Patent GB-477521-A (GB)
Title: Detergents
IPC: C09K23/00
Filed: 1936-06-25
Abstract: <PICT:0477521/IV/1> <PICT:0477521/IV/2> <PICT:0477521/IV/3> One molecular proportion of a fatty oil and one molecular proportion of anhydrous glycerine are reacted with such an excess of fuming sulphuric acid over the equivalent of three molecular proportions of 100 per cent sulphuric acid that the sulphuric acid remaining after the reaction has a concentration of not less than 95 per cent, and the product is neutralized without previous dilution, in the presence of a large excess of already neutralized material.  The glycerine and fatty oil or the glycerine and excess fuming sulphuric acid may be first reacted together or the three components may be mixed simultaneously.  The product may be prepared free from inorganic salts by extraction with alcohol, e.g. butyl alcohol, before or after the neutralization step or the sulphate free sodium, potassium, ammonium, triethanolamine and magnesium salts may be prepared from the calcium salt, the calcium being precipitated by means of carbon dioxide or a carbonate, phosphate or oxalate.  The effect of adding solutions of the following salts to the pure and sulphate containing products is stated: calcium, barium, potassium, magnesium, aluminium, ferric and mercuric chlorides, ammonium and copper sulphates, lead acetate and silver nitrate.  No turbidity or precipitate is given with hydrochloric acid, hard water and sea water.  In an example, glycerine is treated with fuming sulphuric acid and the mixture is reacted with coconut oil.  The glycerine and fuming sulphuric acid are pumped into a mixer 13 shown in Fig. 5, which consists of a cylindrical shell provided with paddles 24, 25 and 26 carried on a vertical shaft, and hollow annular members 27 and 28 through which cooling water is circulated.  Each of the three upper paddles, as shown in Fig. 7, consists of a circular plate with four vanes extending helically above it to throw the liquid outwardly and four helical vanes below the plate to draw the liquid inwardly and propel it downwards to the underlying cooling element.  The fourth paddle 25 is of similar construction but both upper and lower vanes force the liquid outwardly so that some is circulated to the top of the mixer. Before leaving the mixer by the opening 19, the reaction liquid passes cooling members 28 and paddles 26.  The reaction liquid is treated with coconut oil in a second mixer similar in construction to the first, but the hollow annular members are supplied with heating water instead of cooling water and the reaction mixture is, in part returned to the top of the mixer by the second paddle, the upper and lower vanes of which throw the reaction mixture outwardly.  The reaction mixture is passed to a neutralizer, Fig. 9, comprising cooling and mixing elements.  Caustic soda solution enters by pipe 40 and the reaction mixture by the pipe 38, and the resulting neutralized product passes down through a cooling cylinder 41, being mixed by paddles 46 on a vertical shaft 44.  The product then rises and is further cooled by the outer jacket 42; a portion is withdrawn through pipe 43.  Additional cooling means is provided by a coil 50 and circulation is assisted by a large impeller 47 and deflecting members 48 and 49.  A series of scrapers 51 and 52 removes any product that deposits upon the walls of the cooling chambers.  The scrapers are attached to supports which are mounted upon a spider 57 which is rotated by a shaft 58.  Springs 53, 54 press the scrapers against the walls of the cooling chambers.  The supply of caustic soda is controlled by a device which continuously measures the pH value of the contents of the neutralizer.  The product leaving the latter is subjected to a spray drying process, e.g. that described in Specification 291,041, [Class 91].  The following examples illustrate the use of the product as a detergent or emulsifying agent or soap substitute: (1) the product containing sodium sulphate is obtained in the form of flakes by drying it over a heated roll and is milled with water and a perfuming material containing eugenol; it is finally pressed into cakes; (2) the sodium sulphate free product is dried and formed into a bar; (3) a shaving cream free from alkalinity is formed by mixing the product with water, glycerine, stearic acid and a perfume; (4) a dental cream is formed by mixing the product with water, glycerine, calcium carbonate, starch, sodium benzoate and a flavouring material; dicalciumphosphate and magnesium hydroxide may also be present; (5) a face cream is formed by mixing the product with water, glycerine, stearic acid, mineral oil and perfume; (6) a shampoo is formed by drying, pulverizing and screening the product or by mixing the product with perfume and water; oils and bleaching or colouring agents may be present; (7) a mouthwash is formed by mixing the product with chlorthymol, methylsalicylate and water; (8) a solution of the product in water comprises a liquid soap to which oil or naphtha may be added; (9) the product in the form of its calcium salt is mixed with sugar, saccharine, sodium perborate, calcium carbonate and perfume.  