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
Supercritical Fluid Definition Supercritical Fluid Properties Supercritical Fluids Classification Supercritical Fluid Selection for Chemical Reactions Supercritical Ethanol Properties Supercritical Ethanol Applications 1 Contents Introduction
Experimental Section Instrumentation Diethyl Ether Determination Diethyl Ether Identification Effective Parameters on The Reaction Conclusion Providence 2
Supercritical Fluid Definition 3
Supercritical Fluid Properties LiquidSupercritical Fluid Gas (0.6-2)( )(0.6-2) * Density (g.cm -3 ) (0.2-2) * ( )(1-4) * Diffusion Coefficient (cm 2.s -1 ) (0.2-3) * (1-3) * Viscosity (g.cm -1.s -1 ) 4
Supercritical Fluids Classification Non-associating Fluids Associating Fluids Density (g.cm -3 ) Critical Pressure (bar) Critical Temperature ( o C) CO H2OH2O EtOH 5
Supercritical Fluid Selection for Chemical Reactions Critical Temperature and Pressure Solvent Strength Corrosion Toxicity Supercritical Ethanol 6
Supercritical Ethanol Properties Critical Temperature and Pressure 7
Density 8
9 Viscosity
Diffusion Coefficient 10
Dielectric Constant 11
Hydrogen Bonding 12
13
14
Kamlet-Taft Solvent Parameters: Polarity / Polarizability (π ∗ ) Hydrogen-Bond Donating Acidity (α) Hydrogen-Bond Accepting Basicity (β) 15 Polarity
Polarity / Polarizability (π ∗ ) 16
Hydrogen-Bond Donating Acidity (α) 17
Hydrogen-Bond Accepting Basicity (β) 18
Supercritical Ethanol Applications Biodiesel Production Chemical Reaction Extraction Micro and Nano Particle Formation Drying 19
Experimental Section 20
Instrumentation 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
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
23 Ethanol Diethyl Ether
24
25 Diethyl Ether Identification
Effective Parameters on The Reaction : Temperature Flow Rate Catalyst Concentration Pressure Catalyst Type 26
Temperature and Flow Rate Effect Catalyst : PTSA 2(%w/v) Pressure : 80 bar Temperature : ( ) o C Flow Rate : ( ) mL/min 27
Ethanol Conversion 28
Diethyl Ether Selectivity 29
Diethyl Ether Yield 30
Yield(%)Selectivity(%)Conversion(%)Flow Rate(mL.min -1 )Temperature( o C) N.D N.D. 0.2 N.D. 0.4 N.D
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)
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)
Catalyst Type Temperature : 200 o C Flow Rate : 0.1 mL/min Pressure : 80 bar Catalyst Concentration : 2 (%w/v) Yield(%)Selectivity(%)Conversion(%)Catalyst PTSA H 2 SO 4 34
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
36 Providence Synthesis of Other Alkyl Ethers Diethyl Ether Synthesis in The Presence of Heterogeneous Catalysts Diethyl Ether Separation from Ethanol
Thanks for Your Attention
Page 5 dG = ( u 2 -u 1 ) dn u = (dG/ dn) T,P
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.
Page 8
Page 25 Swine Manure Bio-oil T = o C and P= MPas and Purge with N 2 30 gr waste gr ethanol Solid + Bio-oil +Liquid Bio-oil + Liquid Bio-oil Filter Distillation at 60 o C
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.