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

• US 10,590,054 B2
• Filed: 05/29/2019
• Issued: 03/17/2020
• Est. Priority Date: 05/30/2018
• Status: Active Grant

• Current Assignee: Calera Corporation
• Original Assignee: Calera Corporation
• Inventors: Weiss, Michael Joseph, Self, Kyle, Albrecht, Thomas A, Leclerc, Margarete K
• Primary Examiner(s): Cutliff, Yate' K
• Application Number:
  US16/424,878
• Publication Number:
  US 20190367435A1
• Time in Patent Office: 293 Days
• CPC Class Codes: C07C 17/02 to unsaturated hydrocarbons
• CPC Class Codes: C07C 29/09 by hydrolysis
• CPC Class Codes: C07C 29/124 of halides
• CPC Class Codes: C07C 29/64 by simultaneous introduction of -OH groups and halogens
• CPC Class Codes: C07C 31/34 Halogenated alcohols
• CPC Class Codes: C07C 31/36 the halogen not being fluorine
• CPC Class Codes: C25B 3/27 Halogenation

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.

Claims

1. A method to form propylene chlorohydrin (PCH), comprising:

hydrolyzing dichloropropane (DCP) to PCH in an aqueous solution 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;

managanese chloride;

iron chloride;

cobalt chloride;

nickel chloride;

lanthanide chloride; and

triflates.

3. The method of claim 1, wherein the Lewis acid is selected from the group consisting of BCl₃;

AlCl₃;

GaCl₃;

InCl₃;

TlCl₃;

CuCl₂;

ZnCl₂;

TiCl₃;

TiCl₄; and

LaCl₃.

4. The method of claim 1, wherein the Lewis acid is AlCl₃;

GaCl₃;

CuCl₂;

or ZnCl₂.

5. 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.

6. The method of claim 1, wherein the aqueous solution further comprises HCl.

7. The method of claim 6, wherein the HCl is a combination of the other HCl added to the hydrolysis step and the HCl co-produced during the hydrolysis step.

8. The method of claim 7, wherein the HCl is in a concentration of between about 1-20 wt % HCl.

9. The method of claim 1, wherein the aqueous solution further comprises one or more chloride salts.

10. The method of claim 9, 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 10, wherein the one or more chloride salts are in a concentration between about 1-30 wt %.

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

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

16. The method of claim 1, further comprising after hydrolysis, transferring the solution comprising PCH and DCP to epoxidation;

and epoxidizing the PCH with a base to form PO in presence of the DCP.

17. A system to form PCH, comprising:

a hydrolysis reactor comprising DCP in an aqueous solution comprising Lewis acid, wherein the reactor is configured to hydrolyze the DCP to PCH.

18. The system of claim 17, 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;

managanese chloride;

iron chloride;

cobalt chloride;

nickel chloride;

lanthanide chloride; and

triflates.

19. The system of claim 17, wherein the Lewis acid is AlCl₃;

GaCl₃;

CuCl₂;

or ZnCl₂.

20. The system of claim 17, wherein the aqueous solution further comprises HCl.

21. The system of claim 17, wherein the aqueous solution further comprises one or more chloride salts.

22. The system of claim 21, wherein the one or more chloride salts are alkali metal chloride and/or alkaline earth metal chloride.