Patent GB-464952-A (GB)
Title: A process for the production of valuable products from unsaturated hydrocarbons and hydrogen sulphide
IPC: C07C5/03
Filed: 1936-03-13
Abstract: Mercaptans, thioethers, or saturated hydrocarbons or mixtures thereof are produced by reacting a hydrocarbon containing an olefinic linkage between two aliphatic carbon atoms with hydrogen sulphide at an elevated temperature and under super-atmospheric pressure in the presence of a water-binding agent.  Disulphides may also apparently be formed.  The formation of mercaptans and thioethers is favoured by operating in the vapour phase, at temperatures of 35--300 DEG  C. Higher temperatures below 300 DEG  C. and higher pressures favour thioether formation, while under the same temperature and pressure conditions, high yields of thioethers are attained by the use of a longer contact time of the reactants.  For thioether formation, at least 2 mols. monoolefine should be reacted with one mol. hydrogen sulphide, while for mercaptan formation, equivalent quantities or excess of hydrogen sulphide is used.  A quantity of mercaptan or thioether may be added to the reactants to repress formation of the particular compound.  Saturated hydrocarbons are produced by the use of olefines containing at least six carbon atoms, by operating in the liquid phase at temperatures materially above 100 DEG  C. up to 500 DEG  C. and by employing a longer reaction time than is necessary for thioether and mercaptan formation.  A list of suitable olefines is given commencing with ethylene, and includes such analogues as phenyl and naphthyl ethylene, and such polyolefines as divinyl, diallyl, &c. Olefine polymers containing at least six carbon atoms and a branched chain are particularly suitable for conversion to hydrocarbons for use as fuels or as components thereof.  Mixed olefines may be used, or mixtures with relatively unreactive substances such as paraffins, halogenated hydrocarbons, oils or inert gases.  Olefine-containing mixtures obtained by the pyrogenesis of petroleum, petroleum products, shale oil, &c. by the destructive distillation or hydrogenation of coal, peat, pitches, tars, asphalts, &c. are specified.  The mixtures may be fractionated into cuts containing compounds possessing the same number of carbon atoms, e.g. a butane-butene cut.  The hydrogen sulphide used may be pure, or may be used without purification from industrial operations.  Suitable water-binding agents are the anhydrides of carboxylic acids, for example, of acetic propionic, butyric, isobutyric, valeric, isovaleric, caproic, crotonic, malonic, succinic, benzoic, cinnamic, &c. acids.  The reagents may also be initially dried. Sulphide catalysts may be present, sulphides of the following metals being specified: calcium, beryllium, zinc, magnesium, strontium, barium, aluminium, chromium, zirconium, tin, copper, thallium, vanadium, molybdenum, tungsten, arsenic, antimony, platinum, nickel, iron and cobalt.  These may be obtained by treating metals or metal oxides or hydroxides with sulphidizing agents, or with hydrogen sulphide before or during the reaction, or by thermal decomposition of the thiosalts. The catalyst may be employed in powder, granule or pellet form, or precipitated on, say, pumice, silica gel, kieselguhr, or charcoal, or it may be deposited as a film in metal reaction vessels by contacting the surface with hydrogen sulphide or with a sulphide or hydrosulphide solution.  The reaction may be effected under the vapour pressure of the reactants.  The pressure may be increased by the introduction of an inert volatile liquid or gas.  Pressures greater than 250 ats. are undesirable.  Batch, intermittent or continuous operation may be employed, and stirring may be advantageous.  Several examples of effecting the process are given. The mercaptans produced as useful as inhibitors of the solvent action of acids on metals, being particularly useful as constituents of oil well cleaning compositions, as intermediates in the preparation of a variety of organic sulphur-containing compounds, or of dyes of the anthraquinone series, the thioindigos and the indamines; as stabilizers for chlorinated hydrocarbons, the butyl mercaptans being especially suitable for stabilizing carbon tetrachloride and ethylene chloride.  On reaction with aldehydes and ketones, they are converted respectively to mercaptals and mercaptols.  They may be esterified to form thioesters and oxidized to polysulphides.  Compositions useful in ore-flotation operations may be prepared by heating them with phosphorus tri- and pentachlorides.  The mercaptans and thioethers and mixtures containing them are efficaceous as fly repellents and insecticides.  The thioethers or mixtures containing them are solvents for rubber, petroleum resins, meta- and parasulphur chloride resins, and resins such as abietic acid and paracumarone.  Cellulose esters are soluble in mixtures of the thioethers with the lower alcohols.  The thioethers are valuable as intermediates in the preparation of pyroxylin and soporific sulphones.  The hydrocarbons in addition to being useful as fuels or components thereof and of lubricating oils, are used as solvents and as raw material for resin production. Specification 450,760 is referred to.ALSO:Saturated hydrocarbons are produced by reacting a hydrocarbon containing an olefinic linkage between two aliphatic carbon atoms with hydrogen sulphide at an elevated temperature and under super-atmospheric pressure in the presence of a water-binding agent.  Sulphide catalysts may be present, sulphides of the following metals being specified:--calcium, beryllium, zinc, magnesium, strontium, barium, aluminium, chromium, zirconium, tin, copper, thallium, vanadium, molybdenum, tungsten, arsenic, antimony, platinum, nickel, iron and cobalt.  These may be obtained by treating metals or metal oxides or hydroxides with sulphidizing agents, or with hydrogen sulphide before or during the reaction, or by thermal decomposition of the thiosalts. The catalyst may be employed in powder, granule or pellet form, or precipitated on say pumice, silica gel, kieselguhr or charcoal, or it may be deposited as a film in metal reaction vessels by contacting the surface with hydrogen sulphide or with a sulphide or hydrosulphide solution.  The production of the saturated hydrocarbons is favoured by the use of olefines containing at least six carbon atoms, by operating in the liquid phase at temperatures materially above 100 DEG  C. up to 500 DEG  C., and by employing a relatively long reaction time.  A list of suitable olefines is given, commencing with ethylene, and includes such analogues as phenyl and naphthyl ethylene, and such polyolefines as divinyl, diallyl &c.  Olefine polymers containing at least six carbon atoms and a branched chain are particularly suitable for conversion to hydrocarbons for use as fuels or as components thereof.  Mixed olefines may be used, or mixtures with relatively unreactive substances such as paraffins, halogenated hydrocarbons, oils or inert gases.  Olefine-containing mixtures obtained by the pyrogenesis of petroleum, petroleum products, shale-oil, &c., and by the destructive distillation or hydrogenation of coal, peat, pitches, tars, asphalts &c., are specified.  The mixtures may be fractionated into cuts containing compounds possessing the same number of carbon atoms e.g. a butane-butene cut.  The hydrogen sulphide used may be pure, or may be used without purification from industrial operations.  Suitable water-binding agents are the anhydrides of carboxylic acids, for example, of acetic, propionic, butyric, isobutyric, valeric, isovaleric, caproic, crotonic, malonic, succinic, benzoic, cinnamic, &c., acids.  The reagents may also be initially dried. The reaction may be effected under the vapour pressure of the reactants.  The pressure may be increased by the introduction of an inert volatile liquid or gas.  Pressures greater than 250 ats. are undesirable. Batch, intermittent or continuous operation may be employed, and stirring may be advantageous.  Several examples of effecting the process are given.  The hydrocarbons in addition to being useful as fuels or components thereof and of lubricating oils, are used as solvents and as raw material for resin production.  Specification 450,760, [Group IV], is referred to.ALSO:Compositions useful in ore-flotation operations may in many cases be prepared by heating mercaptans with phosphorus tri- and penta-chlorides.