Patent GB-680200-A (GB)
Title: Method of manufacturing detergents and the products obtained by such method
IPC: C11C3/00
Filed: 1947-12-22
Abstract: Detergents are prepared from fatty acid glycerides or sulphonatable fatty acids, their esters (other than the glycerides) or amides, colophony resins or their distillates and mineral oils by treating the primary material with at least 15 per cent of sulphuric acid of about 66 DEG  Baume concentration which is introduced progressively and with agitation, while maintaining the temperature not above 70 DEG  C., then adding to the resultant reaction mixture with agitation an aqueous solution of sodium hydroxide of a concentration of 15 to 20 per cent, ceasing the addition of the aqueous solution of sodium hydroxide when an aqueous layer forms below an oily product layer, decanting while still warm so as to separate the oily layer from the aqueous layer which contains sodium sulphate and excess sulphuric acid, and treating the oily layer with further aqueous sodium hydroxide, added progressively and with agitation until cessation of all exothermic reaction.  It is stated that when fatty acid glycerides are so treated, they are hydrolysed by the acid and the subsequent neutralization saponifies the formed fatty acids.  The aqueous layer removed after the first neutralization step may be treated to recover the sodium sulphate which may be used as a saturated solution to salt out part of the excess sulphuric prior to the neutralization in subsequent preparation of the detergent. The oily product layer may be washed at a stage after continuing and before completing the neutralization.  In the case of non-viscous reaction products, the neutralization may be commenced with sodium carbonate.  The products obtained can be moulded. They may be used themselves as detergents, if desired with fillers or as additives for ordinary soaps (see Group III).  In examples: (1) liquid oil of copra is treated with at least 15 per cent of 66 DEG  Be sulphuric acid added progressively with stirring at 50 DEG  C.; the mass is allowed to stand 5-10 hours and then neutralized by means of 15-20 per cent caustic soda with stirring and aqueous layers are separated by standing and decanting as they occur, and the final product is a malleable mass which is easily moulded; (2) crude palmetto oil; (3) palmetto grease from the refining of vegetable oils; (4) castor oil; and (6) olive oil or ground nut p  oil are treated as in (1), the final product in (3) being washed with non-saturated solutions of sodium sulphate or chloride to eliminate mineral salts; (5) linseed oil is treated as in (1) using at least 20 per cent sulphuric acid; (7) the total oil obtained by slow distillation of colophony is treated as in (1) with 25 per cent sulphuric acid and two layers are formed and neutralization is effected of either the lower layer only or both layers rendered homogenous by stirring; (8) crude shale oil is treated as in (1) with 15 to 25 per cent sulphuric acid added at a rate such that the temperature does not exceed 70 DEG  C. and neutralization effected by adding caustic soda at a rate that the product remains fluid and thereafter the product is dried.  The Specification as open to inspection under Sect. 91 relates to the production of detergents from oils, animal and vegetable greases, fatty acids, their esters (other than glycerides) and amides, petroleum oils, naphthalenic and anthracenic distillates, shale and lignite oils, and resins and colophanes and their oily distillates by sulphonating the primary material with concentrated or fuming sulphuric acid and then effecting a neutralization of the product, using the exothermic heat of reaction only as source of heating to form a product which can be run off and moulded.  Both sulphuric acid and oleum may be used simultaneously or successively in the acid treatment. Neutralization may be effected by an alkaline hydroxide or carbonate; products containing alkali sulphates result when there is used solid alkaline carbonate or concentrated aqueous alkaline hydroxide and relatively pure materials are obtained by progressively adding aqueous alkali hydroxide of a concentration insufficient to cause substantial saponification of the product, e.g. 15-20 per cent caustic soda, separating the salted-out aqueous layer of excess acid and sodium sulphate and then proceeding to full saponification with a more concentrated aqueous alkaline compound, e.g. 35-40 per cent caustic soda.  