The products may also be mixed with soap, sodium carbonate, phosphate or silicate, germicides, phenol, cresol, resorcinol, silver nitrate, mercury bichloride, aluminium chloride, zinc sulphate, alum, isoeugenol, vanillin, methylanthranilate, pumice, whiting, feldspar, solvents, naphtha, talc, titanium dioxide, barium sulphate, chalk, pigments, dyes, deodorants, animal, vegetable or mineral oils, and starch.  The use in the process of tallow, soy bean oil, palm oil, fish oils and garbage grease is specified.  The Specification as open to inspection under Sect. 91 comprises generally the interaction of a fatty oil, anhydrous glycerine and fuming sulphuric acid.  The use of glycol or other polyhydric alcohol instead of glycerine is mentioned, and also esterification with naphthenic and abietic acids and acids obtained by the oxidation of paraffin hydrocarbons.  It is stated that the products may be mixed with emery, ether, alcohol, benzol, glycols and waxes.  This subject-matter does not appear in the Specification as accepted.ALSO:One molecular proportion of a fatty oil and one molecular proportion of anhydrous glycerine are reacted with such an excess of fuming sulphuric acid over the equivalent of three molecular proportions of 100 per cent sulphuric acid that the sulphuric acid remaining after the reaction has a concentration of not less than 95 per cent, and the product is neutralized, without previous dilution, in the presence of a large excess of already neutralized material.  The neutralized product may be used as a detergent or emulsifying agent or as a soap substitute.  The glycerine and fatty oil or the glycerine and excess fuming sulphuric acid may be first reacted together or the three components may be mixed simultaneously.  The product may be prepared free from inorganic salts by extraction with alcohol, e.g. butyl alcohol, before or after the neutralization step or the sulphate free sodium, potassium, ammonium, triethanolamine and magnesium salts may be prepared from the calcium salt, the calcium being precipitated by means of carbondioxide or a carbonate, phosphate or oxalate.  The effect of adding solutions of the following salts to the pure and sulphate containing products is stated: calcium, barium, potassium, magnesium, aluminium, ferric and mercuric chlorides, ammonium and copper sulphates, lead acetate and silver nitrate. No turbidity or precipitate is given with hydrochloric acid, hard water and sea water.  In an example, glycerine is treated with fuming sulphuric acid and the mixture is reacted with coconut oil. The products may be mixed with soap, sodium, carbonate, phosphate, or silicate, germicides, phenol, cresol, resorcinol, silver nitrate, mercurybichloride, aluminium chloride, zinc sulphate, alum, isoeugenol, vanillin, methyl-anthranilate, pumice, whiting, feldspar, solvents, naphtha, talc, titanium dioxide, barium sulphate, chalk, pigments, dyes, deodorants, animal vegetable or mineral oils, and starch.  The use in the process of tallow, soya bean oil, palm oil, fish oils and garbage grease is mentioned.  The Specification as open to inspection under Sect. 91 comprises generally the interaction of a fatty oil, anhydrous glycerine and fuming sulphuric acid.  Naphthenic and abietic acids and acids obtained by the oxidation of paraffin hydrocarbons are specified and also the use, instead of glycerine, of glycols.  It is stated that the products may be mixed with emery, ether, alcohol, benzol, glycols and waxes.  This subject-matter does not appear in the Specification as accepted.ALSO:Products which may be used as soap substitutes are prepared by reacting one molecular proporition of a fatty oil and one molecular proportion of anhydrous glycerine with such an excess of fuming sulphuric acid over the equivalent of three molecular proportions of 100 per cent sulphuric acid that the sulphuric acid remaining after the reaction has a concentration of not less than 95 per cent and thereafter neutralizing the product, without previous dilution, in the presence of a large excess of already neutralized material.  The glycerine and fatty oil or the glycerine and excess fuming sulphuric acid may be first reacted together or the three components may be mixed simultaneously. The product may be prepared free from inorganic salts by extraction with alcohol, e.g. butyl alcohol, before or after the neutralization step or the sulphate free sodium, potassium, ammonium, triethanolamine and magnesium salts may be prepared from the calcium salt, the calcium being precipitated by means of carbon dioxide or a carbonate, phosphate or oxalate.  The effect of adding solutions of the following salts to the pure and sulphate containing products is stated; calcium, barium, potassium, magnesium, aluminium, ferric and