Synthesis of mercaptans from alcohols
AssigneeOccidental Chemical Corporation
InventorsCharles M. Cook, David E. Albright, Michael C. Savidakis
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Abstract
Disclosed is a method of making a mercaptan by reacting an aliphatic alcohol with hydrogen sulfide in a continuous gaseous phase reaction. The reaction is performed in the presence of a catalyst which comprises a catalytically active carrier that contains base and/or acid active sites, an alkali metal or alkaline earth metal bicarbonate, carbonate, oxide, or hydroxide, and a transition metal acid or alkali metal or alkaline earth metal salt thereof. Selectivities of close to 100% are obtained.
Claims19
A method of making a mercaptan comprising passing over each gram of a catalyst about 0.4 to about 8 g per hour of a vaporized alcohol having the formula ROH and at least about a stoichiometric amount of gaseous hydrogen sulfide, where said catalyst comprises
- (1) mixed phase chi eta rho alumina;
- (2) a transition metal compound selected from the group consisting of transition metal acids and alkali metal or alkaline earth metal salts thereof, in an amount of 0 to about 20 wt %, based on the weight of said mixed phase chi eta rho alumina;
- and
- (3) an alkali metal or alkaline earth metal bicarbonate, carbonate, oxide, or hydroxide, in an amount of about 0.1 to about 10 wt % in excess of the amount needed to stoichiometrically react with said transition metal compound, where R is aliphatic from C.sub.1 to C.sub.14.
A method of making a mercaptan comprising passing over each gram of a catalyst about1 to about 4 g per hour of a vaporized primary alcohol having the formula ROH and at least about a stoichiometric amount of gaseous hydrogen sulfide, where said catalyst comprises
- (1) mixed phase chi eta rho alumina having a surface area of about 100 to about 400 m.sup.2 /g;
- (2) 0 to about 20 wt %, based on the weight of said mixed phase chi eta rho alumina, of a tungsten compound selected from the group consisting of tungstic acid and alkali metal and alkaline earth metal salts thereof;
- and
- (3) an alkali metal hydroxide, in an amount of about 0.5 to about 1 wt % in excess of the amount needed to stoichiometrically react with said tungsten compound, where R is hydrocarbon from C.sub.6 to C.sub.12.
A method of making a mercaptan comprising passing over each gram of a catalyst 1.0 to 4.0 g per hour of a vaporized alcohol selected from the group consisting of n-hexanol, n-octanol, and n-dodecyl alcohol and at least about a stoichiometric amount of gaseous hydrogen sulfide, where said catalyst comprises
- (1) mixed phase chi eta rho alumina having a surface area of about 100 to about 400 m.sup.2 /g;
- (2) 0 to about 20 wt %, based on the weight of said alumina, of WO.sub.3 or K.sub.2 WO.sub.4 ;
- and
- (3) potassium hydroxide or rubidium hydroxide, in an amount of about 0.5 is to about 1 wt % in excess of the amount needed to stoichiometrically react with said WO.sub.3 or K.sub.2 WO.sub.4.
Dependencies are inferred from the claim text.