Method for producing epoxides

• US 5,486,627 A
• Filed: 12/02/1994
• Issued: 01/23/1996
• Est. Priority Date: 12/02/1994
• Status: Expired due to Fees

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Swisher, Curtis N., Trent, David L., Quarderer, George J. Jr.
• Primary Examiner(s): Evans, Joseph E.
• Application Number:
  US08/348,639
• Time in Patent Office: 417 Days
• Field of Search: 549/520, 549/521, 549/522
• US Class Current: 549/521
• CPC Class Codes: C07D 301/26 Y being hydrogen

Abstract

Described herein is a method for producing epoxides which is continuous, inhibits formation of chlorinated byproducts, and eliminates or substantially reduces waste water discharge. The method includes:

(a) forming a low chlorides aqueous hypochlorous acid solution;

(b) contacting the low chlorides aqueous hypochlorous acid solution with at least one unsaturated organic compound to form an aqueous organic product comprising at least olefin chlorohydrin;

(c) contacting at least the olefin chlorohydrin with an aqueous alkali metal hydroxide to form an aqueous salt solution product containing at least epoxide; and

(d) isolating the epoxide from the aqueous salt solution;

wherein water is recovered from the product of at least Step (b) and recycled into Step (a) for use in forming the low chlorides aqueous hypochlorous acid solution. In this process, not only is the water internally recycled after Step (b), but a concentrated brine solution is generated in both Steps (a) and (d) which is useful in other processes such as electrochemical production of chlorine and caustic. The chlorine and caustic, in turn, may then be recycled back to the method of this invention.

Claims

1. A method for producing epoxides comprising the steps:

(a) forming a low chlorides aqueous hypochlorous acid solution;

(b) contacting the low chlorides aqueous hypochlorous acid solution with at least one unsaturated organic compound to form an aqueous organic product comprising at least olefin chlorohydrin, wherein the unsaturated organic compound contains from 2 to about 10 carbon atoms and is selected from the group consisting of substituted and unsubstituted olefins and cyclic olefins, the substituted olefins having substituents selected from the group consisting of an alkyl radical, a phenyl radical, and an alkylphenyl radical, each radical being independently either unsubstituted or substituted;

(c) contacting at least the olefin chlorohydrin with an aqueous alkali metal hydroxide to form an aqueous salt solution product containing at least epoxide; and

(d) isolating the epoxide from the aqueous salt solution;

wherein water is recovered from the product of at least Step (b) and recycled into Step (a) for use in forming the low chlorides aqueous hypochlorous acid solution.

2. The method of claim 1 wherein the water is recovered from the product of Step (b) by distilling the organic product comprising at least olefin chlorohydrin from the water.

8. The method of claim 1 wherein the unsaturated organic compound of Step (b) is selected from ethylene, propylene, butylene, 3-chloropropene, allyl alcohol, allyl chloride, 1-hexene, cyclohexene, styrene, and mixtures thereof.

9. The method of claim 1 wherein the unsaturated organic compound of Step (b) is selected from the group consisting of propylene, butylene, and allyl chloride.

10. The method of claim 1 wherein the contacting of Step (b) is done in a continuous process using a continuous stirred tank reactor with backmix stirring sufficient to maintain the HOCI concentration in the reactor of 0.2 weight percent or less.

11. The method of claim 1 wherein the aqueous alkali metal hydroxide of Step (c) is caustic from a chlor-alkali electrochemical cell.

12. The method of claim 1 wherein at least one of the alkali metals in the aqueous alkali metal hydroxide is selected from the group consisting of sodium and potassium.

13. The method of claim 12 wherein the aqueous alkali metal hydroxide comprises aqueous sodium hydroxide.

14. The method of claim 1 wherein the epoxide of Step (d) is isolated from the aqueous salt solution by distillation.

15. The method of claim 1 further comprising recycling the aqueous salt solution from Step (d) to a chlor-alkali electrochemical cell to form products comprising chlorine and caustic.

16. The method of claim 15 wherein the chlorine and caustic are recycled back for use in any of Steps (a), (c), or a combination thereof.

