Patent GB-683625-A (GB)
Title: Di-organo peroxides
IPC: F02B47/00
Filed: 1949-11-29
Abstract: Di-organo peroxides are made from organo hydroperoxides or mixtures thereof by contacting them for less than ninety minutes with acid, or an acidic substance capable of hydrolysing to an acid having a dissociation constant of at least 10-3 in an amount and of sufficient concentration to convert a substantial proportion of said organo hydroperoxides to diorgano peroxides, while maintaining the temperature below about 150 DEG  F.  The organo radicals may be hydrocarbon radicals (e.g. alkyl, cycloalkyl, or alkylcycloalkyl, aralkyl or alkylene) or may contain substituents which do not interfere with the course of the reaction, e.g. chloro, fluoro, bromo, or nitro.  A solvent may be added to the pure hydroperoxide, e.g. pentane, hexane, pale oil, or kerosene. The acid &c. is employed in amounts of 0.1-1.5 mols. per mol. of hydroperoxide and acids or acidic substances specified are sulphuric, hydrochloric, phosphoric, nitric, hydrobromic and oxalic acids and acetyl chloride and dimethyl sulphate.  The hydroperoxide may be prepared by liquid-phase oxidation of a hydrocarbon with an oxygen-containing gas, if desired in presence of an alkaline-reacting inorganic salt and followed by a caustic wash.  The hydroperoxide need not be isolated for the acid treatment.  The di-organo peroxides may be separated or concentrated by fractional distillation or solvent extraction with aqueous methanol or other solvents specified, followed by a caustic and a water wash.  A conventional arrangement of apparatus for these steps is described.  In examples, dimethyl cyclopentyl hydroperoxide, tert.-butyl hydroperoxide, the hydroperoxides derived from n-decane, octene-1, decene-1, ethylcyclohexane, ethylbenzene, o-xylene, monoamylbenzenes and a petroleum distillate containing mainly paraffins and naphthenes with 12 per cent amount of aromatics were each treated with sulphuric acid, and that from n-decane with hydrochloric acid and hydrobromic acid.  The products are added to diesel fuels to increase the cetane number thereof, or if the oil-feed stock chosen for oxidation is a diesel fuel, the product, without separating the peroxide, is an improved diesel fuel.ALSO:Diesel fuels contain di-organo peroxides, made from organo hydroperoxides or mixtures thereof by contacting them for less than ninety minutes with an acid, or an acidic substance capable of hydrolysing to an acid, having a dissociation constant of at least 10-3 in an amount and of sufficient concentration to convert a substantial proportion of said organo hydroperoxides to di-organo peroxides, while maintaining the temperature below about 150 DEG F (see Group IV(b)).  The presence of the di-organo peroxides increases the cetane number of the Diesel fuel.  The fuels may be prepared direct by liquid-phase oxidation of a hydrocarbon with an oxygen containing gas, if desired in presence of an alkaline-reacting inorganic salt and followed by a caustic wash to give a hydrocarbon solution of a hydroperoxide which is subjected to acid treatment as above.  A conventional arrangement of apparatus for these steps is described.  In examples, dimethyl cyclopentyl hydroperoxide, tertbutyl hydroperoxide, the hydroperoxides derived from n-decane, octene-1, decene-1, ethylcyclohexane, ethylbenzene, o-xylene, monoamyl-benzenes, and a petroleum distillate containing mainly paraffins and naphthenes with 12 per cent of aromatics were each treated with sulphuric acid, and that from n-decane with hydrochloric acid and hydrobromic acid.