Professional Documents
Culture Documents
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Outline
Introduction
Objectives
Why supercritical CO2
Experimental results and discussion
Exploratory process studies
Fundamental studies
Solublity
Conclusions
Acknowledgement
Platform chemicals
hydroxymethylfurfural
levulinic acid
methanol
diols
phenolics
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Introduction
GeneralObjective:
Study potential ofsupercritical CO2 assolventfor starch
modification reactions
Literature data:
Remarkably little known on modification chemistry inscCO2
Landmarkpatent:
R.Harris,S.H.Jureller,J.L.Kerschner,P.T.Trzasko,andR.W.
Humphreys,U.S.Patent,5977348(1999)
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Gas
Supercritical
fluid
Liquid
(kg m-3)
100 800
1000
(Pa s)
0.001
0.005 0.01
0.05 0.1
D (m2 s-1)
1. 10-5
1.10-7
1.10-9
Introduction
(a)
(c)
(b)
(d)
Introduction
Approach:
Perform modification reactions in scCO2
System:
model reaction, acetylation selected
Approach:
screening and focussed studies
Fundamental studies on starch-scCO2 interactions
(solubility, gelatinization);
Experimental and modeling
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Introduction
Model reaction : Acetylation of starch
Native starch
Reactants :
Catalyst :
Starch acetate
acetic anhydride
alkaline salt catalyst
(NaOH, NaOAc, Na2CO3)
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Introduction
Reaction network:
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Introduction
Drawbacks current aqueous processes:
Solids content limited to 35- 42%-w
Lowering of selectivity for starch acetate due to hydolysis (SAA)
High costs associated with water removal in work-up scetion
Lab scale
High DS and SAA possible, however application of pyridine,
DMSO instead of water
Toxic, high environmental impact
Supercritical CO2 ??
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Experimental Setup
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Transmitance (%)
a
1612 cm
-1
b
1723 cm
-1
1609 cm
-1
-1
Wav elength (cm )
(b)
Acetyl
group
(a)
ppm
Acetylated starch
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0.25
0.2
Literature [1]:
rates maximal near the critical
point of mixture
0.15
0.1
T = 90 C
0.05
0
80
100
150
200
250
285
Pressure (bar)
1. Savage, P. E., Gopalan, S., Mizan, T. I., Martino, C. J.& Brock, E. E. (1995), AIChe Journal, 41, 1723-1778.
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0.25
0.2
0.15
0.1
0.05
0
80
100
150
200
250
285
Pressure (bar)
Critical region
(oC)
(MPa)
50
9.4 9.8
0.08
70
12.4 12.6
0.09
90
14.5 14.8
0.09
No
yAAH
Particle
sizesa
a.
Condition I c
Condition II d
(m)
(m)
DS
DS
36 - 45
43.64
0.21
0.51
45 - 56
52.33
0.18
0.48
56 - 63
62.55
0.18
0.46
> 63
73.5
0.15
0.29
fractionated with specified sieve trays, b. determined by laser diffraction c.Experiments at 50 oC, 8 MPa , d.Experiments
at 90 oC, 15 MPa
Catalyst screening
P:
T:
C/Sratio
t
15MPa
90C
0.1mol/mol
1h
50-90C
8- 25 MPa
0.1-0.5 (mol/mol)
AAH/S:
time:
Catalyst:
4.35
1h
K2CO3
22 experiments
Output analysed by non-linear regression
Results
Results
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Experimental method :
Gravimetric : Magnetic Suspension
Balance (MSB)
Range : max T = 473 K, max P = 50MPa
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Pressure
Temperature
Solubility
(MPa)
(oC)
0 - 9.5
40
30.9 134
2 - 19.8
100
12.7 - 121.8
0- 39.5
80
0 38
0 - 39.5
120
0 - 32.5
5 - 30
120
9.1 - 37.2
5 - 10
40
29.9 - 54.2
5 - 10
120
22.6 - 43.8
1 - 9.9
50
9.8 73
2.3 - 19.9
120
21.7 - 176.1
Polycaprolactone (PCL)
8 - 20
50
29.3 - 1637.9
Poly(L-lactide)(PLLA)
10.73 - 29.9
50
190 - 699.5
Polystyrene (PS)
Poly(ethylene terephthalate)(PET)
Polypropylene (PP)
Poly(butylenes succinate)(PBS)
Starch
Starch acetate
2-16
2-26
120
120
8-31
14-80
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Concluding Remarks
sCO2 is a suitable solvent for starch acetylation reactions
DS is tunable with pressure
Highest DS values at critical points of mixture
Reactions are intra-particle mass transfer limited
In the range T = 120oC and P = 20 300 bar :
Max S native : 31 mgCO2/g starch
Max S starch acetate : 79 mgCO2/g starch
S starch acetate > S native
Acknowledgement
Sjoerd van der Knoop
Danielle Keyzer
Prof. Z. Knej (University of Maribor)
AVEBE for stimulating discussions
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080908 | 31
DS
T , SAA
080908 | 32
0,55
0,50
0,45
0,40
0,35
0,30
0,25
0,20
0,15
0,10
0,05
0,00
SAAn
DS
50 deg C
70 deg C
90 deg C
50
60
70
80
Pressure (bar)
P , DS
constant
90
100
0,24
0,22
0,20
0,18
0,16
0,14
0,12
0,10
0,08
0,06
0,04
0,02
0,00
50 C
o
70 C
o
90 C
50
60
70
80
90
100
Pressure (bar)
Working at higher
pressure (P > 100 bar)
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
080908 | 34
080908 | 35
Degree of
crystallinity
Relative
crystallinity
Native
0.132
1.00
80
0.125
0.94
150
0.108
0.82
250
0.102
0.77
P , Crystallinity , DG
080908 | 36
Rationalise
Gas-liquid-solid
Gas phase
Liquid phase
Mainly
scCO2
AAH
Catalyst
Dissolved
AAH
Supercritical -solid
Starch
Particle
Water
Supercritical
phase
CO2
AAH
Dissolved
CO2
AA
Catalyst
Possibly
some water
Dissolved
CO2
Possibly
some water
AA
Water
AAH
AAH
Catalyst
Starch
Particle
AA
Catalyst
AA
Dissolved
CO2