17. The method of claim 15 wherein, before recycling to the chlor-alkali electrochemical cell, the aqueous salt solution from Step (d) is combined with an aqueous salt solution produced from forming low chlorides aqueous hypochlorous acid in Step (a).

18. The method of claim 1 wherein the low chlorides aqueous hypochlorous acid solution of Step (a) is formed by a method comprising the steps:

(a) contacting an aqueous alkali metal hydroxide solution with chlorine to produce an aqueous alkali metal hypochlorite solution;

(b) contacting droplets of the aqueous alkali metal hypochlorite solution with chlorine gas to produce aqueous hypochlorous acid;

(c) vaporizing at least about 30 weight percent of the aqueous hypochlorous acid to produce a vapor phase and a liquid phase, the vapor phase comprising chlorine, water vapor, hypochlorous acid, and dichlorine monoxide, the liquid phase comprising hypochlorous acid in an aqueous salt solution;

(d) distilling the liquid phase using a vapor stripping stream containing at least about 20 mole percent chlorine to strip vapor phase hypochlorous acid and dichlorine monoxide from the aqueous salt solution; and

(e) absorbing the vapor phase hypochlorous acid and dichlorine monoxide from both Steps (c) and (d)into water.

19. The method of claim 18 wherein the alkali metal hydroxide is sodium hydroxide and the alkali metal hypochlorite is sodium hypochlorite.

20. The method of claim 18 wherein the alkali metal hydroxide is caustic from a chlor-alkali electrochemical cell.

21. The method of claim 18 further comprising collecting gases after Step (e) and recycling the gases to Step (d) for use in the vapor stripping stream.

22. The method of claim 1 wherein the low chlorides aqueous hypochlorous acid solution of Step (a) is formed by a method comprising:

(a) contacting solid sodium carbonate with a chlorine gas containing composition to form a composition comprising dichlorine monoxide vapor and carbon dioxide vapor; and

(b) absorbing the dichlorine monoxide into water.

23. The method of claim 22 wherein the chlorine gas containing composition further comprises water vapor.

24. The method of claim 22 wherein any unreacted chlorine gas containing composition from Step (a) is recycled back to Step (a) for contact with the solid sodium carbonate.

25. The method of claim 22 wherein solid sodium chloride is formed as a byproduct in Step (a), is dissolved in water, and is recycled to a chlor-alkali electrochemical cell to form products comprising chlorine and caustic.

26. The method of claim 1 wherein the low chlorides aqueous hypochlorous acid solution of Step (a) is formed by a method comprising:

(a) contacting an aqueous alkali metal hydroxide solution with chlorine to produce an aqueous alkali metal hypochlorite solution;

(b) contacting droplets of the aqueous alkali metal hypochlorite solution with chlorine gas to produce hypochlorous acid in an aqueous salt solution;

(c) extracting the hypochlorous acid from the aqueous salt solution using an organic solvent;

(d) stripping the hypochlorous acid from the organic solvent using a non-reactive gas; and

(e) absorbing the stripped hypochlorous acid into water.

27. The method of claim 26 wherein the organic solvent is a ketone.

28. The method of claim 27 wherein the ketone is methyl isobutylketone.

29. The method of claim 26, Step (c), further comprising:

(a) distilling the extracted aqueous salt solution using a vapor stripping stream to strip hypochlorous acid and organic solvent from the extracted aqueous salt solution; and

(b) combining the stripped hypochlorous acid and organic solvent with the extracted hypochlorous acid and organic solvent.

30. The method of claim 26 further comprising a step of recycling the aqueous salt solution to a chlor-alkali electrochemical cell to form chlorine and caustic.

31. The method of claim 26 wherein the non-reactive gas is selected from nitrogen or water vapor.

32. The method of claim 26 further comprising recycling the organic solvent from Step (d) back to Step (c).

3. The method of claim I wherein the water is recovered from the product of Step (b) by extracting the organic product from the water with an organic solvent.

4. The method of claim 3 wherein the organic solvent is a primary straight chain alcohol having from about 6 to about 12 carbon atoms.

5. The method of claim 4 wherein the primary straight chain alcohol is octanol.

6. The method of claim 3 wherein the extracted organic product is separated from the organic solvent.

7. The method of claim 6 wherein the organic solvent is recycled for use in extracting the organic product.