Patent GB-721670-A (GB)
Title: Stabilising and improving hydrocarbon compositions and agents therefor
IPC: B01J13/00
Filed: 1950-09-25
Abstract: A composition consisting of hydrocarbons is stabilized against deterioration by the incorporation therein of a minor proportion of a colloidal basic compound of an alkaline earth metal or magnesium, the particles of the colloid having at least one dimension within the range 0.001-0.5 microns.  Suitable colloidal compounds are the colloidal oxides, hydroxides and sulphides of the alkaline earth metals and magnesium, particularly the colloidal forms of calcium oxide, hydroxide or sulphide, magnesium oxide or hydroxide, barium oxide or hydroxide and strontium hydroxide.  Mixtures of two or more such colloidal compounds or mixtures of such a colloidal compound with an organic salt or alcoholate of an alkaline earth metal or magnesium may be employed.  Examples of hydrocarbons are liquid butanes, pentanes, hexanes, heptanes, octanes, octenes, benzene, toluene, xylene, cumene, indene, hydrindene and alkylnaphthalenes.ALSO:A composition consisting wholly or predominantly of hydrocarbons is stabilized against deterioration or otherwise improved by the incorporation therein of a minor proportion of a colloidal basic compound of an alkaline earth metal or magnesium, the particles of the colloid having at least one dimension within the range 0.001-0.5 microns.  The colloidal compounds prevent deterioration of lubricating oils and greases and liquid fuels on storage, prevent deterioration of lubricating oils and greases during use, and also act as detergents and anti-wear agents in lubricants. The addition of the colloidal compounds to liquid fuels of high sulphur content, allows such fuels to be employed in engines without fouling of the engine and allows such fuels to be employed in the open hearth steel process without reaction between the sulphur and the limestone over the steel puddles.  The use of the colloidal compounds as saponifying agents in the preparation of lubricating greases, employing a slight excess of the colloidal compound so that the final grease contains a small amount of the colloidal compound, results in the formation of greases which have a desirable texture, a high drop point, improved water resistance, and stability under static and dynamic conditions.  Suitable colloidal compounds are the colloidal oxides, hydroxides and sulphides of the alkaline earth metals and magnesium, particularly the colloidal forms of calcium oxide, hydroxide or sulphide, magnesium oxide or hydroxide, barium oxide or hydroxide, and strontium hydroxide.  Mixtures of two or more such colloidal compounds or mixtures of such a colloidal compound with an organic salt or alcoholate of an alkaline earth metal of magnesium may be employed.  Lubricants mentioned are petroleum lubricating oils, polymerized olefins, resinous hydrocarbon materials having lubricating properties such as petroleum resins, and mixtures of hydrocarbon lubricants with minor proportions of synthetic lubricants.  Hydrocarbon compositions containing the colloidal compounds may be used in the form of water-in-oil or oil-in-water emulsions for lubricating purposes.  Lubricating compositions according to the invention may contain additional ingredients such as non-metallic detergents (e.g. phosphatides, fatty oils, and voltolized fatty or mineral oils), antioxidants (e.g. alkyl phenols, amino phenols and amines, of which examples are given), corrosion inhibitors or anti-rusting compounds (e.g. dicarboxylic acids of 16 and more carbon atoms, alkali metal and alkaline earth metal salts of sulphonic acids and fatty acids, and organic compounds containing an acidic radicle in close proximity to a mercapto, nitrile, nitro or nitroso group), oil-soluble urea or thiourea derivatives (e.g. urethanes, allophanates, carbazides and carbazones) and oil-soluble polymeric materials (e.g. polyisobutylene polymers and polymerized unsaturated esters of fatty acids and monohydric alcohols. Lubricating greases according to the invention may be gelled with barium stearate, magnesium stearate, calcium oleate, calcium oleate and calcium 12-hydroxy stearate, and barium stearate and barium acetate.  The greases may in addition contain oxidation inhibitors such as phenyl-alpha-naphthylamine, corrosion inhibitors, anti-wear agents such as zinc dibutyl dithiocarbonate, and fillers such as graphite, mica, clays and asbestos.  Liquid fuels mentioned are gasoline, kerosene, fuel oil and gas oil; they may contain tetra-alkyl lead, antioxidants such as aromatic amines and other improving agents.  Other hydrocarbons mentioned are paraffin wax and petrolatum.  