1. Isfahan University of Technology Department of Chemistry Continuous Synthesis of Diethyl Ether from Sub and Supercritical Ethanol in the Presence of Homogeneous Catalysts By : H. Rastegari Supervisor : Prof. H. S. Ghaziaskar Advisor : Prof. M. Yalpani

2. Supercritical Fluid Definition Supercritical Fluid Properties Supercritical Fluids Classification Supercritical Fluid Selection for Chemical Reactions Supercritical Ethanol Properties Supercritical Ethanol Applications 1 Contents  Introduction

3.  Experimental Section Instrumentation Diethyl Ether Determination Diethyl Ether Identification Effective Parameters on The Reaction  Conclusion  Providence 2

4. Supercritical Fluid Definition 3

5. Supercritical Fluid Properties LiquidSupercritical Fluid Gas (0.6-2)(0.2-0.5)(0.6-2) * 10 -3 Density (g.cm -3 ) (0.2-2) * 10 -5 (10 -3 -10 -4 )(1-4) * 10 -1 Diffusion Coefficient (cm 2.s -1 ) (0.2-3) * 10 -2 (1-3) * 10 -4 Viscosity (g.cm -1.s -1 ) 4

6. Supercritical Fluids Classification  Non-associating Fluids  Associating Fluids Density (g.cm -3 ) Critical Pressure (bar) Critical Temperature ( o C) 0.46673.831.1 CO 2 0.322220.6374.0 H2OH2O 0.28061.4240.8 EtOH 5

7. Supercritical Fluid Selection for Chemical Reactions  Critical Temperature and Pressure  Solvent Strength  Corrosion  Toxicity Supercritical Ethanol 6

8. Supercritical Ethanol Properties Critical Temperature and Pressure 7

9. Density 8

10. 9 Viscosity

11. Diffusion Coefficient 10

12. Dielectric Constant 11

13. Hydrogen Bonding 12

14. 13

15. 14

16. Kamlet-Taft Solvent Parameters: Polarity / Polarizability (π ∗ ) Hydrogen-Bond Donating Acidity (α) Hydrogen-Bond Accepting Basicity (β) 15 Polarity

17. Polarity / Polarizability (π ∗ ) 16

18. Hydrogen-Bond Donating Acidity (α) 17

19. Hydrogen-Bond Accepting Basicity (β) 18

20. Supercritical Ethanol Applications  Biodiesel Production  Chemical Reaction  Extraction  Micro and Nano Particle Formation  Drying 19

21. Experimental Section 20

22. Instrumentation 21 7- Oven1- Feed Container 8- Reactor2- High-Pressure Pump 9- Cooler3- Three Way Valve 10- High Pressure Valve4- Preheater 11- Back Pressure Regulator5- Preheater Cell 12- Collection Vessel6- Thermocouple

23. Diethyl Ether Determination Carrier Gas: Nitrogen ( %99.999) Column Type: Capillary (HP-5) Injector Temperature : 230 o C Detector Temperature : 250 o C Temperature Program : Column Primary Temperature : 40 o C Column Hold Time at 40 o C : 2 min Temperature Increasing Rate: 30 o C/min Final Temperature : 250 o C Hold Time at 250 o C : 5 min 22

24. 23 Ethanol Diethyl Ether

25. 24

26. 25 Diethyl Ether Identification

27. Effective Parameters on The Reaction : Temperature Flow Rate Catalyst Concentration Pressure Catalyst Type 26

28. Temperature and Flow Rate Effect Catalyst : PTSA 2(%w/v) Pressure : 80 bar Temperature : (100-300) o C Flow Rate : (0.1-0.7) mL/min 27

29. Ethanol Conversion 28

30. Diethyl Ether Selectivity 29

31. Diethyl Ether Yield 30

32. Yield(%)Selectivity(%)Conversion(%)Flow Rate(mL.min -1 )Temperature( o C) N.D. 0.1100 N.D. 0.2 N.D. 0.4 N.D. 0.7 12.532.738.20.1150 7.022.030.00.2 5.020.324.50.4 3.318.518.10.7 39.076.251.30.1200 24.560.440.70.2 20.663.632.80.4 14.751.328.80.7 19.031.361.00.1250 31.065.047.00.2 18.348.038.00.4 13.041.032.20.7 5.47.276.50.1300 8.813.465.40.2 11.728.141.80.4 14.643.533.90.7 31

33. Catalyst Concentration Effect Temperature : 200 o C Flow Rate : 0.1 mL/min Pressure : 80 bar PTSA Concentration : 2-4 (%w/v) Yield(%)Selectivity(%)Conversion(%)PTSA Concentration (%w/v) 42.181.352.02 60.494.564.14 32

34. Pressure Effect Temperature : 200 o C Flow Rate : 0.1 mL/min PTSA Concentration : 2 (%w/v) Pressure : (60-80) bar Yield(%)Selectivity(%)Conversion(%)Pressure (bar) 38.375.051.560 41.680.052.080 40.877.053.0100 33

35. Catalyst Type Temperature : 200 o C Flow Rate : 0.1 mL/min Pressure : 80 bar Catalyst Concentration : 2 (%w/v) Yield(%)Selectivity(%)Conversion(%)Catalyst 41.680.052.0PTSA 75.099.077.0H 2 SO 4 34

36.  Synthesis of Diethyl Ether in Sub and Supercritical Ethanol in The Presence of Para Toluene Sulfonic Acid and Sulfuric Acid.  Maximum Yield with Para Toluene Sulfonic Acid: %60  Maximum Yield with Sulfuric Acid: %75 35 Conclusion

37. 36  Providence  Synthesis of Other Alkyl Ethers  Diethyl Ether Synthesis in The Presence of Heterogeneous Catalysts  Diethyl Ether Separation from Ethanol

38. Thanks for Your Attention

40. Page 5 dG = ( u 2 -u 1 ) dn u = (dG/ dn) T,P

41. Page 6 the transition-state theory rate constant : or One could also develop an alternate expression for the transition-state theory rate constant that employs fugacity coefficients rather than activity coefficients. This alternate form of the rate constant is convenient to use when an accurate analytical equation of state is available for the fluid phase.

42. Page 8

43. Page 25 Swine Manure Bio-oil T = 240-360 o C and P= 34.47 MPas and Purge with N 2 30 gr waste + 120 gr ethanol Solid + Bio-oil +Liquid Bio-oil + Liquid Bio-oil Filter Distillation at 60 o C

44. Page 25 Depolymerization of PET T= 543 – 573 K and P= 0.1 – 15 MPas These products were produced by the methanolysis ethanolysis or hydrolysis of the ester bond between TPA and EG.