 4-8M, metal halide in the lower oxidation state in range of 0.1-2M and sodium chloride in range of 1-5M.

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

10. The method of claim 1, wherein the cathode electrolyte comprises water and the cathode is an oxygen depolarized 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 depolarized cathode that reacts hydrochloric acid and oxygen gas to form water.

11. 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.

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

13. The method of claim 1, wherein the metal halide is copper chloride.

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

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

16. 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.

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

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

19. 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.