Patent GB-410087-A (GB)
Title: Improvements in the manufacture and production of wax-like substances
IPC: C11C3/00
Filed: 1932-10-28
Abstract: Wax-like substances are obtained by heating mixtures of higher aliphatic carboxylic acids or their anhydrides or esters to 100--450 DEG  C. at atmospheric or raised pressure and in the liquid phase with a decarboxylating catalyst, and subjecting the products to hydrogenation in the presence or absence of a catalyst.  The starting materials are such that the product of the number of carbon atoms and the number of acid groups is at least ten; thus, mixtures of aliphatic monocarboxylic acids of at least ten carbon atoms, or aliphatic dicarboxylic acids of at least five carbon atoms, may be treated.  Specified starting materials are: (1) natural or synthetic waxes such as bees' wax, flax wax, candelilla wax, shellac wax, cotton seed wax, montan wax, insect wax, spermaceti, sperm oil or wool fat; (2) acids obtainable from such waxes; (3) esters of wax acids with methyl or ethyl alcohol, glycol or glycerol; (4) conversion products of waxes, e.g. oxidation products of montan wax; (5) fatty oils and fats and the corresponding acids, e.g. olive oil, coconut oil, castor oil, linseed oil, arachis oil, cottonseed oil, rape oil, sunflower oil, beef tallow, palm oil, palm kernel oil, sesame oil, soya bean oil, train oil, seal oil and whale oil; hardened oils or fats may also be used; (6) oxidation products of higher paraffin hydrocarbons. Specified decarboxylation catalysts are cobalt, nickel, iron, manganese, molybdenum, copper, zinc, chromium and tungsten, and alloys, oxides and sulphides of these metals, and aluminium oxide; the metallic catalysts may be used for constructing or lining the reaction vessel or as fillings.  Specified catalysts for use in the hydrogenation stage are nickel, cobalt, copper, iron, tungsten and molybdenum and their oxides and sulphides, and alloys such as molybdenum-chromium-nickel, copper-manganese, and molybdenum-zinc. The catalysts in both stages may be used on supports, a number of which are specified, and may be activated by addition of an oxide of an alkali or alkaline earth metal.  The decarboxylation may be effected in the presence of hydrogen, and a single catalyst having decarboxylating and hydrogenating properties may be present in both the decarboxylation and the hydrogenation stages.  The products contain alcohols and/or hydrocarbons having more carbon atoms than the starting materials; they may be used, alone or with natural waxes or wax-like substances such as stearine and paraffin wax, in making polishing compositions or for impregnating or dressing paper and textile materials such as wool, cotton, silk and artificial silk; they may also be used to harden readily fusible waxes and wax-like substances, such as paraffin wax, polychloronaphthalenes, stearic acid, higher aliphatic alcohols, bees' wax and tallow, and they may also be used as lubricants for machinery, alone or with mineral oils; the hydrocarbons obtained in the process may be used as electric insulating materials.  In the examples, (1) montan wax, incompletely bleachedby the process of Specification 305,552, [Class 91], is heated with an iron-kieselguhr catalyst, and the product is hydrogenated in the presence of a nickel-kieselguhr catalyst; a hydrocarbon product of relatively high melting point (104 DEG  C.) is obtained; (2) montan wax, incompletely bleached by the process of Specification 305,552, is heated with iron obtained from iron carbonyl and with a nickel-kieselguhr catalyst, and the product is heated with hydrogen; (3) an acid product, obtained by incomplete saponification of deresinified montan wax, is heated under pressure with iron, hydrogen being forced in towards the end of the heating; the product is further hydrogenated in the presence of a catalyst comprising nickel, kieselguhr, and active charcoal containing a little zinc chloride; (4) montan wax is incompletely bleached by the process of Specification 305,552, and the free acids are esterified with methyl alcohol by the process of Specification 296,145, [Class 91], the crude esters are heated with iron obtained from iron carbonyl, and the product is hydrogenated as in example 3; (5) carnauba wax is heated with iron powder and the product is hydrogenated as in example 3; (6) bleached montan wax is heated with powdered cobalt and the product is hydrogenated in the presence of a nickel-kieselguhr catalyst; (7) fused bleached montan wax is circulated over iron chips, and the mixture of ketones obtained is hydrogenated in the presence of nickel; (8) an oxidation product of montan wax is heated with iron obtained from iron carbonyl, and the product is hydrogenated in the presence of a nickel-kieselguhr catalyst; (9) incompletely bleached montan wax is heated with iron to produce a mixture of ketones, which are then reduced to alcohols with sodium and amyl alcohol; (10) bleached montan wax is heated with cast iron powder, and the product is hydrogenated