ELECTROCHEMICAL HYDROXIDE SYSTEMS AND METHODS USING METAL OXIDATION

• US 20150038750A1
• Filed: 07/30/2014
• Published: 02/05/2015
• Est. Priority Date: 07/31/2013
• Status: Active Grant

• Current Assignee: Calera Corporation
• Original Assignee: Calera Corporation
• Inventors: Weiss, Michael Joseph, Self, Kyle, Gilliam, Ryan J, Mariansky, Gal, Leclerc, Margarete K, Shipchandler, Riyaz Mohammed, Nagar, Jacob
• Granted Patent: US 9,828,313 B2
• Time in Patent Office: Days
• US Class Current: 570/241
• CPC Class Codes: C07C 17/02 to unsaturated hydrocarbons
• CPC Class Codes: C07C 19/01 containing chlorine
• CPC Class Codes: C07C 19/045 Dichloroethanes
• CPC Class Codes: C25B 1/00 Electrolytic production of inorganic compounds or non-metals
• 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 3/23 Oxidation halogenation C25B3/27
• CPC Class Codes: C25B 9/19 with diaphragms

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 an unsaturated hydrocarbon and/or a saturated hydrocarbon to form products. Separation and/or purification of the products as well as of the metal ions in the lower oxidation state and the higher oxidation state, is provided herein.

Claims

1. A system, comprising:

an electrochemical system comprising an anode chamber comprising an anode in contact with an anode electrolyte comprising metal ions wherein the anode is configured to oxidize the metal ions from a lower oxidation state to a higher oxidation state; and

a reactor operably connected to the anode chamber and configured to contact the anode electrolyte comprising the metal ions in the higher oxidation state with an unsaturated and/or saturated hydrocarbon to form one or more organic compounds comprising halogenated or sulfonated hydrocarbon and the metal ion in the lower oxidation state, wherein the reactor has a length;

diameter ratio of between 2-40.

2. The system of claim 1, wherein the reactor is configured to produce the halogenated or sulfonated hydrocarbon with more than 0.5 STY or more than 80% selectivity.

3. The system of claim 1, wherein the reactor has a length/diameter ratio of between about 20-40.

4. The system of claim 1, wherein the reactor is a packed-bed reactor or a trickle-bed reactor.

5. The system of claim 1, wherein the reactor has a packing material comprising structured packing material, unstructured packing material, or combination thereof.

6. The system of claim 5, wherein the structured packing material comprises thin corrugated metal plates or gauzes.

7. The system of claim 6, wherein diameter of the structured packing material is the diameter of the reactor.

8. The system of claim 5, wherein the unstructured packing material comprises raschig rings, pall rings, lessing rings, michael bialecki rings, berl saddles, intalox saddles, super intalox saddles, Tellerette®

rings, or combinations thereof.

9. The system of claim 8, wherein size of the unstructured packing material is between about ¼

of an inch to about 5 inches.

10. The system of claim 1, wherein the unsaturated hydrocarbon is ethylene, the halogenated hydrocarbon is ethylene dichloride, the metal ion is copper chloride, or combinations thereof.

11. The system of claim 1, wherein the electrochemical system further comprises a cathode chamber comprising a cathode in contact with a cathode electrolyte wherein the anode chamber and the cathode chamber are separated by an anion exchange membrane comprising a reinforcing material comprising polymer and wherein thickness of the membrane is between 20-130 um.

12. The system of claim 1, further comprising a separator configured to separate and purify the one or more organic compounds comprising halogenated or sulfonated hydrocarbon from the metal ions.

13. The system of claim 12, wherein the separator comprises reaction separation reactor system, compression-cooling system, liquid-liquid separation system, vapor-liquid separation system, scrubbing system, purification subprocess system, adsorbent, or combinations thereof.

14. The system of claim 13, wherein the liquid-liquid separation system comprises decanter, extractant, or combination thereof;

the vapor-liquid separation system comprises flash column, a distillation column, or combination thereof;

the purification subprocess system comprises decanter, sorbent, distillation column, or combinations thereof; and

/or the scrubber comprises column comprising an alkali.

15. A method, comprising:

contacting an anode with an anode electrolyte wherein the anode electrolyte comprises metal ion;

oxidizing the metal ion from a lower oxidation state to a higher oxidation state at the anode; and

reacting an unsaturated or saturated hydrocarbon with the anode electrolyte comprising the metal ion in the higher oxidation state in an aqueous medium, to form one or more organic compounds comprising halogenated or sulfonated hydrocarbon and the metal ion in the lower oxidation state, wherein the reacting is under one or more of reaction conditions favorable to produce the halogenated or sulfonated hydrocarbon with more than about 0.5 STY.

16. The method of claim 15, wherein the one or more of reaction conditions comprise temperature between 100-200°

C., pressure between 200-300 psig, or combination thereof.

17. The method of claim 15, wherein the one or more of reaction conditions comprise metal ion concentration, ratio of metal ion in the lower oxidation state to the metal ion in the higher oxidation state in the anode electrolyte, partial pressure of the unsaturated or saturated hydrocarbon, partial pressure of water vapor, flow rate of the anode electrolyte, flow rate of the unsaturated or saturated hydrocarbon, density of the anode electrolyte, viscosity of the anode electrolyte, reaction time, or combinations thereof.

18. The method of claim 15, wherein the one or more of reaction conditions are favorable to produce the halogenated hydrocarbon with more than about 80% selectivity.

19. The method of claim 15, wherein the unsaturated hydrocarbon is ethylene, the halogenated hydrocarbon is ethylene dichloride, the metal ion is copper chloride, or combinations thereof.

20. The method of claim 15, further comprising separating and purifying the one or more organic compounds comprising halogenated or sulfonated hydrocarbon from the aqueous medium.

21. The method of claim 20, wherein the separating and purifying comprises reaction separation process, compression-cooling process, liquid-liquid separation process, vapor-liquid separation process, scrubbing process, purification subprocess, adsorption, or combinations thereof.

22. The method of claim 21, wherein the reaction separation comprises reactive distillation, reactive extraction, or combination thereof;

liquid-liquid separation process comprises decantation, extraction, or combination thereof;

the vapor-liquid separation process comprises flash distillation, distillation, or combination thereof;

the purification subprocess process comprises decantation, adsorption, distillation, or combinations thereof; and

/or the scrubber comprises treatment with an alkali.