‫اندازه‌گيری‌حالليت‌‪-2‬اتيل‪-1-‬هگزانول‪-2‌،‬اتيل‌هگزانوئيک‌اسيد‌و‬
‫‪ -2‬اتيل‌هگزيل‪ -2-‬اتيل‌هگزانوات‌و بررسی‌واکنشهای‌‌استری‌و‌اتری‌‬
‫شدن‌و‌اب‌زداي ي‌در‌دی‌اکسيدکربن‌فوق‌بحرانی‬
‫و‬
‫بررسی‌سينتيک‌واکنش‌انيدريد‌استيک‌با‌ايزواميل‌الکل‌در حالل‌الی‬
‫‪1‬‬
‫فهرست‌مطالب‪:‬‬
‫‪‬مقدمه‪:‬‬
‫‪ )1‬تعريف‌فوق‌بحرانی‬
‫‪ )2‬کاربردهای‌سيال‌فوق‌بحرانی‬
‫‪‬بخش‌اول‪:‬‬
‫‪ (1‬انداره‌گيری‌حالليت‌‪-2‬اتيل‪-1-‬هگزانول‌و‌‪-2‬اتيل‌هگزانوئيک‌اسيد‌در‌سامانه‌های‌دو‌و‌سه‌تاي ی‬
‫‪ (2‬مطالعه‌تاثير‌پيوند‌هيدروژنی‌بر‌حالليت‬
‫‪ (3‬بررسی‌حالليت‌‪ -2‬اتيل‌هگزيل‪ -2-‬اتيل‌هگزانوات درسامانه‌های‌دو‌و‌چهارتاي ي‬
‫‪‬بخش‌دوم‪:‬‬
‫‪‬واكنشهاي‌استری‌و‌اتری‌شدن‌و‌ابزداي ی‌در‌دياكسيدكربن‌فوق‌بحراني‬
‫‪‬بخش‌سوم‪:‬‬
‫‪ ‬مطالعه‌سينتيکی‌واكنش‌استری‌شدن‌انيدريد‌استيک‌با‌ايزواميل‌الکل‌در‌حضور‌انزيم‬
‫‪2‬‬
P-T phase diagram for CO2
3
4
A typical SCF system
5
Deware sample collection
6
Effect of different parameters on
solubility
•
•
•
•
•
•
•
Pressure
Temperature
Vapor pressure
Intermolecular interaction
Molecular structure
Matrix effect
Solvent
7
Reactions in SC-CO2
• Esterification
• Etherification
• Dehydration
8
Why esterification is important?
Pharmaceutical
•Esterification
Food additives
Cosmetics
High-pressure lubricants
Advantages of SC-CO2 as solvent for esterification
•Reaction rate enhancement
•Selective esterification
9
Esterification reaction in SC-CO2
T (oC)
P (bar)
1-(p-chlorophenyl)-2,2,2Lipase
trifluoroethanol with Vinyl acetate
31-60
91-145
Oleic acid with Oleyl alcohol
Lipase
40
150
Oleic acid with Citronellol
Lipase
30-41
76-193
Oleic acid with Methanol
PTSA
40
165
Phthalic anhydride with
Methanol
No catalyst
50
97-165
Myristic acid with Ethanol
Lipase
35-70
75
Butyric acid with Isoamyl alcohol
Lipase
40
100
Fatty acid and Butanol
Lipase
36
122
Anhydride acetic with Isoamyl
alcohol
Lipase
40
80-300
Decanoic acid with Methanol
No catalyst
40
340
Reaction
Catalyst
10
Section (I): Solubility
Measurement in
SC-CO2
11
Continuous flow apparatus for solubility measurement
12
Solubility of 2-ethyl-1-hexanol and
2-ethylhexanoic acid in
SC-CO2
13
Literature values for the solubility of 1-hexanol in SC-CO2
at 311 K: Gregorowicz et.al. [28] and this work
102S
Pressure (bar)
This work
Ref. [28]
66
0.1
0.08
74
0.15
0.13
78
0.22
0.23
14
The solubility of alcohol and acid versus expanded gas
flow rate at 99 bar and 313 K
5.0
4.5
4.0
3.5
102S
3.0
2.5
2.0
1.5
1.0
Alcohol
Acid
0.5
0.0
60
160
260
360
460
Flow rate (mL/min)
560
660
760
15
Solubility of alcohol and acid in SC-CO2
7.50
6.50
5.50
10 2 S
4.50
3.50
Alcohol 40 oC
2.50
Acid 40 oC
1.50
Alcohol 50 oC
0.50
Acid 50 oC
-0.50
60
80
100
120
140
Pressure (bar)
160
180
200
16
Chrastil model evaluation for alcohol:
(▲) 313 K; (■) 323 K
8.00
6.00
ln(c)
4.00
2.00
0.00
-2.00
5.0
5.5
6.0
6.5
ln(d)
7.0
7.5
17
Chrastil model evaluation for acid:
(▲) 313 K; (■) 323 K
8.00
6.00
ln(c)
4.00
2.00
