LOW-WASTE TECHNOLOGY OF GLYCIDOL PRODUCTION BY PEROXIDE METHOD

A technological process of manufacturing glycidol designed for the production capacity of 10 thousand tons per year and consisting in the direct oxidation of allyl alcohol with an aqueous solution of hydrogen peroxide in the presence of nanostructured titanium silicate in methanol is proposed. Due to the exothermic process, the solvent is not only a homogenizer of the mixture of the initial reagents of the epoxy process - allyl alcohol and hydrogen peroxide ensuring their interaction on the surface of the solid catalyst: it also prevents overheating of the reaction mass. On the basis of the research trial of the process the optimal parameters of the process were determined: temperature 30-40 °C; pressure 0.25 MPa; the initial hydrogen peroxide : allyl alcohol ratio = 1:(3-4) mass., methanol concentration in the reaction mixture 12-13 mol/l. Hydrogen peroxide conversion is 98%, the yield of the glycidol - 94%, the selectivity is no less than 95%. The process includes three main stages: (1) raw materials preparation, (2) liquid-phase epoxidation of allyl alcohol, (3) distillation of the target product. The scheme involves recirculation of unreacted allyl alcohol and the solvent - methanol. The developed technological process provides the following indicators (per 1 t of commercial glycidol): consumption of allyl alcohol no more than 0.843 t; consumption of hydrogen peroxide no more than 0.50 t (calculated for 100% hydrogen peroxide); consumption of methanol is no more than 0.022 tons All the waste products correspond to the 3-rd or 4-th hazard class.

hydrogen peroxide, epoxidation, allyl alcohol, glycidol, catalyst, methanol, waste water

1. Gus’kov A.K., Makarov M.G., Shvets V.F. the reactivity of alcohols and glycols in reactions with α-oxides. Kinetika i kataliz = Kinetics and Catalysis. 1997; 38(5): 660-665. (in Russ.)

2. Kozlovskiy I.A., Kozlovskiy R.A., Koustov A.V., Makarov M.G., Suchkov J.P., Shvets V.F. Kinetics and products distribution of selective catalytic hydration of ethylene- and propylene oxides in concentrated aqueous solutions. Organic Process. Research & Development. 2002; 6(5): 660-664. DOI: 10.1021/op010099.

3. Platé N., Slivinsky E. Fundamentals of chemistry and technology of monomer. Moscow: Nauka Publ.: MAIK “Nauka / Interperiodika”, 2002. 696 p. (in Russ.)

4. Timofeev V.S., Serafimov L.A. The principles of technology of general organic and petrochemical synthesis. М.: Vysshaya shkola Publ., 2003. 536 p. (in Russ.)

5. Nikolaev A.F., Kryzhanovskii V.K., Burlov V.V. [et al.] The technology of polymeric materials. Ed. by V.K. Kryzhanovsky. Saint Petersburg: Professiya Publ., 2008. 544 p. (in Russ.)

6. The Science and Technology of Rubber. Ed. by J. Mark, B. Erman, F. Eirich. Elsevier academic Press, Third Edition, 2005.

7. New processes of organic synthesis. Ed. by S.P. Chernykh. M.: Khimiya Publ., 1989. 400 p. (in Russ.)

8. Uno M., Okutsu M. Process for production of glycidol: pat. 20090318718 USA. No. 20070304740; filled 14.06.2007, publ. 24.12.2009.

9. Yoo J.-W., Mouloungui Z., Gaset A. Method for producing an epoxide, in particular of glycidol and installation for implementation: pat. 1998040371 WO. No PCT/FR98/00451; filled 06.03.1998, publ. 17.09.1998.

10. Gomez-Jimenez-Aberasturi O., Ochoa-Gomez J.R., Pesquera- Rodriguez A. Solvent-free synthesis of glycerol carbonate and glycidol from 3-chloro-1,2-propanediol and potassium (hydrogen) carbonate. J. Chem. Technol. & Biotechnol. 2010; 85(12): 1663-1670. DOI: 10.1002/jctb.2478.

11. Sulimov A.V., Danov S.M., Ovcharova A.V., Ovcharov A.A., Flid V.R. Regularities of glycidol synthesis by the liquid-phase epoxidation of allyl alcohol with hydrogen peroxide. Russ. Chem. Bull. 2014; 63(12): 2647-2651.

12. Pastukhova Zh.Yu., Nasybulin F.D., Sulimov A.V., Flid V.R., Bruk L.G. Epoxidation of allyl alcohol to glycidol with hydrogen peroxide at titanium silicalite. Tonkie khimicheskie tekhnologii / Fine Chemical Technologies. 2016; 11(4): 26-34. (in Russ.)

13. Flid V.R., Leont'eva S.V., Bruk L. G., Pastukhova Zh.Yu., Sulimov A.V., Danov S.M., Ovcharova A.V., Ovcharov A.A., Flid M.R., Trushechkina M.A. A method of obtaining a granulated catalyst for the epoxidation of olefins increased strength: pat. 2618528 Russian Federation. No. 2016114666; filled15.04.2016; publ. 04.05.17. (in Russ.)

14. Flid V.R., Leont'eva S.V., Flid M.R., Sulimov A.V., Pastukhova Zh.Yu., Nasybulin F.D., Bruk L.G. A method for producing glycidol: Pat. 2604835 Russian Federation. No. 2015149259, filled 17.11.2015; publ. 10.12.16. (in Russ.)