In typical examples: (1) a mixture of tallow and copra, palmetto and ground nut greases are reacted with sulphuric acid and the product neutralized with aqueous caustic soda following either of the procedures mentioned above to give the pure or sulphate contaminated products; (3) copra acids alone or admixed with ground nut fatty acids are similarly treated as in (1), there being then added 1-5 per cent alkaline alginates; (6) colophony oil distillate is treated with sulphuric acid and neutralized by admixing with resin heated with excess caustic soda so forming a detergent having a resinous base; (7) a mixture of copra and ground nut fatty acids and boric acid are treated with sulphuric acid and then oleum and neutralized in the above manner; (8) stearine mixed with copra and palm fatty acids are treated with sulphuric acid and then oleum and neutralized with aqueous sodium and potassium hydroxides; (9) white oil or oleine is treated similarly as in (8) but neutralized with aqueous caustic soda; (10) spindle oil is treated as in (9) to form a caustic cake having degreasing properties.  This subject-matter does not appear in the Specification as accepted.ALSO:Detergents are prepared from fatty acid glycerides or sulphonatable fatty acids, their esters (other than the glycerides) or amides, colophony resins or their distillates and mineral oils by treating the primary material with at least 15 per cent of sulphuric acid of about 66 DEG Baume concentration which is introduced progressively and with agitation, while maintaining the temperature not above 70 DEG  C., then adding to the resultant reaction mixture with agitation an aqueous solution of sodium hydroxide of a concentration of 15 to 20 per cent, ceasing the addition of the aqueous solution of sodium hydroxide when an aqueous layer forms below an oily product layer, decanting while still warm so as to separate the oily layer from the aqueous layer which contains sodium sulphate and excess sulphuric acid, and treating the oily layer with further aqueous sodium hydroxide, added progressively and with agitation until cessation of all exothermic reaction.  It is stated that when fatty acid glycerides are so treated, they are hydrolysed by the acid and the subsequent neutralization saponifies the formed fatty acids.  The aqueous layer removed after the first neutralization step may be treated to recover the sodium sulphate which may be used as a saturated solution to salt out part of the excess sulphuric prior to the neutralization in subsequent preparation of the detergent. The oily product layer may be washed at a stage after continuing and before completing the neutralization.  In the case of non-viscous reaction products, the neutralization may be commenced with sodium carbonate.  The products obtained can be moulded.  They may be used themselves as detergents, if desired with fillers such as crystalline sodium sulphate, for example, the product may be mixed with a saturated solution of sodium sulphate which crystallizes so forming a solid mass of crystals with the active product dispersed between the crystals; or they may be used as additives for ordinary soaps.  Some of the products in particular those obtained from mineral oils are good solvents for sulphur and may be used in conjunction with colloidal sulphur to form sulphur soaps; the products from mineral oils have degreasing properties.  In examples: (1) liquid oil of copra is treated with at least 15 per cent of 66 DEG  B<\>ae sulphuric acid added progressively with stirring at 50 DEG  C.; the mass is allowed to stand 5-10 hours and then neutralized by means of 15-20 per cent caustic soda with stirring and aqueous layers are separated by standing and decanting as they occur, and the final product is a malleable mass which is easily moulded and may be used in washing, e.g. the body and hair; (2) crude palmetto oil; (3) palmetto grease from the refining of vegetable oils; (4) castor oil, and (6) olive oil or ground nut oil are treated as in (1) the final product in (3) being washed with non-saturated solutions of sodium sulphate or chloride to eliminate mineral salts; (5) linseed oil is treated as in (1) using at least 20 per cent sulphuric acid yielding a product which may be incorporated in soap; (7) the total oil obtained by slow distillation of colophony is treated as in (1) with 25 per cent sulphuric acid and two layers are formed and neutralization is effected of either the lower layer only, or both layers rendered homogeneous by stirring; the product may be mixed with say 10 per cent of the above product obtained from castor oil or copra whereby its lathering property is improved; (8) crude shale oil is treated as in (1) with 15 to 25 per cent sulphuric acid added at a rate such that the temperature does not exceed 70 DEG  C. and neutralization effected by adding caustic soda at a rate that the product remains fluid and thereafter the product is dried; the sulphonated acid product dissolves 10-20 per cent of flowers of sulphur and such mixture after neutralization may be added to soap so forming a sulphur soap mixture.  The Specification as open to inspection under Sect. 91, relates to the production of detergents from oils, animal and vegetable greases, fatty acids, their esters (other than glycerides) and amides, petroleum oils, naphthalenic and anthracenic distillates, shale and lignite oils, and resins and colophanes and their oily distillates by sulphonating the primary material with concentrated or fuming sulphuric acid and then effecting a neutraliza