In the examples, compositions are described consisting of (a) mineral lubricating oil and colloidal calcium hydroxide with or without one of the following:-calcium alcoholates, oil-soluble condensation product of octylphenol and formaldehyde, calcium petroleum sulphonate, the blend (calcium salts of octyl phenol-formaldehyde condensation product plus zinc dibutyl dithiocarbamate plus phenyl-alpha-naphthylamine), dibutyl trichloromethane phosphonate, calcium dichlorophenylstearate, and potassium salt of a P2S5 olefine reaction product, (b) mineral lubricating oil, colloidal barium hydroxide and barium petroleum sulphonate, (c) sulphur-containing diesel oil and colloidal calcium hydroxide with or without calcium naphthenate, (d) hydrocarbon motor fuel, colloidal calcium hydroxide, tetra ethyl lead, ethylene bromide and ethylene bromide and ethylene chloride and, (f) mineral lubricating oil thickened to grease structure by a composition obtained by saponifying a mixture of hydrogenated fish oil fatty acids and hydrogenated castor oil with an excess of colloidal calcium hydroxide or of a mixture of colloidal calcium hydroxide and calcium alcoholate.  Coating compositions.  Rust-preventive compositions for metal surfaces, which compositions consist predominantly of hydrocarbons, can be improved by the addition thereto of the colloidal basic compounds of alkaline earth metals or magnesium. The vehicle for such compositions can be volatile hydrocarbons, hydrocarbon waxes, asphaltic materials or mixtures thereof.  The colloidal compounds, particularly colloidal calcium hydroxide, can also be used as flattening or anti-gloss agents in varnish and lacquers based on hydrocarbon solvents and thinners without affecting the transparency of the product.  Preparation of colloidal compounds. Suitable colloids are obtained by mixing a solution of an inorganic salt of an alkaline earth metal of magnesium in an organic solvent with a solution of an alkali metal hydroxide in the organic solvent and removing the alkali metal salt formed from the colloidal product. Thus in the p  preparation of colloidal calcium hydroxide, calcium chloride and sodium hydroxide each in an organic solvent such as an alcohol (e.g. methanol or ethanol) may be reacted, and the salt formed removed by washing the colloidal product with methanol.  The colloidal material thus produced is believed to comprise a mixture of colloidal calcium hydroxide and calcium alcoholate.  This mixture can be hydrolyzed to convert the calcium alcoholate to colloidal calcium hydroxide.  Magnesium chloride or barium chloride or other water-soluble salts such as the nitrates or acetates may be employed instead of the calcium chloride, while potassium hydroxide or other alkali metal hydroxide may be employed instead of the sodium hydroxide.  In the examples, colloidal calcium hydroxide is prepared by reacting methanol or isopropanol solutions of calcium chloride and sodium hydroxide.ALSO:The detrimental effects of acid formation and other forms of deterioration in asphaltic compositions are combated by the incorporation therein of a minor proportion of a colloidal basic compound of an alkaline earth metal or magnesium, the particles of the colloid having at least one dimension within the range 0.001-0.5 microns.  Suitable colloidal compounds are the colloidal oxides, hydroxides and sulphides of the alkaline earth metals and magnesium particularly the colloidal forms of calcium oxide, hydroxide or sulphide, magnesium oxide or hydroxide, barium oxide or hydroxide, and strontium hydroxide.  Mixtures of two or more such colloidal compounds with an organic salt or alcoholate of an alkaline earth metal or magnesium may be employed. Asphaltic compositions mentioned are albino asphalts, and compositions suitable for road, roofing and other protective applications, including rust-preventive compositions for metal surfaces.ALSO:The detrimental effects of acid formation and other forms of deterioration in insecticidal and fungicidal compositions consisting wholly or predominantly of hydrocarbons are combated by the incorporation therein of a minor proportion of a colloidal basic compound of an alkaline earth metal or magnesium, the particles of the colloid having at least one dimension within the range 0.001-0.5 microns.  Suitable colloidal compounds are the colloidal oxides, hydroxides and sulphides of the alkaline earth metals and magnesium, particularly the colloidal forms of calcium oxide, hydroxide or sulphide, magnesium oxide or hydroxide, barium oxide or hydroxide, and strontium hydroxide. Mixtures of two or more such colloidal compounds or mixtures of such a colloidal compound with an organic salt or alcoholate of an alkaline earth metal or magnesium may be employed.  The insecticidal or fungicidal compositions may be used in the form of water-in-oil or oil-in-water emulsions.