Synthesis of mercaptans and sulfides in the liquid phase reaction of hydrogen sulfide with alkylene oxides: assessment of the catalysts effectiveness

A process for producing of β-hydroxyalkyl mercaptans and β-ydroxyalkyl sulfides based on the interaction of liquid hydrogen sulfide with alkylene oxides is proposed. This method provides the highest possible concentration of hydrogen sulfide in the reaction mixture, allows to run the process in a wide range of temperatures, allows the use of catalytic additives, does not require a solvent. The kinetic patterns of interaction of hydrogen sulfide with one of alkylene oxides (propylene oxide) under conditions effective to stay the components of the reaction mixture in the liquid phase. With an excess of propylene oxide in reaction a two consecutive macro stages are occurring: formation of 2-hydroxypropane-1-thiol and the subsequent formation of 1,1’-di(2-hydroxypropane) sulfide. Staged in the formation of sulfide and mercaptan allows to manage the process to obtain quantitatively or mercaptan or sulfide in certain conditions. So, basically 2-hydroxypropane-1-thiol is formed with an excess of hydrogen sulfide. The activity of 14 homogeneous and heterogeneous catalysts (activated carbon, ion exchange resins, metal oxides, water, triethylamine, etc.) are studied. On the basis of the developed mathematical model the principle of determining of the catalytic additives effectiveness is proposed. The most effective catalyst of all tested was the triethylamine which increases the reaction rate more than 100 times: without catalyst the reaction is completed in about 50 hours, in the presence of small amounts of triethylamine – a few minutes.

1. Малиевский А.Д., Ершов В.В., Иванюков Д.В., Никифоров Г.А., Городецкая Н.Н.,Володькин А.А., Америк В.В., Петрова В.Ф. // А.с. СССР № 390114. Б.И. 1973. № 30.

2. Tchitchibabine А., Bestougeff M. // Comp. Rend. 1935. Vol. 200. P. 342.

3. Jungers C. // Chemicka Kinetika. Praha. 1963. P. 108.

4. Hands H.G. // J.Soc. Chem. Ind. 1947. Vol. 66. P. 370.

5. Berbe F. // Bull. Soc. Chim. Belg. 1950. Vol. 59. P. 449.

6. Danehy J.P., Noel C.J. // J. Am. Chem. Soc. 1960. Vol. 82. P. 2511.

7. Repas M., Macho V., Mistrik J.E. // Chem. Zwesti. 1966. Vol. 20. P. 501.

8. Малиевский А.Д., Липкин Г.М., Шокина Л.И, Эмануэль Н.М. // АС. №213833, 4.01, 1968.

9. Малиевский А.Д., Шокина Л.И., Эмануэль Н.М., Часкина Л.Б., Воробьева В.В., Виханский К.Н., Варшавский С.Л. // АС, СССР, №64507, 28.07, 1972.

10. Шокина Л.И., Малиевский А.Д., Степанянц А.У. // Изв. АН СССР. Сер. химич. 1971. Т. 7. С. 1379.

11. Flussing Schwefelwasserstoff // Societe National 1еs Petroles d’Acquitaiene, Paris, 1971.

12. Эмануэль Н.М., Кнорре Д.Г. Курс химической кинетики. М., 1969.

13. Kelen T. // Acta Chim. Acad. Scient. Hung. 1969. Vol. 62. № 1. P. 27–39.

14. Малиевский А.Д., Шокина Л.И. // Изв. АН. Сер. химич. 1999. № 6. С. 1083.

15. Хемминг Р. Численные методы. М.: Наука, 1972. С. 103, 360.

16. Дмитриев В.И. Простая кинетика. Новосибирск: Наука, 1982.