Patent GB-366025-A (GB)
Title: Improvements in the separation of products containing oxygen from hydrocarbons
IPC: C07C7/10
Filed: 1930-10-27
Abstract: Organic oxygen compounds mainly consisting of aliphatic alcohols, fatty acids, fatty acid esters, and aliphatic ketones and aldehydes are separated from mixtures thereof with nonaromatic hydrocarbons containing at least 8 carbon atoms, by treating the liquid mixtures with liquid sulphur dioxide at temperatures below 75 DEG  C., preferably at which the single components are liquid, and preferably in the absence of substantial quantities of water.  The treatment may be carried out in a stirring autoclave with about \ba1/4\be to 5 parts by volume of sulphur dioxide for each part of initial material. On standing, two layers are formed, the upper layer mainly consisting of hydrocarbons, and the lower of a solution of the oxygen compounds in sulphur dioxide, from which the oxygen compounds may be separated by evaporating the sulphur dioxide or by freezing. The process may be carried out in a continuous manner.  If the hydrocarbon content of the initial mixture be high, a single or repeated treatment with liquid sulphur dioxide is sufficient.  If the oxygen containing compounds predominate, the solvent power of sulphur dioxide for the hydrocarbons may be reduced by the addition of from 1 to 10 per cent of aliphatic oxygen containing compounds, for example, methanol, ethanol, n-propanol, isopropanol, formic or acetic acid, methyl or ethyl formate, formamide, acetamide, or ethly urethane.  Initial materials to which the process may be applied include mixtures obtained by the destructive oxidation by means of air, nitrogen oxides, nitric acid, or several such agents conjointly, of aliphatic or naphthenic hydrocarbons such as mineral oil fractions boiling over 180 DEG  C., for example, paraffin wax, ceresine, Russian gas oil, paraffin oil, synthetic oils such as brown coal tar oils, or mixtures obtained by the destructive hydrogenation of tars, oils and the like. By separating the unoxidized hydrocarbons from such oxidation products, carboxylic acids, esters, alcohols of high molecular weight, ketones, lactones, and the like are obtained; if desired, a mixture mainly consisting of high molecular alcohols may be obtained by separating the saponifiable constituents of the mixture before the treatment with sulphur dioxide.  Oxidation products which have been subjected to a further treatment, for example, by heating, distillation, or catalytic hydrogenation may be treated.  Alcohol mixtures obtained by the catalytic dehydrogenation of esters such as animal or vegetable oils, fats and waxes, and of polyhydric alcohols may be separated by means of the process from the hydrocarbons formed by the hydrogenation. Alcohol mixtures obtained by condensing aliphatic or naphthenic hydrocarbons with oxygen compounds such as alkylene oxides or substances forming alkylene oxides may also be separated thereby from the accompanying hydrocarbons.  The oxygen compounds obtained by the above methods may be sulphonated or treated with alkalis, if acids be present, to prepare emulsifying agents. The mixtures of alcohols of high molecular weight free from hydrocarbons so obtained may be used for the preparation of esters, or for the manufacture of wetting, emulsifying and cleansing agents by sulphonation, sulphuric esters or sulphonic acids being obtained according to the method of sulphonation employed, and neutralization with alkaline substances.  According to examples (1) a Pennsylvanian middle oil is oxidized with air in presence of manganese naphthanate, the acid constituents removed by saponification, and the remainder hydrogenated with hydrogen in presence of a nickel-Kieselguhr catalyst; by treating with liquid sulphur dioxide at 25 DEG  C. a mixture consisting chiefly of alcohols is separated from the product, (2) oxidation products of Russian gas oil are separated from accompanying hydrocarbons with liquid sulphur dioxide, (3) unsaponifiable constituents obtained from a product of destructive oxidation of soft paraffin wax after separation of carboxylic acids and hydrogenation in presence of a catalyst obtained by reducing basic copper carbonate containing 2 per cent of molybdic acid, are separated from the unchanged wax by treatment with a mixture of liquid sulphur dioxide and formamide, acetic acid or formic acid, (4) oxygenated compounds obtained by treating paraffin wax with nitrogen dioxide and heating the product to 230 DEG  C. for two hours in a vessel made of or lined with chromium-nickel steel are separated by means of liquid sulphur dioxide from the accompanying hydrocarbons, (5) Spermaceti is hydrogenated in presence of a catalyst obtained by reducing basic copper carbonate containing 2 per cent of vanadium pentoxide, and a mixture consisting mainly of alcohols separated from the product by means of liquid sulphur dioxide, and (6) a paraffin fraction of Pennsylvanian crude oil is treated with ethylene oxide in presence of a Freedel-Crafts catalyst, ice and water is added thereto, and the water-insoluble reaction product after separation from the aqueous layer is treated with liquid sulphur dioxide, a product consisting mainly of alcohols being separated thereby from the accompanying hydrocarbons.  