isfahan university of technology department of chemistry continuous synthesis of diethyl ether from...
TRANSCRIPT
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
11
Contents
Introduction
Experimental Section
Instrumentation Diethyl Ether Determination Diethyl Ether Identification Effective Parameters on The Reaction
Conclusion
Providence
22
Supercritical Fluid Definition
3
Supercritical Fluid Properties
GasSupercritical Fluid
Liquid
Density (g.cm-3)(0.6-2) * 10-3(0.2-0.5)(0.6-2)
Diffusion Coefficient (cm2.s-1)(1-4) * 10-1(10-3-10-4)(0.2-2) * 10-5
Viscosity (g.cm-1.s-1)(1-3) * 10-4(1-3) * 10-4(0.2-3) * 10-2
44
Supercritical Fluids Classification
Non-associating Fluids
Associating Fluids
Critical Temperature
)o C(
CriticalPressure
)bar(
Density(g.cm-3)
CO231.173.80.466
H2O374.0220.60.322
EtOH240.861.40.280
5
Supercritical Fluid Selection for Chemical Reactions
Critical Temperature and Pressure
Solvent Strength
Corrosion
Toxicity
Supercritical Ethanol
66
Supercritical Ethanol Properties
Critical Temperature and Pressure
77
Density
88
99
Viscosity
Diffusion Coefficient
1010
Dielectric Constant
1111
Hydrogen Bonding
1212
1313
14
Kamlet-Taft Solvent Parameters:• Polarity / Polarizability (π )∗• Hydrogen-Bond Donating Acidity (α)
• Hydrogen-Bond Accepting Basicity (β)
1515
Polarity
Polarity / Polarizability (π )∗
1616
Hydrogen-Bond Donating Acidity (α)
1717
Hydrogen-Bond Accepting Basicity (β)
1818
Supercritical Ethanol Applications
Biodiesel Production
Chemical Reaction
Extraction
Micro and Nano Particle Formation
Drying
1919
Experimental Section
20
Instrumentation
21
1 -Feed Container7 -Oven
2 -High-Pressure Pump8 -Reactor
3 -Three Way Valve9 -Cooler
4 -Preheater 10 -High Pressure Valve
5 -Preheater Cell11 -Back Pressure Regulator
6 -Thermocouple12 -Collection Vessel
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 min22
23
Ethanol
Diethyl Ether
Me
SO
Me
SO
Me
SO
Me
SO
O
OH
H O Et
O OH
OEt
H
O
OEt
OH2
O
OEt
H2O
Me
S
Me
SO
O
O C2H5
H O C2H5
SN2
O OH
O
CH3CH2 2O
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 : (100-300) oC
Flow Rate : (0.1-0.7) mL/min
27
0
10
20
30
40
50
60
70
80
90
80 100 120 140 160 180 200 220 240 260 280 300 320
Temperature (C)
Eth
ano
l C
on
vers
ion
(%
)
0.1(mL/min)
0.2(mL/min)
0.4(mL/min)
0.7(mL/min)
Ethanol Conversion
28
0
10
20
30
40
50
60
70
80
90
100
80 100 120 140 160 180 200 220 240 260 280 300 320
Temperature (C )
Die
thyl
Eth
er S
elec
tivity
(%)
0.1 (mL/min)
0.2 (mL/min)
0.4 (mL/min)
0.7 (mL/min)
Diethyl Ether Selectivity
29
0
5
10
15
20
25
30
35
40
45
50
80 100 120 140 160 180 200 220 240 260 280 300 320
Temperature (C)
Die
thyl
Eth
er Y
ield
(%
)
0.1 (mL/min)
0.2 (mL/min)
0.4 (mL/min)
0.7 (mL/min)
Diethyl Ether Yield
30
Temperature(oC)Flow Rate(mL.min-1)Conversion(%)Selectivity(%)Yield(%)
1000.1N.D.N.D.N.D.
0.2N.D.N.D.N.D.
0.4N.D.N.D.N.D.
0.7N.D.N.D.N.D.
1500.138.232.712.5
0.230.022.07.0
0.424.520.35.0
0.718.118.53.3
2000.151.376.239.0
0.240.760.424.5
0.432.863.620.6
0.728.851.314.7
2500.161.031.319.0
0.247.065.031.0
0.438.048.018.3
0.732.241.013.0
3000.176.57.25.4
0.265.413.48.8
0.441.828.111.7
0.733.943.514.631
Catalyst Concentration Effect
Temperature : 200 oC
Flow Rate : 0.1 mL/min
Pressure : 80 bar
PTSA Concentration : 2-4 (%w/v)
PTSA Concentration (%w/v)Conversion(%)Selectivity(%)Yield(%)
252.081.342.1
464.194.560.4
32
Pressure Effect
Temperature : 200 oC Flow Rate : 0.1 mL/min PTSA Concentration : 2 (%w/v) Pressure : (60-80) bar
Pressure (bar)Conversion(%)Selectivity(%)Yield(%)
6051.575.038.3
8052.080.041.6
10053.077.040.8
33
Catalyst Type
Temperature : 200 oC Flow Rate : 0.1 mL/min Pressure : 80 bar Catalyst Concentration : 2 (%w/v)
CatalystConversion(%)Selectivity(%)Yield(%)
PTSA52.080.041.6
H2SO477.099.075.0
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 = ( u2-u1) 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 = 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
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.