0.00
-2.00
5.0
5.5
6.0
ln(d)
6.5
7.0
18
Chrastil Parameters for alcohol and acid in
SC-CO2
ln c  k ln d  a / T  b
Compound
k
a
b
R2
Alcohol
4.3
-12246.5
21.8
0.9899
Acid
3.9
-11535.7
15.3
0.9812
19
Role of Hydrogen Bonding on Solubility
Diminution of Carboxylic Acids and Alcohols in
SC-CO2
20
Binary and ternary solubility of alcohol at 313 K
5.00
102S
4.00
3.00
2.00
Binary
Ternary
1.00
0.00
100
110
120
130
140
150
Pressure (bar)
160
170
180
190
21
Binary and ternary solubility of acid at 313 K
5.50
5.00
4.50
102S
4.00
Binary
Ternary
3.50
3.00
2.50
2.00
1.50
100
110
120
130
140
150
Pressure (bar)
160
170
180
190
22
Solubility of alcohol and acid in SC-CO2 (ternary
system)
3.50
Alcohol
Acid
102S
3.00
2.50
2.00
1.50
100
120
140
160
Pressure (bar)
180
200
23
Selectivity of alcohol relative to acid in SC-CO2
2.00
Selectivity
1.50
1.00
0.50
0.00
90
110
130
150
Pressure (bar)
170
190
24
Selectivity of alcohol relative to acid in SC-CO2
1.40
1.20
Selectivity
1.00
0.80
0.60
0.40
0.20
0.00
0
5
10
15
20
25
Time (min)
30
35
40
45
50
25
FT-IR spectrum of alcohol, acid and their mixture
3700
3410 3120
2830 2540
2250
1960 1670
1380 1090
800
Absorbance, a.u.
2.7
2.3
2EHA
1.9
2E1H
1.5
2E1H + 2EHA
1.1
0.7
0.3
-0.1
Wavenumber, cm-1
26
3700
3600
3500
3400
3300
3200
3100
0.3
Absorbance, a.u.
2E1H
0.2
2E1H + 2EHA
0.1
0
-0.1
Wavenumber, cm-1
27
IR spectra of ethanol: 1) in hexane; 2) at 298 K
28
TFA spectra at 25 oC and 82.7 bar in CO2
29
Solubility of 2-ethyl-hexyl-2-ethyl hexanoate in
binary and quaternary systems in
SC-CO2
O
O
H3C
C2H5
CH3
C2H5
30
Effect of flow rate on solubility of ester in
SC-CO2 at pressure of 170 bar and temperature of 313 K
1.80
1.60
1.40
102S
1.20
1.00
0.80
0.60
0.40
100
150
200
Flow Rate (mL/min)
250
300
31
Solubility of ester in SC-CO2 at temperature of 313 K and flow
rate of 250 ml/min
2.30
2.10
1.90
1.70
102S
1.50
1.30
1.10
0.90
0.70
0.50
0.30
100
150
200
Pressure (bar)
250
300
32
The solubility of ester in SC-CO2 at pressure of 170
bar and flow rate of 250 ml/min
1.80
1.60
102S
1.40
1.20
1.00
0.80
0.60
310
320
330
340
Temperature (K)
350
360
33
The solubility of alcohol, acid, and ester in SC-CO2 at
temperature of 313 K and flow rate of 250 ml/min
1.20
Alcohol
Acid
Ester
1.00
2
10 S
0.80
0.60
0.40
0.20
0.00
80
130
180
Pressure (bar)
230
34 280
Assume mechanism for solubility diminution of
ester
O
O
H3C
CH3
C2H5
C2H5
...... H
O
H3C
O
C2H5
.O
.
.
H
CH3
C2H5
35
Solubility diminution of ester
T (oC)
P (bar)
SD (%)
140
150
313
170
75
201
253
313
333
353
72
170
78
75
36
The solubility of alcohol, acid, and ester in SC-CO2 at
pressure of 170 bar and flow rate of 250 ml/min
0.80
Alcohol
Acid
Ester
2
10 S
0.60
0.40
0.20
0.00
310
320
330
340
Temperature (K)
350
37
360
Section (II):
Continuous esterification and
dehydration reactions in SC-CO2
SC-CO2
H3C
(CH2)3
CH
CH2OH + H3C
(CH2)3
CH
COOH
Cat.
