Patent GB-795927-A (GB)
Title: Improvements in and relating to the preparation of peracids
IPC: C07C409/26
Filed: 1954-11-23
Abstract: An aliphatic monocarboxylic peracid having 2 or 3 carbon atoms in the molecule is obtained by reacting a saturated aliphatic monoaldehyde having 2 or 3 carbon atoms in the molecule with molecular oxygen at a temperature below 15 DEG  C., preferably at about -5 DEG  to 0 DEG C., the reaction being carried out either in the presence of an organic solvent or by using an excess of the aldehyde to form an aldehyde monoperacylate dissolved in the resulting liquid reaction mixture and then decomposing the aldehyde monoperacylate at a temperature of at least - 10 DEG  C. to form the per acid, the aldehyde formed during such decomposition being immediately and continuously removed in vapour form from the reaction mixture. Specified organic solvents are acetone, acetic acid, acetal, methyl ethyl ketone, ethyl acetoacetate and butyl acetate.  The oxygen used can be in admixture with an inert gas, e.g. air may be used and the oxidation is preferably carried out in the presence of an oxidation catalyst, e.g. a heavy metal salt, such as a salt of cobalt, copper, or iron but preferably catalysis is effected by irradiating the aldehyde with ultra-violet light or by the presence of a small amount of ozone in the oxygen.  The solution of aldehyde monoperacylate must be kept cold prior to the decomposition step, a storage temperature of 0 DEG  C. and below being preferred.  The decomposition of the monoperacylate can be carried out catalytically or non-catalytically and in the former case the use of an acidic esterification catalyst, e.g. sulphuric acid or p-toluene sulphonic acid is preferred.  The catalytic decomposition may be carried out at temperatures as low as - 10 DEG  C. but no catalyst is required when decomposition is effected at temperatures of 50 DEG  C. or above.  It is preferred to carry out the decomposition step non-catalytically, e.g. by feeding the aldehyde monoperacylate, which may be dissolved in the liquid reaction mixture, into the kettle of a conventional still (comprising a kettle provided with a fractionating column) which contains an inert solvent under reflux.  The solvent used must either have a boiling-point higher than that of the per-acid or must form an azeotrope with the per-acid.  The still is operated under reduced pressure to provide a kettle temperature within the range of 50 DEG to 150 DEG  C. depending on the nature of the solvent used and the condenser at the still head is maintained at such a temperature that the peracetic acid and the solvent are condensed while the aldehyde liberated in the reaction is allowed to go past the still head and is recovered in a cold trap or scrubbing system along with any low boiling material to be removed.  The peracid is continuously removed from the still head in the form of a solution in the solvent used. In another method the solution of aldehyde monoperacylate is completely vaporized in a heated zone and heated to a temperature within the range of about 50 DEG  to 250 DEG  C. and the vapours passed to a condenser or dephlegmator which is maintained at such a temperature as to condense the per-acid and solvent while allowing the aldehyde to pass through along with any low-boiling material present and the aldehyde may be recovered by condensation or by absorption in a suitable solvent.  The heated zone in this procedure may be a section or coil of piping or tubing heated externally, e.g. by steam, or it may be a jacketed kettle, a flask immersed in a heated oil bath or a calandria.  In another method the vapours from the pyrolysis zone are fed continuously to a fractionating column, near the middle thereof, with the aldehyde being taken off at the head of the column.  For complete removal of the aldehyde from the peracid it is preferred to feed inert solvent vapours or an inert gas into the bottom of the fractionating column so as to effect vaporization of any dissolved aldehyde, the per-acid being obtained as a residue at the bottom of the column, in the form of a solution in the inert solvent.  Suitable solvents for use in the continuous rectification process which is preferably carried out under reduced pressure are those boiling between 21 DEG  and 110 DEG  C., e.g. acetone and ethyl acetate.  Several examples are given for the production of acetaldehyde monoperacetate and its decomposition to form peracetic acid and an example is also given for the production of propionaldehyde monoperpropionate and its decomposition to form perpropionic acid.