Electrochemical, halogenation, and oxyhalogenation systems and methods

• US 10,266,954 B2
• Filed: 10/28/2016
• Issued: 04/23/2019
• Est. Priority Date: 10/28/2015
• Status: Active Grant

• Current Assignee: Calera Corporation
• Original Assignee: Calera Corporation
• Inventors: Albrecht, Thomas A., Gilliam, Ryan J., Self, Kyle, Weiss, Michael Joseph
• Primary Examiner(s): Rufo, Louis J
• Application Number:
  US15/338,235
• Publication Number:
  US 20170121832A1
• Time in Patent Office: 907 Days
• CPC Class Codes: C25B 1/01 Products
• CPC Class Codes: C25B 15/081 Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
• CPC Class Codes: C25B 3/11 Halogen containing compounds
• CPC Class Codes: C25B 3/27 Halogenation
• CPC Class Codes: C25B 9/19 with diaphragms
• CPC Class Codes: C25B 9/23 comprising ion-exchange membranes in or on which electrode material is embedded
• CPC Class Codes: C25B 9/73 of the filter-press type
• CPC Class Codes: C25B 9/75 having bipolar electrodes
• CPC Class Codes: C25B 9/77 having diaphragms

Abstract

Disclosed herein are methods and systems that relate to electrochemically oxidizing metal halide with a metal ion in a lower oxidation state to a higher oxidation state; halogenating an unsaturated hydrocarbon or a saturated hydrocarbon with the metal halide with the metal ion in the higher oxidation state; and oxyhalogenating the metal halide with the metal ion from a lower oxidation state to a higher oxidation state in presence of an oxidant. In some embodiments, the oxyhalogenation is in series with the electrochemical oxidation, the electrochemical oxidation is in series with the oxyhalogenation, the oxyhalogenation is parallel to the electrochemical oxidation, and/or the oxyhalogenation is simultaneous with the halogenation.

Claims

1. A method, comprising:

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

contacting a cathode with a cathode electrolyte;

applying a voltage to the anode and the cathode and oxidizing the metal halide with metal ion in a lower oxidation state to a higher oxidation state at the anode;

(ii) halogenating an unsaturated hydrocarbon or a saturated hydrocarbon with the metal halide with the metal ion in the higher oxidation state in the saltwater to result in one or more organic compounds or enantiomers thereof and the metal halide with the metal ion in the lower oxidation state; and

(iii) oxyhalogenating the metal halide with the metal ion in the lower oxidation state to the higher oxidation state in presence of an oxidant

wherein the step (i) is in series with the step (iii).

2. The method of claim 1, wherein the oxidizing, the halogenating and the oxyhalogenating steps are carried out in saltwater.

3. The method of claim 2, wherein the saltwater comprises alkali metal halide.

4. The method of claim 3, wherein the alkali metal halide is sodium chloride or potassium chloride.

5. The method of claim 1, wherein the oxidant is HX gas, or HX solution and a gas comprising oxygen, wherein X is a halogen selected from fluoro, chloro, iodo, and bromo.

6. The method of claim 5, wherein the HX is HCl and the oxyhalogenation is oxychlorination.

7. The method of claim 1, wherein when the electrochemical step (i) is in series with the step (iii), the method further comprises delivering the anode electrolyte comprising the saltwater and the metal halide with the metal ion in the lower and the higher oxidation state from the step (i) to halogenating step (ii) for the halogenation of the unsaturated hydrocarbon or the saturated hydrocarbon and then delivering the metal halide with the metal ion in the lower oxidation state in the saltwater of the halogenating step (ii) to the step (iii) wherein the step (iii) oxyhalogenates the metal halide with the metal ion from the lower oxidation state to the higher oxidation state.

8. The method of claim 7, further comprising delivering the metal halide with the metal ion in the higher oxidation state in the saltwater of the oxyhalogenation step (iii) to the anode electrolyte of step (i).

9. The method of claim 8, wherein concentration of the metal halide with the metal ion in the lower oxidation state exiting the electrochemical reaction and entering the halogenation reaction is between about 0.5-2M;

concentration of the metal halide with the metal ion in the lower oxidation state exiting the halogenation reaction and entering the oxyhalogenation reaction is between about 0.7-2.5M;

concentration of the metal halide with the metal ion in the lower oxidation state exiting the oxyhalogenation reaction and entering the electrochemical reaction is between about 0.6-2.5M;

or combinations thereof.

10. The method of claim 1, wherein the oxidant is X₂ gas alone;

or HX gas and/or HX solution in combination with gas comprising oxygen or ozone;

hydrogen peroxide;

HXO or salt thereof;

HXO₃ or salt thereof;

HXO₄ or salt thereof;

or combinations thereof, wherein each X independently is a halogen selected from fluoro, chloro, iodo, and bromo.

11. The method of claim 1, wherein the yield of the one or more organic compounds is more than 90 wt % and/or the space time yield (STY) of the one or more organic compounds is more than 0.5.

12. The method of claim 1, wherein metal ion in the metal halide is copper and the unsaturated hydrocarbon is ethylene, propylene, or butylene which reacts with the metal halide with the metal ion in the higher oxidation state to form ethylene dichloride, propylene dichloride or dichlorobutane, respectively.

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

14. A system, comprising:

an electrochemical cell comprising an anode in contact with an anode electrolyte wherein the anode electrolyte comprises metal halide and saltwater;

a cathode in contact with a cathode electrolyte; and

a voltage source configured to apply a voltage to the anode and the cathode wherein the anode is configured to oxidize the metal halide with the metal ion from a lower oxidation state to a higher oxidation state;

a halogenation reactor operably connected to the electrochemical cell and an oxyhalogenation reactor wherein the halogenation reactor is configured to receive the anode electrolyte comprising the metal halide with the metal ion in the higher oxidation state from the electrochemical cell and/or configured to receive the metal halide solution with the metal ion in the higher oxidation state from the oxyhalogenation reactor and halogenate an unsaturated hydrocarbon or a saturated hydrocarbon with the metal halide with the metal ion in the higher oxidation state to result in one or more organic compounds or enantiomers thereof and the metal halide solution with the metal ion in the lower oxidation state; and

the oxyhalogenation reactor operably connected to the electrochemical cell and/or the halogenation reactor and configured to oxyhalogenate the metal halide with the metal ion from the lower oxidation state to the higher oxidation state in presence of an oxidant,

wherein the electrochemical cell is in series with the oxyhalogenation reactor.

15. The system of claim 14, wherein the electrochemical cell, the halogenation reactor and the oxyhalogenation reactor are all configured to carry out the reactions in saltwater.