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Acetylation of Starch in Supercritical CO2

H. Muljana, F. Picchioni, L.P.B.M. Janssen and H.J. Heeres


Chemical Engineering Department
University of Groningen
The Netherlands

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Outline
Introduction
Objectives
Why supercritical CO2
Experimental results and discussion
Exploratory process studies
Fundamental studies
Solublity
Conclusions
Acknowledgement

Green chemical reaction engineering at RUG


Biofuels
Catalytic pyrolysis oil upgrading
Biodiesel from Jatropha Curcas

Platform chemicals
hydroxymethylfurfural
levulinic acid
methanol
diols
phenolics

Bio based (performance) materials


Novel polymers from valerolactone
Starch and cellulose modification

Catalytic biomass conversions

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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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Why use supercritical solvents


Liquid like density and gas like diffusivity
Properties

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

Supercritical conditions for sCO2 relatively mild: Pc = 73 bar, Tc = 31 oC


Green properties: non toxic, relatively inert, non flammable
Easy of separation

High pressure equipment required


Complex phase behaviour for mixtures

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

Pmax 350 bar

Process studies; initial screening


Process variables
Pressure: 8-25 MPa
Fixed
Temperature (90C)
Catalyst (NaOAc)
Output
Degree of substitution (DS)
Acetic anhydride conversion (Xaah)
Selectivity to desired starch acteylation reaction (Ssa)

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Product analyses: FT-IR

Transmitance (%)

a
1612 cm

-1

b
1723 cm

-1

1609 cm

-1

4000 3500 3000 2500 2000 1500 1000 500

-1
Wav elength (cm )

Product analyses: NMR

(b)

Acetyl
group

(a)

ppm

Product analyses: SEM

Native potato starch

Acetylated starch

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Optimization study- Effect of pressure


0.3
DS
Selectivity

0.25

DS max : 150 bar


SAAn max : 150 bar

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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Optimization study- Effect of pressure


0.3
DS
Selectivity

0.25

0.2

0.15

0.1

0.05

0
80

100

150

200

250

285

Pressure (bar)

Critical point mixture

Overview supercritical properties


Table 2. The critical region of AAH-CO2 mixtures at different temperatures
T

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

Effect of starch particle size


Table 3. Comparison of the DS for various starch particle sizes at different reaction conditions

Particle
sizesa

a.

Average Particle Size


(dv)b

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

Mainly surface reaction, intra particle mass transfer limited

Catalyst screening
P:
T:
C/Sratio
t

15MPa
90C
0.1mol/mol
1h

Catalyst basicity plays


a role
NaOAc exception?

Systematic process studies


T:
P:
C/S:

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

Max DS: 0.5

Results

AAH intake as additional variable

Pressure shows an optimum

Catalyst intake as additional variable

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Solubility of sCO2 in starch


Definition solubility :
S = (mCO2 dissolved)/mpolymer

Experimental method :
Gravimetric : Magnetic Suspension
Balance (MSB)
Range : max T = 473 K, max P = 50MPa

MSB schematic drawing (Nalawade S, 2005)

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Solubility Study: Results


DS SA: 0.5

S starch acetate> S native


Muljana et al. Accepted for publication in Polymer Engineering and Science

Solubility data; comparison


Polymer

Pressure

Temperature

Solubility

(MPa)

(oC)

(mg CO2/g sample)

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

FT-IR measurements for SA at high pressure

S starch acetate> S native

Lewis acid base


interaction

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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

Acetylation Study Results

DS

T , SAA

Good performance of scCO2

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

Acetylation Study Effect of pressure and temperature

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)

Determination of supercritical properties

(a)

(b)

(c)

(d)

(e)

(f)

(g)

(h)

080908 | 34

Gelatinization study (1) DSC Results

P : 80 bar 250 bar


T > , P >, DG >

080908 | 35

Gelatinization study (2) XRD results


P (bar)

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

P , broader amorphous region

080908 | 36

Optimization study- Effect of pressure

a. 150 bar, 1 h, DS = 0.29

b. 200 bar, 1 h, DS = 0.23

d. 200 bar, 24 h, DS = 0.31

b. 150 bar, 24 h, DS = 0.61

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