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Acetic Acid, Diacetin & Triacetin
By: S. Afsari
Quaternary Solubility of
in Supercritical Carbon Dioxide
Superadvisor: Dr. Ghaziaskar
Contents
o Introduction o Supercritical Regiono Supercritical fluids and CO2 as a SF.o Advantages of Supercritical Sys.o Factors effecting on supercritical solubilityo Apparatuso SFE systemso ACAC and Glycerol Acetyls in supercritical
systemso Solubility measurements in ScCO2 and possible
separation techniques
Why GlycerolAcetyls?
Transesterification of vegetable oils
+ 3 HOCH3
NaOH or KOH Catalyst
+
Glycerol acetylation
Diacetin Triacetin
Structure
Formula
Molecular weight 176.17
Melting point -30 ºC
Boiling point 259 ºC
253 OH(CH3COO)HC
Structure
Formula
Molecular weight 176.17
Melting point -30 ºC
Boiling point 259 ºC
353 (CH3COO)HC
Supercritical Region
C
Tscco21
Supercritical FluidsSc Fluid Critical T
(ºC )Critical P
(bar)Critical ρ )g/mL(
(CO2) 1.31 8.73 466.0
(H2O) 0.374 6.220 3220.
(N2O) 4.36 5.52 4530.
(NH3) .4132 2.113 2350.
(C4H10) .6196 7.33 2320.
(SF6) 5.45 3.37 7370.
(Xe) .616 3.58 0991.
(CH2F2) 1.78 8.57 4240.
(CH4) 6.82- 0.46 1630.
(C3H8) 7.96 5.42 2200.
(C2H6O) 9.126 .054 2420.
(C6H6) 5.289 2.49 0030.
1) Low critical T2)Cheap3) available3) Inexplosive4) Nontoxic
ХХХ
CO2 Phase Diagram
Gas likeliquid like
Ability of controlling Solubility
High diffusion
Low viscosity
Easy separation of solvent from solute
Factors Effecting Solubility in Supercritical Fluids
Pressure
Temperature
Solute StructureSolvent Structure
Sample MatrixHildebrand Parameter:
r(Liq)r1/2
c /ρρ1.25Pδ
cr ρ/ρρ
Cr(Liq) 2.66ρρ ρ0.47Pδ 1/2
c
Factors Effecting Solubility in Supercritical Fluids
Pressure
Temperature
Solute StructureSolvent Structure
Sample Matrix
0.000
0.200
0.400
0.600
0.800
1.000
1.200
60 80 100 120 140 160 180 200
Pressure
y X
100
40 C 60 C
40ºC
60ºC
Factors Effecting Solubility in Supercritical Fluids
Pressure
Temperature
Solute StructureSolvent Structure
Sample Matrix
1)Solute Structure
2)Solute Vapor pressure
3)Solute-Solvent interactions
Factors Effecting Solubility in Supercritical Fluids
Pressure
Temperature
Solute StructureSolvent Structure
Sample Matrix
ScF Density(g/ml)
Solubility (mole fraction X 100) Supercritical Fluid
0.39 4.750.81 2.420.94 1.17
3CHF2CO62HC
Naphthalene
Factors Effecting Solubility in Supercritical Fluids
Pressure
Temperature
Solute StructureSolvent Structure
Sample Matrix1)Chemical
properties
2)Physical properties
Apparatus
Gas Meter
Introduction
2 port cylindrical cells
Apparatus
Gas Meter
Back Pressure Adjuster
Apparatus
Gas Meter
Sampling Collection solvent
Solute
Apparatus
Gas Meter
SFE Systems
• On-line
• Off-line
Different possible analyzing methods
Simple & practical separationHigher sensitivity
Lower repeatability
Higher repeatabilityLower solvent consumptionLower time consuming procedure
Fluctuations in flow rate
Solubility
Gas meter: V, T
Weighting GC
RTPVn
2CO 2COn
Analyten Analyten
