Documente Academic
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653
UNIVERSITY OF AMSTERDAM
van t Hoff Institute for Molecular Sciences
Nieuwe Achtergracht 166, 1018 WV Amsterdam
Tel.+31-20-525.6468, E-mail: A.A.Kiss@uva.nl
Web: staff.science.uva.nl/~ktony
Acknowledgement
Jurriaan Beckers
Marjo C. Mittelmeijer-Hazeleger
STW Dutch Technology Foundation
NWO/CW Project Nr. 700.54.653
k
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a
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you
A.A.Kiss@uva.nl
2/24
Emission type
CO2 Light
B20
B100
Biomass
50%
CO2
90%
Biodiesel
A.A.Kiss@uva.nl
3/24
Project goals
Development of an active and selective solid
acid catalyst for fatty acids esterification.
Continuous biodiesel production process
based on catalytic reactive distillation.
Catalyst requirements
Water-tolerant
Long life
Inexpensive
4/24
Applications
O
CH3
CH3
CH3
Cosmetics
Food
Bio-diesel
Bio-stuff
A.A.Kiss@uva.nl
5/24
STEARINERIE-DUBOIS
A.A.Kiss@uva.nl
6/24
Process comparison
Current process
Novel process
Batch esterification
High alcohol / acid ratios
Homogeneous catalysis
Difficult separation
Corrosive & toxic
Reduced investment costs
Reduced energy consumption
Increased process controllability
Enhanced overall rates
Continuous esterification
Reactive distillation
Heterogeneous catalysis
Easy separation
Environmentally friendly
Make up
Fatty acid
Steam
Water
Alcohol
Fatty ester
7/24
(n=10)
(n=12)
(n=14)
(n=16)
(n=18)
Aliphatic alcohols:
Methanol
Ethanol
Propanol
2-Ethyl hexanol
CH3(CH2)5CH=CH(CH2)7COOH
CH3(CH2)7CH=CH(CH2)7COOH
A.A.Kiss@uva.nl
8/24
Reaction pathways
REACTANTS
Fatty Acid
Alcohol
esterification
dehydration
etherification
Fatty Ester
Main product
Excess of alcohol
Ether
Water
Alkene
Secondary products
9/24
Reaction mechanism
Catalyst
H
OH
OH
C
R
OH
OH
Secondary reactions:
C
R
2 Alcohol
Ether + H2O
Alcohol
Alkene + H2O
2 Acid
Anhydride + H2O
OH
R'
HO
OH
OH
+
HO
R'
Catalyst
OH
OH
OH
+
HO
OH
OH2
O
R'
C
R
OH
R'
H 2O
R'
O
R'
O
R'
10/24
Surface hydrophobicity
Water tolerant.
Not enough acid sites.
C
O
OH
H+
H+
OH
C
H+
OH
H+
OH
Proper trade-off
hydrophobicity-acidity.
Good catalytic activity.
Water sensitive.
Easy deactivation.
H 2O
H 2O
H+
H 2O
H 2O
H2O
H + OH
H 2O
H2O
H+
OH
H+ H+
H 2O
11/24
HeteropolyAcids
Oxides, sulphates
Composite materials
CH3-(CH2)10-COOH + C8H15OH
Dodecanoic acid
2 Ethyl hexanol
Acid catalyst
CH3-(CH2)10-COOC8H15 + H2O
2 Ethyl hexyl dodecanoate
Amberlyst
Nafion
Carbon-based catalysts
Polysulfonated aromatics
= Not tested yet
A.A.Kiss@uva.nl
12/24
Catalyst screening
Reaction profiles for esterification of dodecanoic acid with 2-ethylhexanol
100
H2SO4 1%wt
Amberlyst 5%wt
80
60
Zeolites
40
Non-catalyzed
20
Conversion / [%]
Conversion / [%]
100
Amberlyst
80
SZ
Nafion
60
Non-catalyzed
40
20
Alcohol:Acid = 1:1
T=130C
Alcohol:Acid = 1:1
T=150C, 3%wt catalyst
0
0
30
60
90
120
Time / [min]
30
60
90
120
Time / [min]
13/24
Zeolites structure
Diffusion
limitations ?!
