1. Acetic Acid, Diacetin & Triacetin By: S. Afsari Quaternary Solubility of in Supercritical Carbon Dioxide Superadvisor: Dr. Ghaziaskar

2. Contents o oIntroduction o oSupercritical Region o oSupercritical fluids and CO 2 as a SF. o oAdvantages of Supercritical Sys. o oFactors effecting on supercritical solubility o oApparatus o oSFE systems o oACAC and Glycerol Acetyls in supercritical systems o oSolubility measurements in ScCO 2 and possible separation techniques

3. Why Glycerol Acetyls?

5. Transesterification of vegetable oils + 3 HOCH 3 NaOH or KOH Catalyst +

6. Glycerol acetylation

7. Diacetin Triacetin Structure Formula Molecular weight 176.17 Melting point -30 ºC Boiling point 259 ºC Structure Formula Molecular weight 176.17 Melting point -30 ºC Boiling point259 ºC

8. Supercritical Region C T scco21

9. Supercritical Fluids Sc FluidCritical T (ºC) Critical P (bar) Critical ρ (g/mL) (CO 2 )1.318.73466.0 (H 2 O)0.3746.2203220. (N 2 O)4.365.524530. (NH 3 ).41322.1132350. (C 4 H 10 ).61967.332320. (SF 6 )5.453.377370. (Xe).6163.580991. (CH 2 F 2 )1.788.574240. (CH 4 )6.82-0.461630. (C 3 H 8 )7.965.422200. (C 2 H 6 O)9.126.0542420. (C 6 H 6 )5.2892.490030. 1) Low critical T 2)Cheap 3) available 3) Inexplosive 4) Nontoxic Х Х Х

10. CO 2 Phase Diagram

11. Gas like liquid like Ability of controlling Solubility High diffusion Low viscosity Easy separation of solvent from solute

12. Factors Effecting Solubility in Supercritical Fluids Pressure Temperature Solute Structure Solvent Structure Sample Matrix Hildebrand Parameter:

13. Factors Effecting Solubility in Supercritical Fluids Pressure Temperature Solute Structure Solvent Structure Sample Matrix 40ºC 60ºC

14. Factors Effecting Solubility in Supercritical Fluids Pressure Temperature Solute Structure Solvent Structure Sample Matrix 1)Solute Structure 2)Solute Vapor pressure 3)Solute-Solvent interactions

15. Factors Effecting Solubility in Supercritical Fluids Pressure Temperature Solute Structure Solvent Structure Sample Matrix ScF Density (g/ml)Solubility (mole fraction X 100) Supercritical Fluid 0.394.75 0.812.42 0.941.17 Naphthalene

16. Factors Effecting Solubility in Supercritical Fluids Pressure Temperature Solute Structure Solvent Structure Sample Matrix 1)Chemical properties 2)Physical properties

17. Apparatus Gas Meter

18. Introduction

19. 2 port cylindrical cells

20. Apparatus Gas Meter

21. Back Pressure Adjuster

22. Apparatus Gas Meter

23. Sampling Collection solvent Solute

24. Apparatus Gas Meter

26. SFE Systems On-line On-line Off-line Off-line Different possible analyzing methods Simple & practical separation Higher sensitivity  Lower repeatability Higher repeatability Lower solvent consumption Lower time consuming procedure  Fluctuations in flow rate

27. Solubility Gas meter: V, T Gas meter: V, T Weighting Weighting GC GC Mole fraction: g/L in CO 2

28. Sample: Solvent: Et-OH ACAC DAG TAG :89% :9% :6%

29. y×100 Pressure (bar) System Stability Checking

30. CO 2 Volume (L) W (mg) Purge Test

31. Effective Parameters on Solubility in ScCO 2 Temperature Pressure Flow Rate Weight of sample Weight of Sample ACAC y×100 CO 2 Volume (L)

32. Weight of Sample TAG y×100 CO 2 Volume (L)

33. Weight of Sample DAG y×100 CO 2 Volume (L)

34. Effective Parameters on Solubility in ScCO 2 Temperature Pressure Flow Rate Weight of sample Weight of Sample y×100 CO 2 Volume (L)