C2H5
C2H5
C2H5
H3C
(CH2)3
CH
O C CH
H2
C
O
(CH2)3
CH3
+
Water
C2H5
38
Apparatus
39
Modified sample collection
40
Purge test for alcohol, acid, and ester
Recovery (%)
Purge Test
Ester
Alcohol
Acid
Glass beads
71.37
66.48
72.10
n-hexane
93.56
89.38
94.51
Modified
95.69
94.61
96.80
41
The effect of temperature on the continuous formation
of ester in SC-CO2
Yield (%)
T (oC)
Ester
Ether
Alkene
75
15.2
ND
84.8
110
27.4
1.6
71.05
140
0.2
0.9
98.8
42
The effect of temperature on the continuous formation of
ester in SC-CO2
Yield (%)
T (oC)
Ester
Ether
Alkene
140
0.2
0.9
98.8
110
7.1
1.5
91.5
43
The effect of pressure on the continuous formation
of ester in SC-CO2
Yield (%)
P (bar)
Ester
Ether
Alkene
150
22.2
2.1
75.4
200
21.0
2.0
77.0
250
27.4
2.9
69.7
44
The effect of mole ratio on the continuous formation of
ester in SC-CO2
Yield (%)
r
Ester
Ether
Alkene
0.5
24.6
3.4
72.0
1.0
22.5
2.1
75.4
2.0
31.9
11.6
56.6
45
The effect of flow rate on the continuous formation of
ester in SC-CO2
Yield (%)
F (mL.min-1)
Ester
Ether
Alkene
0.4
15.2
N.D.
84.8
0.6
12.2
N.D.
87.8
0.8
16.2
N.D.
84.0
46
Usability of Amberlyt 15 on the continuous formation of
ester in SC-CO2
Yield (%)
Amberlyst 15
Ester
Ether
Alkene
No used
22.2
2.1
75.4
Used
17.8
4.6
77.6
47
The effect of different parameters on the continuous formation of
ester in SC-CO2
Parameter
YieldAlkene (%)
75
84.8
T (oC)
110
71.05
140
98.8
150
75.4
P (bar)
200
77.0
250
69.7
0.5
72.0
r
1.0
75.4
2.0
65.6
0.4
84.8
F (mL.min-1)
0.6
87.8
0.8
84.0
48
1) Synthesis of dimethyl phthalate
COOCH3
COOH
+
COOH
2 CH3OH
+ 2 H2 O
COOCH3
49
2) The continuous formation of ester in SC-CO2
Yield (%)
Catalytst
ZrO2
Ester
Ether
Alkene
40.4
N.D.
N.D.
50
Durability of ZrO2
Number of repeat
Alcohol conversion (%)
1
34.4
2
8.9
3
6.8
51
Assumed mechanism for esterification
RCOOH
k1
Cat
RCOO
RCOO
Cat
k _1
Cat (Inhibition)
k _3
k _2
k4
k3
k2
RCOO
R'OH
RCOOR'
Cat
RCOO OR'
52
Conclusion
In bibnary system solubility of alcohol is greater
than acid but in ternary one there is similar
solubility. This may be due to hydrogen bonding.
Binary solubility of ester is more than quaternary
solubility.
The yield of alkene in SC-CO2 with amberlyst 15
is very high.
