acetic acid, diacetin & triacetin
DESCRIPTION
Quaternary Solubility of in Supercritical Carbon Dioxide. Acetic Acid, Diacetin & Triacetin. By: S. Afsari . Superadvisor: Dr. Ghaziaskar. Contents. Introduction Supercritical Region Supercritical fluids and CO 2 as a SF. Advantages of Supercritical Sys. - PowerPoint PPT PresentationTRANSCRIPT
![Page 1: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/1.jpg)
Acetic Acid, Diacetin & Triacetin
By: S. Afsari
Quaternary Solubility of
in Supercritical Carbon Dioxide
Superadvisor: Dr. Ghaziaskar
![Page 2: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/2.jpg)
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
![Page 3: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/3.jpg)
Why GlycerolAcetyls?
![Page 4: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/4.jpg)
![Page 5: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/5.jpg)
Transesterification of vegetable oils
+ 3 HOCH3
NaOH or KOH Catalyst
+
![Page 6: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/6.jpg)
Glycerol acetylation
![Page 7: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/7.jpg)
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
![Page 8: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/8.jpg)
Supercritical Region
C
Tscco21
![Page 9: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/9.jpg)
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
![Page 10: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/10.jpg)
CO2 Phase Diagram
![Page 11: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/11.jpg)
Gas likeliquid like
Ability of controlling Solubility
High diffusion
Low viscosity
Easy separation of solvent from solute
![Page 12: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/12.jpg)
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
![Page 13: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/13.jpg)
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
![Page 14: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/14.jpg)
Factors Effecting Solubility in Supercritical Fluids
Pressure
Temperature
Solute StructureSolvent Structure
Sample Matrix
1)Solute Structure
2)Solute Vapor pressure
3)Solute-Solvent interactions
![Page 15: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/15.jpg)
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
![Page 16: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/16.jpg)
Factors Effecting Solubility in Supercritical Fluids
Pressure
Temperature
Solute StructureSolvent Structure
Sample Matrix1)Chemical
properties
2)Physical properties
![Page 17: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/17.jpg)
Apparatus
Gas Meter
![Page 18: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/18.jpg)
Introduction
![Page 19: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/19.jpg)
2 port cylindrical cells
![Page 20: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/20.jpg)
Apparatus
Gas Meter
![Page 21: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/21.jpg)
Back Pressure Adjuster
![Page 22: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/22.jpg)
Apparatus
Gas Meter
![Page 23: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/23.jpg)
Sampling Collection solvent
Solute
![Page 24: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/24.jpg)
Apparatus
Gas Meter
![Page 25: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/25.jpg)
![Page 26: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/26.jpg)
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
![Page 27: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/27.jpg)
Solubility
Gas meter: V, T
Weighting GC
RTPVn
2CO 2COn
Analyten Analyten
Mole fraction:
g/L in CO2
CO2
solute
VWS
2COothersolute
solute
nnnny
![Page 28: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/28.jpg)
Sample:
Solvent: Et-OH
ACAC
DAG
TAG
:89%
:9%
:6%
![Page 29: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/29.jpg)
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
![Page 30: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/30.jpg)
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
![Page 31: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/31.jpg)
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)
![Page 32: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/32.jpg)
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)
![Page 33: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/33.jpg)
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)
![Page 34: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/34.jpg)
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)
![Page 35: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/35.jpg)
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
![Page 36: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/36.jpg)
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
![Page 37: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/37.jpg)
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
![Page 38: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/38.jpg)
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(
![Page 39: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/39.jpg)
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
![Page 40: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/40.jpg)
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
![Page 41: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/41.jpg)
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
![Page 42: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/42.jpg)
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
![Page 43: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/43.jpg)
Separation of ACAC under Subcritical Situation
?
![Page 44: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/44.jpg)
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
![Page 45: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/45.jpg)
Solvent Attributes of ScCO2
CO2C
O
O CCH3
OH
OC
CH3
OH
O
![Page 46: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/46.jpg)
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
![Page 47: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/47.jpg)
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(
![Page 48: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/48.jpg)
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
![Page 49: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/49.jpg)
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(
![Page 50: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/50.jpg)
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
![Page 51: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/51.jpg)
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
![Page 52: Acetic Acid, Diacetin & Triacetin](https://reader035.vdocument.in/reader035/viewer/2022081503/5681634a550346895dd3da1f/html5/thumbnails/52.jpg)
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