35. Effective Parameters on Solubility in ScCO 2 Temperature Pressure Flow RateWeight of sample Ө (ºC): 30,40,60,75 P (bar): 70,100,120,140,160,180 y×100 Pressure (bar) 40ºC 60ºC 75ºC ACAC

36. TAG Ө: 40ºC, P: 70 bar Ө: 60ºC, P: 70 bar Ө: 75ºC, P: 70 bar Ө: 75ºC, P: 100 bar y×100 Pressure (bar) 40ºC 60ºC 75ºC

37. DAG Ө: 40ºC, P: 70 bar Ө: 60ºC, P: 70 bar Ө: 60ºC, P: 100 bar Ө: 75ºC, P: 70 bar Ө: 75ºC, P: 100 bar y×100 Pressure (bar) 40ºC 60ºC 75ºC

38. Separation ACAC, DAG, TAG α%α% Pressure (bar)

39. Separation of ACAC Expanded CO2 (L) Elapsed time (min) Extracted ACAC (mg) Extracted ACAC (%) 52822.122.5 105688.7210 20111192.1321 30167294.8633 40222339.0637 50278341.2838 Ө: 60ºC P: 70 bar

40. Separation of ACAC Expanded CO2 (L) Elapsed time (min) Extracted ACAC (mg) Extracted ACAC (%) 52822.122.5 105688.7210 20111192.1321 30167294.8633 40222339.0637 50278341.2838 Ө: 60ºC P: 70 bar Et-OH ACAC n-hexanol

41. Separation of ACAC Expanded CO2 (L) Elapsed time (min) Extracted ACAC (mg) Extracted ACAC (%) 528171.782.5 1056473.2110 1583664.7349 20111761.0856 Ө: 75ºC P: 100 bar

42. Separation TAG & DAG Ө: 40ºC, P: 70 bar Ө: 60ºC, P: 70 bar Ө: 75ºC, P: 70 bar Ө: 75ºC, P: 100 bar TAG Ө: 40ºC, P: 70 bar Ө: 60ºC, P: 70 bar Ө: 60ºC, P: 100 bar Ө: 75ºC, P: 70 bar Ө: 75ºC, P: 100 bar DAG Ө=60 ºC, P=70 bar ACAC Ө=60 ºC, P=100 bar TAG 1)Incomplete extraction 2)Low efficiency

43. Separation of ACAC under Subcritical Situation ?

44. Factors Effecting Solubility in Supercritical Fluids Pressure Solute Structure Solvent Structure Sample Matrix 1)Chemical properties 2)Physical properties Binary and Quaternary Solubility of Acetic Acid y×100 Pressure (bar) Binary Quaternary

45. Solvent Attributes of ScCO 2 CO2CO2 C O O C CH 3 OH O C CH 3 OH O

46. Factors Effecting Solubility in Supercritical Fluids Pressure Solute Structure Solvent Structure Sample Matrix 1)Chemical properties 2)Physical properties y×100 Pressure (bar) Ө= 40ºC

47. Factors Effecting Solubility in Supercritical Fluids Pressure Solute Structure Solvent Structure Sample Matrix 1)Chemical properties 2)Physical properties Ө= 75ºC y×100 Pressure (bar)

48. Bartle Equation y: Solubility (mole fraction) T: temperature (K) ρ: CO2 density in P & T ( ) y x b m

49. Experimental Solubility Correlation ACAC ACAC DAG DAG TAG TAG Ө: 40ºC, 75ºC Ө: 40ºC, 75ºC P: 100-180 bar P: 100-180 bar Ө: 60ºC Ө: 60ºC P: 100-180 bar P: 100-180 bar ρ (g/L) Pressure (bar)

50. Experimental Solubility Correlation ACAC Ln(yP/P ref ) ρ-ρ ref

51. Experimental Solubility Correlation ACAC y=0.0044x+1.56470.0044-5860.329919.1553 Line Eq.c ( )b (K)a Ln(yP/P ref ) ρ-ρ ref

52. Experimental Solubility Correlation y=0.0044x+1.56470.0044-5860.329919.1553 Line Eq.c ( )b (K)a ACAC 8.0y=0.0048x-1.54190.0048-5775.715.7948 AARD%Line Eq.c ( )b (K)a DAG 12.0y=0.0049x-1.72700.0049-5307.149514.2032 AARD%Line Eq.c ( )b (K)a TAG