Methods and systems to form propylene chlorohydrin from dichloropropane using lewis acid

Patent metadata

Field	Value
Publication number	US-10807927-B2
Application number	US-202016751769-A
Country	US
Kind code	B2
Filing date	Jan 24, 2020
Priority date	May 30, 2018
Publication date	Oct 20, 2020
Grant date	Oct 20, 2020

Abstract

There are provided methods and systems to form propylene chlorohydrin by hydrolysis of dichloropropane in presence of Lewis acid and to further form propylene oxide from the propylene chlorohydrin.

First claim

What is claimed is:

1. A methods to form propylene chlorohydrin (PCH), 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 metal chloride with metal ion in higher oxidation state and the saltwater to result in one or more products comprising dichloropropane (DCP), and the metal chloride with the metal ion in the lower oxidation state;
(iii) separating the one or more products comprising DCP; and
(iv) hydrolyzing the DCP to PCH in an aqueous medium comprising Lewis acid.

2. The method of claim 1 , wherein the Lewis acid is selected from the group consisting of silicon chloride; germanium chloride; tin chloride; boron chloride; aluminum chloride; gallium chloride; indium chloride; thallium chloride; phosphorus chloride; antimony chloride; arsenic chloride; copper chloride; zinc chloride; titanium chloride; vanadium chloride;
chromium chloride; manganese chloride; iron chloride; cobalt chloride; nickel chloride;
lanthanide chloride; and triflates.

3. The method of claim 1 , wherein metal ion in the metal chloride 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.

4. The method of claim 1 , wherein the Lewis acid is selected from the group consisting of BCl 3 ; AlCl 3 ; GaCl 3 ; InCl 3 ; TlCl 3 ; CuCl 2 ; ZnCl 2 ; TiCl 3 ; TiCl 4 ; and LaCl 3 .

5. The method of claim 4 , wherein the metal chloride is copper chloride.

6. The method of claim 1 , wherein the Lewis acid is AlCl 3 ; GaCl 3 ; CuCl 2 ; or
ZnCl 2 and the metal chloride is CuCl and CuCl 2 .

7. The method of claim 1 , wherein the Lewis acid is in a concentration in a range of about 0.1-6 mol/kg of the solution.

8. The method of claim 1 , wherein the aqueous medium further comprises HCl, wherein the HCl is other HCl added to the hydrolysis step and/or is the HCl co-produced during the hydrolysis step.

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

10. The method of claim 1 , wherein the aqueous medium further comprises one or more chloride salts, wherein the one or more chloride salts are alkali metal chloride and/or alkaline earth metal chloride.

11. The method of claim 10 , wherein the one or more chloride salts are sodium chloride, lithium chloride, potassium chloride, calcium chloride, magnesium chloride, barium chloride, strontium chloride, or combination thereof.

12. The method of claim 1 , wherein concentration of the DCP in the hydrolysis reaction is between about 10-95% by volume.

13. The method of claim 1 , wherein the hydrolysis results in the PCH formed with selectivity of between 10-95 wt % and/or STY of more than 0.01.

14. The method of claim 1 , further comprising carrying out the hydrolysis in reaction conditions selected from temperature between 20° C.-200° C., pressure between 0-350 psig, residence time of less than two hours, and combinations thereof.

15. The method of claim 1 , further comprising after hydrolysis, transferring the aqueous medium comprising PCH and DCP to epoxidation; and epoxidizing the PCH with a base to form PO.

16. The method of claim 1 , further comprising transferring the metal chloride in the lower oxidation state and the saltwater from the chlorination reaction to an oxychlorination reaction where metal ion of the metal chloride from the lower oxidation state is oxidized to the higher oxidation state in presence of an oxidant.

17. The method of claim 16 , further comprising obtaining HCl from the hydrolysis reaction and using the HCl as the oxidant.

18. A system to form PCH, comprising:
(i) an electrochemical cell comprising an anode chamber comprising an anode and an anode electrolyte wherein the anode electrolyte comprises metal chloride and saltwater and the anode is configured to oxidize the metal chloride with metal ion in a lower oxidation state to a higher oxidation state; a cathode chamber comprising a cathode and a cathode electrolyte; and a voltage source configured to apply voltage to the anode and the cathode;
(ii) a chlorination reactor operably connected to the anode chamber of the electrochemical cell and configured to obtain the anode electrolyte and chlorinate 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 DCP and the metal chloride with the metal ion in the lower oxidation state; and
(iii) a hydrolysis reactor operably connected to the chlorination reactor and configured to obtain the one or more products comprising DCP from the chlorination reactor and configured to hydrolyze the DCP to PCH in an aqueous medium comprising Lewis acid.

19. The system of claim 18 , wherein the Lewis acid is selected from the group consisting of silicon chloride; germanium chloride; tin chloride; boron chloride; aluminum chloride; gallium chloride; indium chloride; thallium chloride; phosphorus chloride; antimony chloride; arsenic chloride; copper chloride; zinc chloride; titanium chloride; vanadium chloride;
chromium chloride; manganese chloride; iron chloride; cobalt chloride; nickel chloride;
lanthanide chloride; and triflates.

20. The system of claim 18 , further comprising an oxychlorination reactor operably connected to both the chlorination reactor and/or the hydrolysis reactor and configured to obtain aqueous medium from the chlorination reactor comprising the metal chloride with metal ion in the lower oxidation state and the higher oxidation state and/or obtain HCl produced in the hydrolysis reactor and configured to oxidize the metal chloride with metal ion in the lower oxidation state to the higher oxidation state using an oxidant comprising the HCl and oxygen.

Assignees

• Calera Corp

Inventors

• Weiss Michael Joseph
• Self Kyle
• Albrecht Thomas A
• Leclerc Margarete K

Classifications

• C25B3/11

  Halogen containing compounds · CPC title

• C25B3/27

  Halogenation · CPC title

• C07C29/124 Primary

  of halides · CPC title

• C07C31/36

  the halogen not being fluorine · CPC title

• C07C29/09 Primary

  by hydrolysis · CPC title