Systems and methods using lanthanide halide

• US 10,556,848 B2
• Filed: 09/19/2018
• Issued: 02/11/2020
• Est. Priority Date: 09/19/2017
• Status: Active Grant

• Current Assignee: Calera Corporation
• Original Assignee: Calera Corporation
• Inventors: Leclerc, Margarete K, Cole, Emily A, Albrecht, Thomas A, Kostowskyj, Michael, Gilliam, Ryan J, Weiss, Michael J, Self, Kyle
• Primary Examiner(s): Bahta, Medhanit W
• Application Number:
  US16/135,357
• Publication Number:
  US 20190119186A1
• Time in Patent Office: 510 Days
• CPC Class Codes: C07C 17/013 by addition of halogens
• CPC Class Codes: C07C 17/02 to unsaturated hydrocarbons
• CPC Class Codes: C07C 17/04 to unsaturated halogenated hydrocarbons
• CPC Class Codes: C07C 17/06 combined with replacement of hydrogen atoms by halogens
• CPC Class Codes: C07C 17/093 by replacement by halogens
• CPC Class Codes: C07C 17/15 with oxygen as auxiliary reagent, e.g. oxychlorination
• CPC Class Codes: C07C 17/152 of hydrocarbons
• CPC Class Codes: C07C 17/154 of saturated hydrocarbons
• CPC Class Codes: C07C 17/156 of unsaturated hydrocarbons
• CPC Class Codes: C07C 17/158 of halogenated hydrocarbons
• 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 9/23 comprising ion-exchange membranes in or on which electrode material is embedded

Abstract

There are provided methods and systems related to use of one or more lanthanide halides in an electrochemical oxidation of metal halide in anolyte where the metal ion is oxidized from lower oxidation state to higher oxidation state at an anode; and then further use of the one or more lanthanide halides and the metal halide with the metal ion in the higher oxidation state in a halogenation reaction of an unsaturated hydrocarbon or a saturated hydrocarbon to form one or more products comprising halohydrocarbon.

Claims

1. A method, comprising:

contacting an anode with an anode electrolyte wherein the anode electrolyte comprises metal halide, one or more lanthanide halides, and water wherein the one or more lanthanide halides are in concentration range of between about 0.4-10 mol %;

contacting cathode with a cathode electrolyte;

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

reacting an unsaturated hydrocarbon or a saturated hydrocarbon with the metal halide in the higher oxidation state and the one or more lanthanide halides in the anode electrolyte, to result in one or more products comprising halohydrocarbon.

2. The method of claim 1, wherein lanthanide in the lanthanide halide is selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and combinations thereof.

3. The method of claim 1, wherein the lanthanide halide is cerium halide and/or lanthanum halide.

4. The method of claim 3, wherein the cerium halide is CeCl₃.7H₂O.

5. The method of claim 1, wherein the anode electrolyte further comprises salt.

6. The method of claim 1, wherein the one or more lanthanide halides result in more than 90% selectivity of the halohydrocarbon.

7. The method of claim 1, wherein the one or more lanthanide halides reduce temperature of the reaction by more than 5°

C. with substantially same or higher selectivity and/or space time yield (STY) of the halohydrocarbon as compared to when no lanthanide halide is used.

8. The method of claim 1, wherein the metal halide in the lower oxidation state and the metal halide in the higher oxidation state is CuCl and CuCl₂, respectively.

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

10. The method of claim 1, wherein the unsaturated hydrocarbon is ethylene, propylene, or butylene which reacts with the anode electrolyte comprising the metal halide in the higher oxidation state and the one or more lanthanide halides to form one or more products comprising ethylene dichloride, propylene dichloride or 1,4-dichlorobutane, respectively.

11. The method of claim 1, wherein the saturated hydrocarbon is methane, ethane, propane, or butane which reacts with the anode electrolyte comprising the metal halide in the higher oxidation state and the one or more lanthanide halides to form one or more products comprising dichloro methane, ethylene dichloride, propylene dichloride or 1,4-dichlorobutane, respectively.

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

13. 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.

14. 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.

15. The method of claim 1, wherein metal ion in the metal halide is copper.

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. A method, comprising:

contacting an anode with an anode electrolyte wherein the anode electrolyte comprises copper (I) chloride, copper (II) chloride, sodium chloride, cerium (III) chloride, and water;

contacting cathode with a cathode electrolyte;

applying voltage to the anode and the cathode and oxidizing the copper (I) chloride to copper (II) chloride at the anode; and

reacting an unsaturated hydrocarbon or a saturated hydrocarbon with the copper (II) chloride and the cerium (III) chloride in the anode electrolyte, to result in one or more products comprising halohydrocarbon.