SHARP DISTILLATION FOR QUATERNARY SYSTEMS

Conditions of sharp distillation were considered for zeotropic quaternary system (two pairs of components are characterized by relative volatility close to 1) and systems with one (with minimum or maximum boiling point) and two (with minimum and maximum boiling point) binary azeotropes. Regions of compositions for which sharp distillation is effective (distillate and bottom flows don't contain common components) were determined on the basis of analyzing diagrams of unit manifolds of distribution coefficients (distribution coefficients of two components are higher than one, and those of another two components - lower than one). This kind of separation can be recommended if it doesn’t cause an increase in the number of apparatuses in the separation flowsheet. If the system contains azeotropes of saddle type that can generate separatric manifolds, the possibility and expedience of sharp separation decreases. The conclusions were confirmed by simulation of the distillation process in AspenPlus V.10.0 for real and industrially important quaternary systems: ethyl acetate - benzene - toluene - butyl acetate; acetone - methanol - ethanol - propanol-2; methyl acetate - methanol - acetic acid - acetic anhydride and cyclohexene - cyclohexane - cyclohexanone - phenol. Mathematical modeling was carried out using local compositions models Wilson and NRTL-HOC. The relative error of vapor-liquid equilibrium description is less than 4%. The vapor-liquid equilibrium was simulated, a phase diagram was constructed and analyzed, the parameters of sharp distillation column operation (the number of stages, the feed-stage and reflux ratio) were determined for all systems. The effectiveness of using sharp distillation for the system with phenol was confirmed for a wide range of compositions.

distillation, sharp separation, vapor-liquid equilibrium, azeotrope, relative volatility

1. Zharov V.T., Serafimov L.A. Phisico-chemical basis of distillation and rectification. Leningrad: Khimiya Publ., 1975. 240 р. (in Russ.)

2. Timofeev V.S., Serafimov L.A., Timoshenko V.S. Principles of technology of basic organic and petrochemical synthesis. Moscow: Visshaya shkola Publ., 2010. 408 p. (in Russ.)

3. Serafimov L.A., Chelyuskina T.V., Mavletkulova P.O. Special regimes of multicomponent distillation and their importance for chemical engineering. Theoretical Foundations of Chemical Engineering. 2013; 47(4): 306-314.

4. Serafimov L.A., Chelyuskina T.V., Mavletkulova P.O. Finding optimal multicomponent distillation flowsheets. Theoretical Foundations of Chemical Engineering. 2015; 49(1): 41-49.

5. Serafimov L.A., Frolkova A.V., Chelyuskina T.V. Konovalov's first law validity for nonideal multicomponent zeotropic mixtures. Theoretical Foundations of Chemical Engineering. 2008; 42(1): 37-44.

6. Serafimov L.A., Frolkova A.V. Observance of Konovalov's first law in distillation and rectification processes. Vestnik MITHT (Fine Chemical Technologies). 2008; 3(2): 46-52. (in Russ.)

7. Pettit J.H. Minimum boiling points and vapor compositions. J. Phys. Chem. 1989; 3: 349-363.

8. Iliuta M.C., Thyrion F.C., Landauer O.M. Salt effect on the isobaric vapor-liquid equilibrium of the methyl acetate + methanol system. J. Chem. Eng. Data. 1996; 41: 713-717.

9. Aarna A., Kaps T. Vapor-liquid isobaric equilibrium in phenol + oxygen compound binary mixtures. Eesti NSV Tead. Akad. Toim., Keem., Geol. 1974; 23: 16-21.

10. Ogorodnikov S.K., Lesteva T.M., Kogan V.B. Azeotropic mixtures. Handbook. Under the editorship of prof. V.B. Kogan. Leningrad: Khimiya Publ., 1971. 1407 p. (in Russ.).

11. Frolkova A.V., Shashkova Yu.I., Frolkova A.K. Separation of methylacetate + methanol + acetic acid + acetic anhydride system using distillation methods. Proceed. of the 45th Int. Conf. of SSCHE. May 21–25, 2018. Tatranske Matliare, Slovakia. P. 109-112.

12. Logachev D.S., Makhnarylova E.G., Frolkova A.V. Separation of quaternary mixture methanol – methyl acetate – ethanol – propanol-2 by different methods. Vestnik obrazovaniya i nauki = Bulletin of Education and Science. 2017; 5(29): 15-20. (in Russ.)

13. Chelyuskina T., Bedretdinov F., Pronina D. Mathematical modeling of vapor-liquid equilibrium of industrial mixture butyl propionate – propionic acid – butyl butyrate – butyric acid. Proceed. of the 43rd Int. Conf. of SSCHE. May 23–27, 2016. Tatranske Matliare, Slovakia. P. 129.