Patent GB-255020-A (GB)
Title: Oxidized products, processes of making same, and apparatus therefor
IPC: C07C27/10
Filed: 1926-03-02
Abstract: 255,020. Penniman, W. B. D. July 7, 1925, [Convention date]. Mineral and tar oils; motor spirit, paraffin, and mineral waxes; fats, extracting by solvents.-The oxidation of crude petroleum and its distillates, shale oils and tars, waxes, sludges, petroleum residues, asphaltic oils, asphalt, malthas, cracked oils and residues from cracking stills, wood tar oils and wood tar, peat and lignite distillates, coal tar oils and coal tars. and oils containing powdered coal. coke, or peat, sulphur &c. in suspension, is effected by passing air or other oxygencontaining gas through a layer of the material of a depth sufficient substantially to deoxygenate the air &c., the pressure being at or below atmospheric pressure. Or the oxidation may be carried out in a series of treatment zones, the pressure in one of them being at or below atmospheric pressure, and the pressure in the other zones being below, at, or above atmospheric pres. sure. The products of oxidation include aldehydes, fatty acids, alcohols, ketones, solvents. gums, and substances adapted for use as motor fuels or burning oils. The oxidizing gas may be enriched with oxygen or be diluted with steam, and the process is preferably carried out at a temperature of 600-900‹ F., though the temperature range may extend from 300 to 1000‹ F. Catalysts such as aluminium chloride, the oxides of manganese, lead, iron, chromium, vanadium, zinc, copper, or calcium may be added, and also neutralizing agents such as quick lime, limestone, or alkali carbonates. The depth of the oil layer under treatment is preferably maintained substantially constant, as by intermittently or continuously feeding fresh oil to, and withdrawing treated oil from, the reaction chamber. Baffles may be provided in the reaction chamber to impeae the passage of air therethrough, to assist the circulation of the oil, or to cause any separated solid materials, such as carbon, to be deposited in a desired part of the apparatus. The reaction chamber may be externally heated, or the, oil &c. and air &c. may be preheated and the temperature in the chamber be maintained solely by, the heat of reaction. The oxidation and disintegration products of the oil &c. removed by the currentof air &c. are condensed, another decxygenated air may be passed through silica gel or absorbent carbon to extract residual vapours. As shown in Fig. 1, the apparatus for carrying out the process may comprise a vertical still adapted to be heated by a gas fired furnace, a condenser tube and coil 24. 25, and a receiver 26, the members 24-26 being preferably constructed of copper, chromium nickel chrome steel, monel metal or other acid-resisting material; or enamel lined condenser tubes may be employed. Oil is supplied to the still by a pump 5, pipe 6, coil 12, and pipe 8, and air by a pump 9, pipe 10, coil 7, and pipe 13 having at its lower end an upwardly directed nozzle 14 or a series of radially extending perforated pipes. Alternatively, air may be drawn through the apparatus bv a suction pump 9. More than one air supply line may be provided, and when a multistage oxidation is effected, using a battery of stills working under different pressures, each, may be fitted at its upper part with a dephlegmator and heat interchanger. Residual material may be withdrawn by a pipe 16. In an example, a mid-continental gas oil containing one per cent of sulphur was treated at 500‹ F. at approximately atmospheric pressure. The temperature during treatment rose to and was maintained at 725- 750‹ F. The distillate obtained was run into a wooden tank and separated, on standing, into an upper water-insoluble layer, an intermediate mixed layer, and a lower layer containing a water solution of organic substances. Any watersoluble constituents in the upper layer were washed out with water. From the upper layer acids, phenols. aldehydes &c. may be removed by agitation with a ten per cent solution of caustic soda: or acids may first be removed by sodium carbonate solution, and aldehydes and phenols then be separated by caustic soda: or aldehydes may first be removed by a concentrated solution of sodium bisulphite, which mav be produced from the uslphur dioxide formed during the process, when a sulphur bearing oil is treated. The material remaining after the treatment with caustic soda may be washed with water, treated with a small amount of sulphuric acid, and distilled, the distillates up to 400‹ F., which may contain up to three per cent of oxygen, being used as a gasoline substitute; or they may be mixed with ordinary gasoline, benzol, acetone &c. The residues from the distillation may be returned to the still for further treatment. From the sludge obtained by the treatment with sulphuric acid, alcohols may be recovered by diluting the sludges with water and then steam stilling it. The upper layer may be first purified by passage through fuller's earth, silica gel, or heated bauxite; or it may be redistilled with aluminium chloride; or it may, following the treatment with sodium carbonate or caustic soda, be distilled with five per cent of aniline or with phenol to separate aldehydes. The caustic soda solution from the distillate may be acidified and steam stilled to isolate the volatile fatty acids and phenoloid bodies, which are then separated from each other by sodium carbonate. The lower water soluble layer of the distillate, containing lower fatty acids, . aldehydes, ketones, and alcohols, was subjected to fractional distillation between 20‹ and 95‹ C. The earlier fractions were practically pure acetaldehyde; the later fractions were treated with caustic soda and redistilled, whereby a clear liquid of boiling point range 40-85‹ C., was otbained, which may be added to gasoline or kerosene to give it antiknock properties, or be used as a solvent for shellac. gums, cellulose esters etc.; or for the extraction of fats. The residue from this distillation may be treated with sulphuric acid and steam stilled, the gummy residue being either used for making gums or being combined with aniline, hydrazine, or phenol. The oil &c. withdrawn from the still during the process may be treated to recover fatty acids or may be returned to the still. Before treatment, the oil &c. may be chlorinated, nitrated, sulphated &c. Specification 252.327 is referred to. Reference has been directed by the Comptroller to Specifications 2666/80. [Class 55. Gas manufacture] : 16182/05: 131,301 and 131,302, [both in Class 2 (iii) Dyes &c.] ; 131,303 and 181,034.