Isfahan University of Technology Department of Chemistry

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Isfahan University of TechnologyDepartment 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
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• Contents
• Introduction

• Supercritical Fluid Definition
• Supercritical Fluid Properties
• Supercritical Fluids Classification
• Supercritical Fluid Selection for Chemical
  Reactions
• Supercritical Ethanol Properties
• Supercritical Ethanol Applications

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• Experimental Section
• Instrumentation
• Diethyl Ether Determination
• Diethyl Ether Identification
• Effective Parameters on The Reaction
• Conclusion
• Providence

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Supercritical Fluid Definition
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Supercritical Fluid Properties
Liquid Supercritical 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 (cm2.s-1)
(0.2-3) 10-2 (1-3) 10-4 (1-3) 10-4 Viscosity (g.cm-1.s-1)
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• Supercritical Fluids Classification
• Non-associating Fluids
• Associating Fluids

Density (g.cm-3) Critical Pressure (bar) Critical Temperature (o C)
0.466 73.8 31.1 CO2
0.322 220.6 374.0 H2O
0.280 61.4 240.8 EtOH
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• Supercritical Fluid Selection for Chemical
  Reactions
• Critical Temperature and Pressure
• Solvent Strength
• Corrosion
• Toxicity
• Supercritical Ethanol

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Supercritical Ethanol Properties Critical
Temperature and Pressure
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Density
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Viscosity
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Diffusion Coefficient
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Dielectric Constant
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Hydrogen Bonding
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• Kamlet-Taft Solvent Parameters
• Polarity / Polarizability (p )
• Hydrogen-Bond Donating Acidity (a)
• Hydrogen-Bond Accepting Basicity (ß)

Polarity
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Polarity / Polarizability (p )
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Hydrogen-Bond Donating Acidity (a)
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Hydrogen-Bond Accepting Basicity (ß)
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• Supercritical Ethanol Applications
• Biodiesel Production
• Chemical Reaction
• Extraction
• Micro and Nano Particle Formation
• Drying

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Experimental Section
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Instrumentation
7- Oven 1- Feed Container
8- Reactor 2- High-Pressure Pump
9- Cooler 3- Three Way Valve
10- High Pressure Valve 4- Preheater
11- Back Pressure Regulator 5- Preheater Cell
12- Collection Vessel 6- Thermocouple
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Diethyl Ether Determination Carrier Gas
Nitrogen ( 99.999) Column Type Capillary
(HP-5) Injector Temperature 230 oC
Detector Temperature 250 oC Temperature
Program Column Primary Temperature
40 oC Column Hold Time at 40 oC 2 min
Temperature Increasing Rate 30 oC/min
Final Temperature 250 oC Hold
Time at 250 oC 5 min
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Diethyl Ether
Ethanol
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Diethyl Ether Identification
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Effective Parameters on The Reaction
Temperature Flow Rate Catalyst
Concentration Pressure Catalyst Type
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Temperature and Flow Rate Effect
Catalyst PTSA 2(w/v) Pressure
80 bar Temperature (100-300) oC
Flow Rate (0.1-0.7) mL/min
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Ethanol Conversion
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Diethyl Ether Selectivity
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Diethyl Ether Yield
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Yield() Selectivity() Conversion() Flow Rate(mL.min-1) Temperature(oC)
N.D. N.D. N.D. 0.1 100
N.D. N.D. N.D. 0.2
N.D. N.D. N.D. 0.4
N.D. N.D. N.D. 0.7
12.5 32.7 38.2 0.1 150
7.0 22.0 30.0 0.2
5.0 20.3 24.5 0.4
3.3 18.5 18.1 0.7
39.0 76.2 51.3 0.1 200
24.5 60.4 40.7 0.2
20.6 63.6 32.8 0.4
14.7 51.3 28.8 0.7
19.0 31.3 61.0 0.1 250
31.0 65.0 47.0 0.2
18.3 48.0 38.0 0.4
13.0 41.0 32.2 0.7
5.4 7.2 76.5 0.1 300
8.8 13.4 65.4 0.2
11.7 28.1 41.8 0.4
14.6 43.5 33.9 0.7
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Catalyst Concentration Effect Temperature
200 oC Flow Rate 0.1 mL/min
Pressure 80 bar PTSA Concentration
2-4 (w/v)
Yield() Selectivity() Conversion() PTSA Concentration (w/v)
42.1 81.3 52.0 2
60.4 94.5 64.1 4
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Pressure Effect Temperature 200 oC
Flow Rate 0.1 mL/min PTSA
Concentration 2 (w/v) Pressure
(60-80) bar
Yield() Selectivity() Conversion() Pressure (bar)
38.3 75.0 51.5 60
41.6 80.0 52.0 80
40.8 77.0 53.0 100
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Catalyst Type Temperature 200 oC
Flow Rate 0.1 mL/min Pressure
80 bar Catalyst Concentration 2 (w/v)
Yield() Selectivity() Conversion() Catalyst
41.6 80.0 52.0 PTSA
75.0 99.0 77.0 H2SO4
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Conclusion

• 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

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• Providence

• Synthesis of Other Alkyl Ethers
• Diethyl Ether Synthesis in The Presence of
  Heterogeneous Catalysts
• Diethyl Ether Separation from Ethanol

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Thanks for Your Attention
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Page 5
dG ( u2-u1) dn u (dG/ dn)T,P
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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.
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Page 8
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Page 25 Swine Manure Bio-oil
T 240-360 oC and P 34.47 MPas and Purge
with N2 30 gr waste 120 gr ethanol
Solid Bio-oil Liquid Bio-oil Liquid
Bio-oil
Filter
Distillation
at 60 oC
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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.
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