Specification 7309/14, [Class 91, Oils &c.], is referred to.ALSO:Organic oxygen compounds mainly consisting of aliphatic alcohols, fatty acids, fatty acid esters, and aliphatic ketones and aldehydes, are separated from mixtures thereof with non-aromatic hydrocarbons containing at least 8 carbon atoms, by treating the liquid mixtures with liquid sulphur dioxide at temperatures below 75 DEG  C., preferably at which the single components are liquid, and preferably in the absence of substantial quantities of water.  The treatment may be carried out in a stirring autoclave with about \ba1/4\be-5 parts by volume of sulphur dioxide for each part of initial material.  On standing, two layers are formed, the upper layer mainly consisting of hydrocarbons, and the lower of a solution of the oxygen compounds in sulphur dioxide, from which the oxygen compounds may be separated by evaporating the sulphur dioxide or by freezing.  The process may be carried out in a continuous manner.  If the hydrocarbon content of the initial mixture be high, a single or repeated treatment with liquid sulphur dioxide is sufficient.  If the oxygen-containing compounds predominate, or if it is desired to isolate a pure product free from hydrocarbons, the solvent power of sulphur dioxide for the hydrocarbons may be reduced by the addition of from 1 to 10 per cent of aliphatic oxygen containing compounds, for example, methanol, ethanol, n-propanol, isopropanol, formi or acetic acid, methyl or ethyl formate, formamide, acetamide, or ethyl urethane.  Initial materials to which the process may be applied include mixtures obtained by the destructive oxidation by means of air, nitrogen oxides, nitric acid, or several such agents conjointly, of aliphatic or naphthenic hydrocarbons such as mineral oil fractions boiling over 180 DEG  C., for example, paraffin wax, ceresine, Russian gas oil, paraffin oil, synthetic oils such as brown coal tar oils, or mixtures obtained by the destructive hydrogenation of tars, oils, and the like.  By separating the unoxidized hydrocarbons from such oxidation products, carboxylic acids, esters, alcohols of high molecular weight, ketones, lactones, and the like are obtained; if desired, a mixture mainly consisting of high molecular alcohols may be obtained by separating the saponifiable constituents of the mixture before the treatment with sulphur dioxide.  Oxidation products which have been subjected to a further treatment, for example, by heating, distillation, or catalytic hydrogenation may be treated.  Alcohol mixtures obtained by the catalytic dehydrogenation of esters such as animal or vegetable oils, fats, and waxes, and of polyhydric alcohols may be separated by means of the process from the hydrocarbons formed by the hydrogenation.  Alcohol mixtures obtained by condensing aliphatic or naphthenic hydrocarbons with oxygen compounds such as alkylene oxides or substances forming alkylene oxides may also be separated thereby from the accompanying hydrocarbons.  The oxygen compounds obtained by the above methods may be sulphonated or treated with alkalies, if acids be present, to prepare emulsifying agents.  The mixtures of alcohols of high molecular weight free from hydrocarbons so obtained may be used for the preparation of esters, or for the manufacture of wetting, emulsifying, and cleansing agents by sulphonation, sulphuric esters or sulphonic acids being obtained according to the method of sulphonation employed, and neutralization with alkaline substances. According to examples (1) a Pennsylvanian middle oil is oxidized with air in presence of manganese naphthenate, the acid constituents removed by saponification, and the remainder hydrogenated with hydrogen in presence of a nickel-kieselguhr catalyst; by treating with liquid sulphur dioxide at 25 DEG  C. a mixture consisting chiefly of alcohols is separated from the product; (2) oxidation products of Russian gas oil are separated from accompanying hydrocarbons with liquid sulphur dioxide; (3) unsaponifiable constituents obtained from a product of destructive oxidation of soft paraffin wax after separation of carboxylic acids and hydrogenation in presence of a catalyst obtained by reducing basic copper carbonate containing 2 per cent of molybdic acid, are separated from the unchanged wax by treatment with a mixture of liquid sulphur dioxide and formamide, acetic acid, or formic acid; (4) oxygenated compounds obtained by treating paraffin wax with nitrogen dioxide and heating the product to 230 DEG  C. for two hours in a vessel made of or lined with chromium-nickel steel are separated by means of liquid sulphur dioxide from the accompanying hydrocarbons; (5) spermaceti is hydrogenated in presence of a catalyst obtain