Continuous Biodiesel Production

NWO/CW Project Nr. 700.54.
653
Continuous Biodiesel Productionction

Reactive Distillation Makes It Happenappen
Tony KISS, A.C. Dimian, G. Rothenberg, F. Omota
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
a
k
n
h
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STW – Dutch Technology Foundation u
y
o
NWO/CW Project Nr. 700.54.653

Entrainer-Based Reactive Distillation
☺
for Synthesis of Fatty Acids Esters
Cognis, Oleon, Sulzer and Uniquema
A.A.Kiss@uva.nl 2/24
Biodiesel = green energy
Emission type B20 = 20% biodiesel B20 B100

Biodiesel = mono-alkyl esters of fatty acids
Total unburned hydrocarbons –20% –67%
CarbonSafe,monoxiderenewable,(CO) non-toxic, biodegradable–12%–48%

Carbon dioxide (CO2) –16% –79%
CO2 Light Raw materials: vegetable oils, fat, recycled grease
Particulate matter –12% –47% CO2
Positive life cycle energy balance +2% +10%
Nitrogen oxides (NO )
Positive socialx
x
impact
Sulphur oxides (SO ) –20% –100%
Polycyclic Aromatic Hydroc rbons (PAH) –13% –80%
Less emissions than regular petroleum diesel
Nitrated PAH's (nPAH) –50% –90%
Biomass Biodiesel
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
Long life Easy to use

Inexpensive Available on industrial scale
Applications
O
CH3 O CH
3
CH3
Cosmetics Food
Why fatty esters?

Food industry
Pharmaceuticals
Cosmetics
Plasticizers
Bio-detergents
Bio-diesel
Pharmaceuticals
Bio-stuff
Industrial key players
STEARINERIE-DUBOIS
Process comparison
Current process Novel process
Batch esterification Continuous esterification
High alcohol / acid ratios Reactive distillationation
Homogeneous catalysis Heterogeneous catalysis
Difficult separation Easy separation
Corrosive & toxic Environmentally friendly
• Reduced investment costs Make up
• Reduced energy consumption Fatty acid

Steam
• Increased process controllability Alcohol
Water
• Enhanced overall rates Fatty ester
The key to success is an active & selective solid acid catalystcatalyst..
Fatty acids & alcohols
Saturated fatty acids: CH3-(CH2)n-COOH
Lauric acid (n=10)
Myristic acid (n=12) Aliphatic alcohols:
Palmitic acid (n=14) Methanol
Stearic acid (n=16) Ethanol
Arachidic acid (n=18) Propanol
…
2-Ethyl hexanol
Unsaturated fatty acids

Palmitoleic acid: CH3(CH2)5CH=CH(CH2)7COOH
Oleic acid: CH3(CH2)7CH=CH(CH2)7COOH
Reaction pathways
REACTANTS
Fatty Acid Alcohol
esterification
etherification dehydration
Fatty Ester Ether Water Alkene
Main product Secondary products
Excess of alcohol Water removal by distillation

Reaction mechanism
Catalyst
RCOOH + R’OH ↔ RCOOR’ + H2O
+ +
O H OH
C C
Secondary reactions:
R OH R OH
2 Alcohol Ether + H2O
Alcohol Alkene + H2O
OH
+
OH 2 Acid Anhydride + H2O
R'
C HO C
R OH
R OH
+
HO
R'
Catalyst
OH OH + + O +
OH OH H
C C
R OH + C R' C R'
R OH2 C R' H2O
+ R O R O R O
HO O
R' R'
Similar mechanism for hetero- and homogeneous catalysis.

Surface hydrophobicity
Water tolerant. C OH
Not enough acid sites. +
O H
hydrophobic surface with isolated acid site
Proper trade-off
hydrophobicity-acidity.
O C C OHO C OH Good catalytic activity.
OHO
+ +
H H
H+
hydrophobic surface with adjacent acid site
H2O H2O
Water sensitive. H2O H2O H2O H2O

H2 O
Easy deactivation. + H+
H2O H + + H2O
H+ OH H+ OH H H
hydrophilic surface/ numerous acid sites
Influence of surface hydrophobicity on catalytic activity.