without removing the iron; (11) deresinified montan wax is heated with iron, and the product is hydrogenated in the presence of molybdenum sulphide precipitated on kieselguhr; further hydrogenation in the presence of a nickel-kieselguhr catalyst may follow; (12) an oxidation product of montan wax is heated with iron and the product is hydrogenated in the presence of a copper-kieselguhr catalyst; (13) an acid oxidation product of paraffin wax is heated with iron obtained from iron carbonyl, and the resulting mixture of ketones is hydrogenated in the presence of a cobalt catalyst or a catalyst prepared from nickel carbonate and bleaching earth; (14) tall oil is hardened by hydrogenation in the presence of a nickel-kieselguhr catalyst, and then heated with iron obtained from iron carbonyl; the product is hydrogenated in the presence of a nickel-kieselguhr catalyst; (15) beef tallow is heated with iron powder and the product is hydrogenated in the presence of a molybdenum-chromium catalyst; the catalyst is prepared by absorbing solutions of chromium nitrate and ammonium molybdate in active charcoal containing phosphoric acid, and reducing the product in hydrogen; (16) olive oil is heated with iron obtained from iron carbonyl, and the product is hydrogenated in the presence of a catalyst prepared by precipitating nickel carbonate on kieselguhr and reducing the product; (17) crude fatty acids from train oil are hardened by treatment with hydrogen in the presence of iron powder and a nickel-kieselguhr catalyst; the product is then heated without pressure of hydrogen, and finally hydrogenated without further addition of a catalyst; (18) seal oil is treated with hydrogen in the presence of a nickel-kieselguhr catalyst, and then heated with iron powder without supplying hydrogen; the product is hydrogenated in the presence of a nickel catalyst; the product is useful as a substitute for ozokerite in polishing compositions; a specified composition contains, besides the product, ordinary paraffin wax, benzine, and a mixture of montanic acid ethylene glycol ester and calcium montanate obtainable by the process of Specification 296,145; (19) purified acids from train oil are hardened by hydrogenation in the presence of a nickel-kieselguhr catalyst, and then heated with iron powder; the product is finally hydrogenated in the presence of copper precipitated on active carbon; (20) a fused mixture of hardened train oil acids with incompletely bleached montan wax is heated with iron, and the product is hydrogenated in the presence of molybdenum oxide and chromium oxide precipitated on kieselguhr; (21) as in example 20, except that nickel-kieselguhr is used as the hydrogenation catalyst; (22) train oil acids are heated with iron, and a portion of the product is hydrogenated in the presence of a nickel-kieselguhr catalyst; the hydrogenated and nonhydrogenated portions are mixed, and the mixture is incorporated with paraffin wax, benzine, and a mixture of montanic ester ethylene glycol ester and calcium montanate obtainable by the process of Specification 296,145; the product is useful as a floor polish; (23) the mixture of hydrogenated and nonhydrogenated products used in example 22 is mixed with paraffin wax, turpentine, Sudan I and Nigrosine dissolved in oleic acid, and a mixture of montanic acid butylene glycol ester and calcium montanate obtainable by the process of Specification 296,145; the product is useful as a floor polish.  Specifications 356,731, 364,574; 384,314, [Group IV], 398,982; and 405,850, [Group VIII], also are referred to.ALSO:Wax-like substances are obtained by heating mixtures of higher aliphatic carboxylic acids or their anhydrides or esters to 100-450 DEG  C. at atmospheric or raised pressure and in the liquid phase with a decarboxylating catalyst, and subjecting the products to hydrogenation in the presence or absence of a catalyst.  The starting materials are such that the product of the number of carbon atoms and the number of acid groups is at least ten; thus, mixtures of aliphatic monocarboxylic acids of at least ten carbon atoms, or aliphatic dicarboxylic acids of at least five carbon atoms, may be treated.  Specified starting materials are (1) natural or synthetic waxes such as bees' wax, flax wax, candelilla wax, shellac wax, cotton seed wax, montan wax, insect wax, spermaceti, sperm oil or wool fat; (2) acids obtainable from such waxes; (3) esters of wax acids with methyl or ethyl alcohol, glycol or glycerol; (4) conversion products of waxes, e.g. oxidation products of montan wax; (5) fatty oils and fats and the corresponding acids, e.g. olive oil, coconut oil, castor oil, linseed oil, arachis oil, cotton seed oil, rape oil, sunflower oil, beef tallow, palm oil, palm kernel oil, sesame oil, soya bean oil, train oil, seal oil and whale oil; hardened oils or fats may also be used; (6) oxidation products of higher paraffin hydrocarbons.  Specified decarboxylation catalysts are cobalt, nickel, iron, manganese, molybdenum, copper, zinc,