Patent GB-252327-A (GB)
Title: Oxidized products, processes of making same, and apparatus therefor
IPC: C07C27/10
Filed: 1926-03-02
Abstract: 252,327. Penniman, W. B. D. May 20, 1925, [Convention date]. Mineral and tar oils and waxes, purifying etc.; motor spirit; fats, extracting by solvents.-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, are oxidized to yield motor fuels, burning oils, aldehydes, fatty acids, alcohols, ketones, solvents, gums &c., by passing air or other oxygen-containing gas under pressure through a heated layer of the material of a depth sufficient substantially to deoxygenate the air &c.. the material being in the liquid state or suspended in a suitable liquid carrier. The oxidizing gas may be enriched with oxygen or diluted with steam. The process is preferably carried out at a temperature of 60-900‹ F., though the tem. perature range may extend from 300 to 1,000‹ 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 alkaline 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 reactions chamber. Baffles may be provided in the reactions chamber to impede the passage of air therethrough, to assist the circulation of the oil, or to cause any separated solid, 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 oils &c. removed by the current of air &c. are condensed with or without pressure, and the deoxygenated air may be passed through silica gel or absorbent carbon to extract residual vapour. As shown in Fig. 1, the apparatus for carrying out the process may comprise a vertical still 1 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 con. structed of copper, chromium or nickel chrome steel, morel 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. More than one air supply line may be provided, and a battery of stills may be employed, each being fitted at its upper part with a dephlegmator and heat interchanger. Residual material may be withdrawn by a pipe 10. In an example, a mid-continentle gas oil was treated at 500‹ F. under 300 1bs. pressure, air being supplied at 300 cubic feet per minute under a pump pressure of 350 1bs. 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 water soluble 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 aldehyde may first be removed by a concentrated solution of sodium bisulphate, which may be produced from the sulphur 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 sludge 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 aldehyde. The caustic soda solution from the distillate may be acidified and steam stilled to isolate the volatile fatty acids and phenloid bodies, which are then separated by sodium carbonate. The lower water soluble layer of the distillates, containing about three per cent of acids, mainly acetic acid. seven per cent of aldehydes, mainly acetaldehyde and propionaldehyde. three per cent of ketones, and five per cent of alcohols was subjected to distillations in twelve fractions between 20‹ and 95‹ C. The first two fractions were mainly acetaldehyde; the last nine were treated with caustic soda and redistilled. whereby a liquid of boiling point range 40-85‹ C. was obtained, which may be added to gasoline or kerosene to give. it antiknock properties, 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, hydrozine 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. The Specification as open to inspection under Sect. 91 (3) (a) comprises also the carrying out of the process at atmospheric pressure. This subject-matter does not. appear in the Specification as accepted. Reference has been, directed by the Comptroller to Specifications 16182/05 and 131,303.