Purification of tertiary hydroperoxides containing primary and secondary hydroperoxide contaminants

• US 4,891,101 A
• Filed: 11/23/1988
• Issued: 01/02/1990
• Est. Priority Date: 11/23/1988
• Status: Expired due to Fees

• Current Assignee: ARCO Chemical Technology LP A Partnership of de
• Original Assignee: ARCO Chemical Technology, Inc. (Lyondellbasell Industries NV)
• Inventors: Sullivan, Carl J.
• Primary Examiner(s): Manoharan, Virginia
• Application Number:
  US07/275,483
• Time in Patent Office: 405 Days
• Field of Search: 203/14, 203/36, 203/37, 203/43, 203/60, 203/59, 203/DIG. 6, 203/38, 568/576
• US Class Current: 203/36
• CPC Class Codes: C07C 407/003 Separation; Purification; Stabilisation; Use of additives
• CPC Class Codes: C07C 409/04 the carbon atom being acyclic
• CPC Class Codes: Y10S 203/06 Reactor-distillation

Abstract

Primary and secondary hydroperoxide contaminants in a tertiary hydroperoxide composition obtained by oxidation of a branched hydrocarbon are removed by contacting the tertiary hydroperoxide with a carboxylic acid derivative such as an anhydride and a basic compound such as sodium hydroxide. A tertiary hydroperoxide such as tertiary butyl hydroperoxide is purified with minimal loss of the desired tertiary hydroperoxide.

Claims

1. A process for purifying a tertiary hydroperoxide composition comprised of a tertiary hydroperoxide and an undesired primary or secondary hydroperoxide contaminant which comprises the steps of:

(A) contacting the tertiary hydroperoxide composition with

(a) a basic compound selected from the group consisting of alkali metal oxides, alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkaline earth oxides, alkaline earth hydroxides, alkaline earth carbonates, alkaline earth bicarbonates, and amines, and

(b) a carboxylic acid derivative selected from the group consisting of anhydrides, esters, acid halides, and amides

at a temperature of between about 20°

C. and 175°

C. and for a period of from about 30 seconds to 1 hour to decompose said primary or secondary hydroperoxide contaminant, and

(B) separating a purified tertiary hydroperoxide composition from said basic compound, said carboxylic acid derivative, and said primary or secondary hydroperoxide decomposition product.

2. The process of claim 1 wherein said tertiary hydroperoxide is tertiary butyl hydroperoxide.

3. The process of claim 1 wherein said basic compound is an alkali metal hydroxide.

4. The process of claim 1 wherein said tertiary hydroperoxide composition is contacted with from about 0.3 to 5.0 milliequivalents of said carboxylic acid derivative per gram of total hydroperoxide present.

5. The process of claim 1 wherein said tertiary hydroperoxide composition is contacted with from about 1.5 to 3.5 milliequivalents of said basic compound per milliequivalents of said carboxylic acid derivative.

6. The process of claim 1 wherein said carboxylic acid derivative is an anhydride.

7. The process of claim 6 wherein said anhydride is maleic anhydride.

8. The process of claim 1 wherein said tertiary hydroperoxide composition is separated by liquid-liquid extraction.

9. The process of claim 1 wherein said tertiary hydroperoxide composition is separated by azeotropic distillation.

10. The process of claim 1 wherein said tertiary hydroperoxide composition additionally comprises a tertiary alcohol.

11. The process of claim 1 wherein said tertiary hydroperoxide composition additionally comprises water.

12. A process for purifying a tertiary butyl hydroperoxide composition comprising tertiary butyl hydroperoxide and an undesired primary or secondary hydroperoxide contaminant which comprises the steps of:

(A) contacting the tertiary butyl hydroperoxide composition with

(a) from about 0.3 to 5.0 milliequivalents of a carboxylic acid anhydride per gram of total hydroperoxide present and

(b) from about 1.5 to 3.5 milliequivalents of an alkali metal hydroxide per milliequivalent of said carboxylic acid anhydride at a temperature of between about 20°

C. and 175°

C. for a period of from about 30 seconds to 1 hour to decompose said primary or secondary hydroperoxide contaminant; and

(B) separating a purified tertiary butyl hydroperoxide composition from said carboxylic acid anhydride, said alkali metal hydroxide, and primary or secondary hydroperoxide decomposition product.

13. The process of claim 12 wherein said alkali metal hydroxide is sodium hydroxide.

14. The process of claim 12 wherein said carboxylic acid anhydride is maleic anhydride.

15. The process of claim 12 wherein said tertiary butyl hydroperoxide composition is separated by liquid-liquid extraction.

16. The process of claim 12 wherein said tertiary butyl hydroperoxide composition is separated by azeotropic distillation.

17. A process for purifying a tertiary butyl hydroperoxide composition comprising tertiary butyl hydroperoxide and an undesired primary or secondary hydroperoxide contaminant which comprises the steps of:

(A) contacting the tertiary butyl hydroperoxide composition with

(a) from about 0.3 to 5.0 milliequivalents of maleic anhydride per gram of total hydroperoxide present and

(b) from about 1.5 to 3.5 milliequivalents of sodium hydroxide per milliequivalent of maleic anhydride at a temperature of between about 30°

C. to 80°

C. for a period of from about 1 to 30 minutes to decompose said primary or secondary hydroperoxide contaminant; and

(B) separating a purified tertiary butyl hydroperoxide composition from said maleic anhydride, said sodium hydroxide, and said primary or secondary hydroperoxide decomposition product.

18. The process of claim 17 wherein said tertiary butyl hydroperoxide composition is separated by liquid-liquid extraction.

19. The process of claim 17 wherein said tertiary butyl hydroperoxide composition is separated by azeotropic distillation.