Mole fraction:
g/L in CO2
CO2
solute
VWS
2COothersolute
solute
nnnny
Sample:
Solvent: Et-OH
ACAC
DAG
TAG
:89%
:9%
:6%
0
0.5
1
1.5
2
2.5
3
3.5
100 120 140 160 180 200
experimantal
refrence
Pressure )bar( Solubility of 1-Decanol )y×100(refrence experimental
110 1.05 1.07120 1.183 1.15160 1.652 1.587180 1.882 3.17
y×10
0
Pressure (bar)
System Stability Checking
0
10
20
30
40
50
60
70
0 0.5 1 1.5 2 2.5 3 3.5
ACAC
TA
DA
CO2 Volume (L)
W (m
g)Purge Test
Effective Parameters on Solubility in ScCO2
TemperaturePressure
Flow RateWeight of sample
Weight of Sample
0.0
50.0
100.0
150.0
200.0
250.0
300.0
350.0
400.0
0 2 4 6 8 10 12 14 16 18 20
6.0 g
3.0 g
1.5 g
0.8 g
ACAC
y×10
0
CO2 Volume (L)
Weight of Sample
0.001.002.003.004.005.006.007.008.009.00
10.00
0 2 4 6 8 10 12 14 16 18 20 22
6.0 g
3.0 g
1.5 g
0.8 g
TAG
y×10
0
CO2 Volume (L)
Weight of Sample
0.001.002.003.004.005.006.007.008.009.00
10.00
0 2 4 6 8 10 12 14 16 18 20 22
6.0 g
3.0 g
1.5 g
0.8 g
DAG
y×10
0
CO2 Volume (L)
Effective Parameters on Solubility in ScCO2
TemperaturePressure
Flow RateWeight of sample
Weight of Sample
0.0
50.0
100.0
150.0
200.0
250.0
300.0
350.0
400.0
0 2 4 6 8 10 12 14 16 18 20
6.0 g
3.0 g
1.5 g
0.8 g
y×10
0
CO2 Volume (L)
Effective Parameters on Solubility in ScCO2
TemperaturePressure
Flow RateWeight of sampleӨ (ºC): 30,40,60,75
P (bar): 70,100,120,140,160,180
0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
60 80 100 120 140 160 180 200
y×10
0
Pressure (bar)
40ºC
60ºC
75ºC
ACAC
TAG
0.00
0.20
0.40
0.60
0.80
1.00
1.20
60 80 100 120 140 160 180 200
Ө: 40ºC, P: 70 barӨ: 60ºC, P: 70 barӨ: 75ºC, P: 70 barӨ: 75ºC, P: 100 bar
mSSC blm
m
blblm ksSS
y×10
0
Pressure )bar(
40ºC
60ºC
75ºC
DAG
0.000
0.200
0.400
0.600
0.800
1.000
1.200
1.400
60 80 100 120 140 160 180 200
Ө: 40ºC, P: 70 barӨ: 60ºC, P: 70 barӨ: 60ºC, P: 100 barӨ: 75ºC, P: 70 barӨ: 75ºC, P: 100 bar
y×10
0
Pressure )bar(
40ºC
60ºC
75ºC
SeparationACAC, DAG, TAG
100
1
*
n
ii
j
m
m
86
88
90
92
94
96
98
100
102
60 80 100 120 140 160 180 200
75 C
60 C
40 C
α%
Pressure )bar(
Separation of ACAC
Expanded CO2)L(
Elapsed time)min(
Extracted ACAC)mg(
Extracted ACAC)%(
5 28 22.12 2.510 56 88.72 1020 111 192.13 2130 167 294.86 3340 222 339.06 3750 278 341.28 38
Ө: 60ºCP: 70 bar
Separation of ACAC
Expanded CO2)L(
Elapsed time)min(
Extracted ACAC)mg(
Extracted ACAC)%(
5 28 22.12 2.510 56 88.72 1020 111 192.13 2130 167 294.86 3340 222 339.06 3750 278 341.28 38
Ө: 60ºCP: 70 bar
Et-OH
ACAC
n-hexanol
Separation of ACAC
Expanded CO2)L(
Elapsed time)min(
Extracted ACAC)mg(
Extracted ACAC)%(
5 28 171.78 2.510 56 473.21 1015 83 664.73 4920 111 761.08 56
Ө: 75ºCP: 100 bar
SeparationTAG & DAG
Ө: 40ºC, P: 70 barӨ: 60ºC, P: 70 barӨ: 75ºC, P: 70 barӨ: 75ºC, P: 100 bar
TAG
Ө: 40ºC, P: 70 barӨ: 60ºC, P: 70 barӨ: 60ºC, P: 100 barӨ: 75ºC, P: 70 barӨ: 75ºC, P: 100 bar
DAG
Ө=60 ºC, P=70 bar ACACӨ=60 ºC, P=100 bar TAG
1)Incomplete extraction
2)Low efficiency
Separation of ACAC under Subcritical Situation
?