53
Lipase-catalyzed esterification of acetic anhydride
with isoamyl alcohol in n-hexane:
a kinetic study
H
H3C C CH2CH2 OH
CH3
+
O
O
CH3
O
n-Hexane
HC
Novozyme 3
CH3
CH3
O (CH2)2 C CH3
H
O
OH
+ H3C
O
54
Mechanism enzyme reaction
E+A
EA
FP
F
+P
Ping-Pong
B
FB
E + H2N-CHR-COOH
E-NH2
+ O=CR'-COOH
EQ
E
E-NH2
E
+Q
+ O=CR-COOH
+ H2N-CHR'-COOH
55
Experimental
Typical capillary GC separation
56
Calibration curve for isoamyl acetate and
isoamyl alcohol
12.0
10.0
yAlcohol = 1.9067x + 0.2
Conc. (M)/Conc.(M) Decane
R2 = 0.9987
8.0
6.0
yAnhydride = 1.6193x + 0.1603
R2 = 0.9994
4.0
Alcohol
2.0
Acetate
0.0
0.0
1.0
2.0
3.0
4.0
Area/Area decane
5.0
6.0
7.0
57
Effect of speed of agitation on esterification yield
100
Yield (%)
80
100 RPM
200 RPM
300 RPM
60
40
20
0
0
10
20
30
Time (min)
40
50
60
58
Effect of substrate concentration on initial reaction
10.0
9.0
8.0
R (mmol.min-1.g-1)
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
0
0.1
0.2
0.3
0.4
C (M)
0.5
0.6
0.7
59
Time course of isoamyl acetate concentration
and conversion of isoamyl alcohol
0.35
0.30
Concentration (M)
0.25
0.20
Ester
Alcohol
0.15
0.10
0.05
0.00
0
20
40
60
Time (min)
80
100
120
60
Effect of acetic anhydride concentration on initial
reaction rate
0,4M Al
0,3M Al
0,2M Al
0,1M Al
0,075M Al
0,05M Al
12.0
R(mmol.min-1.g-1)
10.0
8.0
6.0
4.0
2.0
0.0
0.0
0.1
0.2
0.3
C (M)
0.4
0.5
0.6
61
Reciprocal initial reaction rate versus reciprocal acetic
anhydride concentration
0.6
1/R (mmol.min-1.g-1)
0.5
0.4
0.3
0.2
0.05M Alc.
0.075M Alc.
0,1M Alc.
0,2M Alc.
0.1
0.0
0.0
5.0
10.0
15.0
1/C (M)
20.0
25.0
62
Effect of acetic acid concentration on isoamyl
acetate yield
100.0
Yield(%)
80.0
60.0
0.0M Ac
0.1M Ac
0.3M Ac
40.0
20.0
0.0
0
20
40
60
Time (min)
80
100
120
63
Kinetic parameters for esterification reaction
Rmax [ Al ][ An]
R
[ Al ][ An]  K mAl [ An](1  [ An] / K iAn )  K mAn [ Al ]
Parameter
Value
Dimension
Rmax
52.9
Mmol.min-1.g-1
KmAl
0.825
Mmol.mL-1
0.361
Mmol.mL-1
0.592
Mmol.mL-1
KmAn
KiAn
64
0,4M Al
0,3M Al
0,2M Al
0,1M Al
0,075M Al
0,05M Al
12.0
R(mmol.min-1.g-1)
10.0
8.0
6.0
4.0
2.0
0.0
0.0
0.1
0.2
0.3
C (M)
0.4
0.5
0.6
65
Conclusion
The Isoamyl acetate synthesis with enzyme is very
selective (100% selectivity).
The reaction mechanism is Ping-Pong with
anhydrid acetic as an inhibitor.
66
‫از‌حضور‌شما‌در‌اين‌سمينار‌سپاسگزارم‬
‫‪67‬‬
‫پايان‬
‫‪68‬‬
Solubility of Naphthalene in SC-CO2
69
Solubility of MHET in various solvents at 130 oC
COOCH2CH2OH
COOH
70
Reaction rate enhancement
O
O
O
O
C
OMe
C
OH
+ MeOH
O
71
Esterification: Selective ethoxylation of
terephthalic acid
CO2H
COOCH2CH2OH
+
CO2H
Terphtalic acid
O
CO2CH2CH2OH
Catal.
SCF
CO2H
SCF
CO2CH2CH2OH
MHTE
72
The effect of temperature on reaction rate
T (oC)
Reaction rate (mmol.min-1)
50
39.7
90
67.8
110
141.2
130
176.9
Ea= 227 Kcal.mol-1
73
Memory effect of enzyme in organic solvents
74
Hydrogenation: The dependence of the product
distribution on the teperature of reactor wall
75
-2(-iD gniniatnoc )IIPA naxoleD(
2exyl( phosphoric acid h-lyhte
EHPA( as ion exchanger2)D
Deloxan ®, a polysiloxane material
76
Selectivity = SAcid/SAlcohol
SDi = (Sb-Sq)×100/Sb
AARD  (1 / N )1
N
Scalc  Sexp
Sexp
77
Schematic representation of an inferred enzyme-substrate complex
(A: CO2 molecules)
78
Quadrupole-Quadrupole CO2/C10H8 interaction
O
C
O
79
Schematic representation of relative solvent reorganization require
for photodimerization leading to the syn versus anti configuration
80
‫از‌حضور‌شما‌در‌اين‌سمينار‌سپاسگزارم‬
‫‪81‬‬
‫از‌حضور‌شما‌در‌اين‌سمينار‌سپاسگزارم‬
‫‪82‬‬