Electrochemical, chlorination, and oxychlorination systems and methods to form propylene oxide or ethylene oxide

• US 10,619,254 B2
• Filed: 04/26/2018
• Issued: 04/14/2020
• Est. Priority Date: 10/28/2016
• Status: Active Grant

• Current Assignee: Calera Corporation
• Original Assignee: Calera Corporation
• Inventors: Self, Kyle, Weiss, Michael Joseph, Gilliam, Ryan J, Albrecht, Thomas, Mariansky, Gal
• Primary Examiner(s): Rufo, Louis J
• Application Number:
  US15/963,637
• Publication Number:
  US 20180245223A1
• Time in Patent Office: 719 Days
• CPC Class Codes: C07C 17/08 to unsaturated hydrocarbons
• CPC Class Codes: C07C 19/01 containing chlorine
• CPC Class Codes: C07C 19/045 Dichloroethanes
• CPC Class Codes: C07C 29/64 by simultaneous introduction of -OH groups and halogens
• CPC Class Codes: C07C 31/36 the halogen not being fluorine
• CPC Class Codes: C07D 301/24 by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
• CPC Class Codes: C07D 303/04 containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
• CPC Class Codes: C25B 3/27 Halogenation

Abstract

Disclosed herein are methods and systems that relate to various configurations of electrochemical oxidation, chlorine oxidation, oxychlorination, chlorination, and epoxidation reactions to form propylene oxide or ethylene oxide.

Claims

1. A method, comprising:

(i) contacting an anode with an anode electrolyte in an electrochemical cell wherein the anode electrolyte comprises metal chloride and saltwater;

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

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

(ii) withdrawing the anode electrolyte from the electrochemical cell and chlorinating propylene with the anode electrolyte comprising the metal chloride with the metal ion in the higher oxidation state in the saltwater to result in one or more products comprising propylene chlorohydrin (PCH) and 1,2-dichloropropane (DCP) and the metal chloride with the metal ion in the lower oxidation state;

or withdrawing the anode electrolyte from the electrochemical cell and chlorinating ethylene with the anode electrolyte comprising the metal chloride with the metal ion in the higher oxidation state in the saltwater to result in one or more products comprising chloroethanol (CE) and ethylene dichloride (EDC) and the metal chloride with the metal ion in the lower oxidation state;

(iii) separating the one or more products comprising PCH and DCP or separating the one or more products comprising CE and EDC from the saltwater;

(iv) hydrolyzing the DCP to the PCH in the one or more products comprising PCH and DCP or hydrolyzing the EDC to the CE in the one or more products comprising CE and EDC; and

(v) epoxidizing the one or more products comprising PCH and DCP or the one or more products comprising CE and EDC with a base to form propylene oxide (PO) or ethylene oxide (EO), respectively.

2. The method of claim 1, further comprising oxychlorinating the metal chloride with the metal ion in the lower oxidation state in the saltwater after step (ii) and/or step (iii) to the metal ion in the higher oxidation state in presence of HCl and oxygen.

3. The method of claim 2, further comprising recirculating the metal chloride with the metal ion in the higher oxidation state back to step (ii).

4. The method of claim 1, wherein the chlorination results in between 20-90 wt % yield of PCH or between 20-90 wt % yield of CE.

5. The method of claim 1, further comprising forming sodium hydroxide in the cathode electrolyte and using the sodium hydroxide as the base to form the propylene oxide or the ethylene oxide.

6. The method of claim 1, wherein the one or more products from propylene or ethylene further comprise hydrochloric acid (HCl).

7. The method of claim 6, further comprising forming sodium hydroxide in the cathode electrolyte and using the sodium hydroxide to neutralize the HCl.

8. The method of claim 2, wherein the oxidizing, the chlorinating and the oxychlorinating steps are carried out in saltwater.

9. The method of claim 1, wherein the saltwater comprises alkali metal chloride.

10. The method of claim 9, wherein the alkali metal chloride is sodium chloride or potassium chloride.

11. The method of claim 2, wherein concentration of the metal chloride with the metal ion in the lower oxidation state entering the oxychlorination reaction is between about 0.5-2M;

concentration of the metal chloride with the metal ion in the lower oxidation state entering the chlorination reaction is between about 0.1-1.8M;

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

or combinations thereof.

12. The method of claim 2, further comprising separating the metal chloride solution from the one or more products comprising PCH or the CE after the chlorinating step and delivering the metal chloride solution back to the electrochemical reaction and/or the oxychlorination reaction.

13. The method of claim 1, wherein yield of the PO or yield of the EO is more than 90 wt % and/or space time yield (STY) of the PO or STY of the EO is more than 0.1.

14. The method of claim 1, wherein the metal chloride with the metal ion in the lower oxidation state is CuCl and the metal chloride with the metal ion in the higher oxidation state is CuCl₂.

15. A system, comprising:

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

a cathode in contact with a cathode electrolyte; and

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

/or an oxychlorination reactor operably connected to the electrochemical cell and/or chlorination reactor and configured to oxychlorinate the metal chloride with the metal ion from the lower oxidation state to the higher oxidation state in presence of HCl and oxygen;

a chlorination reactor operably connected to the electrochemical cell and/or the oxychlorination reactor wherein the chlorination reactor is configured to receive the metal chloride with the metal ion in the higher oxidation state from the electrochemical cell and/or configured to receive the metal chloride solution with the metal ion in the higher oxidation state from the oxychlorination reactor and chlorinate propylene or ethylene with the metal chloride with the metal ion in the higher oxidation state to result in one or more products comprising PCH and DCP or one or more products comprising CE and EDC, respectively, and the metal chloride solution with the metal ion in the lower oxidation state;

a separator operably connected to the chlorination reactor and configured to separate the one or more products comprising PCH and DCP or the one or more products comprising CE and EDC from the metal chloride solution in the saltwater;

a hydrolyzing chamber operably connected to the separator and configured to receive the one or more products comprising PCH and DCP or the one or more products comprising CE and EDC from the separator and hydrolyze the DCP to the PCH or hydrolyze the DCE to the CE; and

an epoxide reactor operably connected to the hydrolyzing chamber and configured to epoxidize the one or more products comprising PCH and DCP or the one or more products comprising CE and EDC with a base to form PO or EO, respectively.

16. The system of claim 15, wherein the electrochemical cell, the chlorination reactor and the oxychlorination reactor are all configured to carry out the reactions in saltwater.