Factors Effecting Solubility in Supercritical Fluids
Pressure
Solute StructureSolvent Structure
Sample Matrix1)Chemical
properties
2)Physical properties
Binary and Quaternary Solubility of Acetic Acid
0
2
4
6
8
10
12
14
16
60 80 100 120 140 160 180 200
y×10
0
Pressure )bar(
Binary
Quaternary
Solvent Attributes of ScCO2
CO2C
O
O CCH3
OH
OC
CH3
OH
O
Factors Effecting Solubility in Supercritical Fluids
Pressure
Solute StructureSolvent Structure
Sample Matrix1)Chemical
properties
2)Physical properties
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
60 80 100 120 140 160 180 200
Diacetin
Triacetin
y×10
0
Pressure )bar(
Ө= 40ºC
Factors Effecting Solubility in Supercritical Fluids
Pressure
Solute StructureSolvent Structure
Sample Matrix1)Chemical
properties
2)Physical properties
0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
60 80 100 120 140 160 180 200
Diacetin
Triacetin
Ө= 75ºC
y×10
0
Pressure )bar(
Bartle Equation
refref
ρρcTba
PyPln
1.0barPref 3ref 700Kg.mρ
y: Solubility (mole fraction)T: temperature (K)ρ: CO2 density in P & T ( )3Kg.m
y xb m
Experimental Solubility Correlation
ACACDAGTAGӨ: 40ºC, 75ºC P: 100-180 bar
Ө: 60ºCP: 100-180 bar0
100
200
300
400
500
600
700
800
900
60 70 80 90 100 110 120 130 140 150 160 170 180 190
40 C
60 C
75 C
ρ )g
/L(
Pressure )bar(
Experimental Solubility Correlation
ACAC
y = 0.0044x + 0.4412R2 = 0.9758
y = 0.004x + 1.4445R2 = 0.9925
y = 0.0044x + 2.3226R2 = 0.9727
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
-500 -400 -300 -200 -100 0 100 200
75 C
60 C
40 C
Ln(y
P/Pre
f)
ρ-ρref
Experimental Solubility Correlation
ACAC44120
15313.
.
ba
3226215348
..
ba
y=0.0044x+1.56470.0044-5860.329919.1553Line Eq.c ( )b (K)a 13.Kgm y = 0.0044x + 1.5647
R2 = 1y = 0.004x + 1.4445
R2 = 0.9925
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
-300 -250 -200 -150 -100 -50 0
Calculated
Experimantal
Ln(y
P/Pr
ef)
ρ-ρref
Experimental Solubility Correlation
4412015313
..
ba
3226215348
..
ba
%*%exp,
exp., 1001
ti
ticalcdi
xxx
nAARD
y=0.0044x+1.56470.0044-5860.329919.1553Line Eq.c ( )b (K)a 13.Kgm
ACAC
8.0y=0.0048x-1.54190.0048-5775.715.7948
AARD%Line Eq.c ( )
b (K)a 13.Kgm
DAG
12.0y=0.0049x-1.72700.0049-5307.1495
14.2032
AARD%Line Eq.c ( )
b (K)a 13.Kgm
TAG