CH3
2-ethylhexyl dodecanoate
7.78
O
O
CH3
4.86
CH3
A.A.Kiss@uva.nl
14/24
Sulphated zirconia
Reaction profiles for esterification of dodecanoic acid with 2-ethylhexanol
SZ 2%w
60
160C
-1
180C
Non-catalyzed
40
2.3% min
20
0
-1
20 min
SZ
Nafion
Non-Catalyzed
40
SZ
60
Nafion
-1
7.3% min
-1
3.4% min
180C
80
Non-Catalyzed
80
Amberlyst
Conversion / [%]
Initial rate
Alcohol:Acid = 1:1
2%wt SZ Catalyst
Amberlyst
100
60 min
1.2% min
160C
100
20
0
0
20
40
60
80
Conversion / [%]
Conversion / [%]
100
0%
1%
2%
3%
SZ
80
60
40
20
0
Time / [min]
T=150C
T=160C
T=170C
15/24
Experiments + Simulations
Integration of experimental results with simulations of the
reactive distillation (RD) setup, in AspenTech AspenPlus
Distillate
RD column sections
Reflux
a
a.
b.
Recovery of alcohol
Feeds
c.
Reaction zone
Alcohol
d.
e.
Fatty acid
Recycle
e
Biodiesel
A.A.Kiss@uva.nl
16/24
Thermodynamic analysis
Water
Tb=100 C
Tb=298 C
Dodecanoic acid
Tb=334 C
2-Ethylhexyl dodecanoate
O
2-Ethylhexanol
Tb=186 C
CH3
CH3
CH3
Tb=302 C
n-Propyl dodecanoate
n-Propanol
Tb=97 C
CH3
CH3
Tb=267 C
Methyl dodecanoate
Methanol
Tb=65 C
O
O
CH3
A.A.Kiss@uva.nl
CH3
17/24
CPE analysis
VLE
One liquid phase
T > 100C
low conversion
open system
alcohol excess
water removal
T < 100C
Chemical reaction
and
phase equilibrium
T > 100C
T < 100C
closed system
reactants molar ratio=1
P > 1 bar
LLE
VLLE
A.A.Kiss@uva.nl
18/24
RD process methanol
Acid, 298C
Ester, 267C
1
X2 (acid+ester)
0.8
Feasible RD process.
High purity products.
0.6
0.4
0.2
0
Alcohol, 65C
RDC
Dodecanoic acid
0.2
0.4
0.6
X1 (water+acid)
0.8
Water, 100C
Distillation
column
Water 99.9 %
A.A.Kiss@uva.nl
19/24
Fatty acid
Highest
reaction rate
Alcohol
Alcohol
20/24
Entrainer-based RD flowsheet
100
Entrainer
Make up
No entrainer
99
98
100
Decanter
Fatty acid
With entrainer
Stripper
150
200
250
300
3
Steam
Water
Alcohol
Evaporator
Biodiesel
Enhanced mass transfer and reduced catalyst loading when entrainer is used.
A.A.Kiss@uva.nl
21/24
RDC profiles
Liquid composition and temperature profiles
Separation zone
Reaction zone
Separation
500
0.8
0.6
1-Propanol
0.4
n-Propyl acetate
n-Propyl laurate
Water
0.2
Temperature, K
Reaction
Lauric acid
450
400
350
0
0
10
15
Stage
20
25
30
A.A.Kiss@uva.nl
10 15 20 25
Stage
22/24
Reaction
Separation
Break azeotropes
Handle difficult separations
A.A.Kiss@uva.nl
23/24
Conclusions
Surface hydrophobicity and acid sites density
determines catalyst's activity & selectivity.
Catalysts with small pores (e.g. zeolites) are not
suitable. Resins are active but not thermally-stable.
Sulphated zirconia is active, selective and stable.
Biodiesel production by reactive distillation is feasible.
GREEN ENERGY
Biodiesel
A.A.Kiss@uva.nl
24/24