Patent GB-913585-A (GB)
Title: Preparation of mercaptans
Filed: 1961-05-19
Abstract: Catalysts for the reaction between an alcohol and hydrogen sulphide to produce a mercaptan comprise a metal oxide dehydration catalyst activated by a heteropoly acid or an alkali or alkaline earth metal salt thereof.  The catalyst is prepared by saturating the metal oxide with an aqueous solution of the heteropoly acid or salt thereof and then evaporating the water, the amount of heteropoly acid or salt thereof is preferably such that 0,1 to 10% and most preferably 0,5 to 5% by weight of the dry catalyst is heteropoly compound.  The dehydration catalyst base is preferably alumina but may also be titania, silica, chromia or oxides of tungsten, uranium or molybdenum.  Suitable heteropoly compounds are phosphotungstic acid, phosphomolybdic acid, borotungstic acid, boromolybdic acid, potassium phosphotungstate, silicotungstic acid, a mixture of phosphotungstic acid and its potassium salt, calcium phosphotungstate, or a mixture of potassium cerium and rhubidium phosphotungstates.  Specification 913,584 and U.S.A.  Specifications 2,647,150, 2,786,079, 2,820,062, 2,820,063 and 2,886,515 are referred to.ALSO:Mercaptans are prepared by reacting hydrogen sulphide with a compound containing an alcoholic or phenolic hydroxyl group or an ether not having the etheric oxygen in a ring in the presence of a dehydrating catalyst promoted by a heteropoly acid or alkali metal or alkaline earth metal salt thereof. The starting materials are preferably alcohols and acyclic ethers containing 1-18 carbons, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, iso-pentanol, n-octanol, n-dodecanol, hexadecanol, octadecanol, phenol, and substituted compounds containing heat stable groups e.g. halogen, nitro groups, dimethyl ether, methyl ethyl ether, diethyl ether, di n-butyl ether, ethyl n-butyl ether, ethyl hexyl ether, diisopropyl ether, di n-hexyl ether, t-butyl ethyl ether, anisole and diphenyl ether. The dehydration catalyst may be alumina, titania, silica, chromia and oxides of tungsten, uranium, or molybdenum.  The catalyst is saturated with an aqueous solution of a heteropoly acid compound such as phosphotungstic acid, phosphomolybdic acid, borotungstic acid and boromolybdic acid, of such a concentration that the resulting catalyst when dried contains from 0.1 to 10% of the heteropoly acid. The reaction is preferably carried out at from 100 to 500 DEG C. and more particularly from 250 to 400 DEG C. possibly under increased pressure at a space velocity of 10-400 cc. of hydroxy compound or ether vapour per hour cc. of catalyst, which may be in a fixed or a fluidised bed.  The ratio of hydrogen sulphide to hydroxy compound or ether is preferably from 0.5:1 to 20:1.  Examples illustrate the reactions of butanol, octanol, n-dodecyl alcohol, methanol, ethanol, diethyl ether, dimethyl ether, propanol and phenol with H2S, using phosphotungstic acid, the potassium salt thereof, silicotungstic acid, a mixture of phosphotungstic acid and the potassium salt thereof, calcium phosphotungstate or a mixture of potassium, cerium and rhubidium phosphotungstates on alumina, and phosphotungstic acid on thoria-alumina.  In some instances small amounts of sulphide are formed.  When ethanol is used with a phosphotungstate containing catalyst ethylene produced as a byproduct may be recycled to be reacted with hydrogen sulphide to produce the mercaptan. Specification 913,584 and U.S.A. Specifications 2,647,150, 2,786,079, 2,820,063 and 2,886,515 are referred to.