REDUCTION OF CONTENT OF CARBOXYLIC ACIDS AND DERIVATIVES THEREOF IN OLEUM, DISULFURIC ACID OR CONCENTRATED SULFURIC ACID

Abstract

The present invention concerns a process for the reduction of content of carboxylic acids and derivatives thereof in oleum, disulfuric acid or concentrated sulfuric acid. The invention further concerns a process for the manufacture of carboxylic acid anhydrides comprising the process for the reduction of content of carboxylic acids and derivatives thereof from oleum, disulfuric acid or concentrated sulfuric acid.

Claims

1. A process for the reduction of content of carboxylic acids and derivatives thereof in oleum, disulfuric acid or concentrated sulfuric acid, the process comprising submitting a first fraction comprising oleum, disulfuric acid or concentrated sulfuric acid with a first content of carboxylic acid or at least one derivative thereof to a gas stripping operation in order to obtain a second fraction comprising oleum, disulfuric acid or concentrated sulfuric acid with a second content of carboxylic acid or at least one derivative thereof, wherein the second content of carboxylic acid or at least one derivative thereof in the fraction comprising oleum, disulfuric acid or concentrated sulfuric acid is lower than the first content.

2. The process according to claim 1, wherein carboxylic acid and/or carboxylic acid anhydride is comprised in the first fraction comprising oleum, disulfuric acid or concentrated sulfuric acid.

3. Process The process according to claim 1, wherein the carboxylic acid is a halogenated carboxylic acid, wherein the halogenated carboxylic acid is a compound of formula (I) HalR.sub.2C(O)OH, wherein Hal is selected from the group consisting of F, Cl and Br, and wherein R is independently selected from the group consisting of H, F, Cl, Br, alkyl and aryl .

4. The process according to claim 3, wherein Hal is F.

5. The process according to claim 4, wherein the compound of formula (I) is trifluoroacetic acid.

6. Process The process according to claim 2, wherein the carboxylic acid anhydride is a compound of formula (II) HalR.sub.2C(O)OC(O)CR.sub.2Hal, wherein Hal is selected from the group consisting of F, Cl and Br, and wherein R is independently selected from the group consisting of H, F, Cl, Br, alkyl and aryl.

7. The process according to claim 1, wherein the oleum contains from 5 to 95 wt % free SO.sub.3.

8. Process The process according to claim 1, wherein the sulfuric acid has a concentration of equal to or more than 20%.

9. The process according to claim 1, wherein the gas stripping operation is performed using at least one gas selected from the group consisting of air, oxygen, CO.sub.2, exhaust gas, and inert gases.

10. The process according to claim 1, wherein the gas stripping operation is performed continuously in a countercurrent or co-current way, or batchwise in a countercurrent or co-current way.

11. The process according to claim 1, wherein the first fraction submitted to the gas stripping operation has a temperature of from 10 to 160 C. in the gas stripping operation.

12. The process according to claim 1, wherein the stripping operation is performed at a pressure of from 50 to 500 mbar.

13. A process for the manufacture of a carboxylic acid anhydride comprising a step of reacting a compound of formula (III) R.sub.3C(O)OH, wherein R independently is selected from the group consisting of H, F, Cl, Br, alkyl and aryl, with sulfuric acid, oleum and/or disulfuric acid, and which further comprises the process according to claim 1.

14. The process according to claim 13, wherein the compound of formula (III) is a compound of formula (I) HalR.sub.2C(O)OH, wherein Hal and R are as defined.

15. A process for the manufacture of an agrochemically or pharmaceutically active compound or an intermediate thereof, the process comprising a step wherein a fraction of oleum, disulfuric acid or concentrated sulfuric acid having a content of carboxylic acids is generated, and wherein the fraction of oleum, disulfuric acid or concentrated sulfuric acid having a content of carboxylic acids is submitted to the process according to claim 1.

16. The process according to claim 6, wherein the compound of formula (II) is trifluoroacetic acid anhydride.

17. The process according to claim 7, wherein the oleum contains from 25 to 80 wt % free SO.sub.3.

18. The process according to claim 17, wherein the oleum contains from 50 to 70 wt % free SO.sub.3.

19. The process according to claim 9, wherein the inert gases comprise helium, nitrogen, argon, or xenon.

20. The process according to claim 14, wherein Hal is F.

Description

EXAMPLE 1

[0032] A first fraction of 98% H.sub.2SO.sub.4, obtained by the reaction of CF.sub.3COOH to CF.sub.3C(O)OC(O)CF.sub.3, manufactured by a procedure similar to the procedure described in EP2810931, after a reduction of CF.sub.3COOH by distillation and dilution of the oleum sump to 98% H.sub.2SO.sub.4 in the ceramic lined Pfaudler reaction vessel, was fitted with a subsurface dip pipe. The fraction comprised 2.8% CF.sub.3COOH (TFA) as measured by IC. At a temperature of approximately 130 C., a nitrogen flow of about 5 m.sup.3/h was introduced into the fraction. The results of the reduction of content of CF.sub.3COOH (TFA) in the fraction as measured by IC are given in the table below:

TABLE-US-00001 TFA [%] Elapsed time 2.8 0:00:00 2.2 4:00:00 0.78 6:00:00 0.33 8:00:00 0.08 12:00:00 0.03 16:00:00

[0033] The resulting fraction was suitable to be submitted to conventional waste water treatment without additional treatment necessary for any freight of organic CF.sub.3 contaminants. The gas flow emerging from the stripping operation was submitted to a scrubber cascade alternating equipped with an aqueous solution of KOH and H.sub.2O.sub.2.