Solid acid catalysts
Zeolites and clays
Beta, Y, MOR, ZSM-5
HeteropolyAcids CH3-(CH2)10-COOH + C8H15OH
Dodecanoic acid 22 EthylEthyl hexanolhexanol
Oxides, sulphates Acid catalyst
Composite materials CH3-(CH2)10-COOC8H15 + H2O

2 Ethyl hexyl dodecanoaoatete
Amberlyst
Nafion
Carbon-based catalysts
Polysulfonated aromatics
= Not tested yet …
Catalyst screening
Reaction profiles for esterification of dodecanoic acid with 2-ethylhexanol
100 100
H2SO4 1%wt Amberlyst
80 Amberlyst 5%wt 80 SZ
Conversion / [%]
Conversion / [%]
Nafion
60 60
Zeolites Non-catalyzed
40 40
Non-catalyzed
20 20
Alcohol:Acid = 1:1 Alcohol:Acid = 1:1
T=130°C T=150°C, 3%wt catalyst
0 0
0 30 60 90 120 0 30 60 90 120
Time / [min] Time / [min]
Organic resins are not thermo-stable. Zeolites have low activity.

Zeolites – structure
*BEA – Beta, tetragonal MFI – ZSM-5, orthorhombic
Diffusion
limitations ?!
MOR – Mordenite, orthorhombic

12.82 Å O 7.78 Å
O 4.86 Å
3.06 Å CH CH3
3
2-ethylhexyl dodecanoate CH3

Sulphated zirconia
Reaction profiles for esterification of dodecanoic acid with 2-ethylhexanol
Amberlyst
Initial rate 100
100
Nafion
SZ
Amberlyst
20
Non-Catalyzed
Conversion/[%]
Non-CatalyzedNafion
Alcohol:Acid = 1:1
SZ
80
2%wt SZ Catalyst -1
80 7.3% min 60
180°C
40
Conversion / [%]
-1
160°C 3.4% min
0 20 min 60 min
60 SZ 2%w 180°C 2.3% min-1
40 Non-catalyzed 1.2% min

-1
100 0% 1% 2% 3% SZ
160°C
/ [%]
80
20
Conversion
60
20
40
0 0 T=150°C T=160°C T=170°C
0 20 40 60 80
Time / [min]
Similar activity for esterification with 1-propanol and methanol.

Experiments + Simulations
Integration of experimental results with simulations of the
reactive distillation (RD) setup, in AspenTech AspenPlus™
Distillate
Reflux
RD column sections
a a. Rectifying section (water)
Fatty acid
b b. Recovery of alcohol
Feeds c c. Reaction zone
Alcohol d d. Recovery of fatty acid
Recycle e. Stripping section (ester)
e
Biodiesel
Thermodynamic analysis
Water Dodecanoic acid Tb=298 ºC
Tb=100 ºC 2-Ethylhexyl dodecanoate Tb=334 ºC
O
2-Ethylhexanol CH3 O CH
Tb=186 ºC 3
CH3
n-Propyl dodecanoate Tb=302 ºC

n-Propanol O CH3
O
Tb=97 ºC CH3
Methyl dodecanoate Tb=267 ºC

O
Methanol O
CH3
CH3
Tb=65 ºC
CPE analysis
One liquid phase • T > 100ºC VLE

• low conversion
• alcohol excess • open system
• T < 100ºC Chemical reaction• water removal
and
phase equilibrium• T > 100ºC
• T < 100ºC
• closed system
• reactants molar ratio=1 • P > 1 bar
LLE VLLE
RD process – methanol
Ester, 267ºC Acid, 298ºC
1
0.8
(acid+ester)
0.6
Feasible RD process. 0.4
High purity products.
X
0.2
0
1
Alcohol, 65ºC 0 0.2 0.4 0.6 0.8
Water, 100ºC
X1 (water+acid)
Distillation
RDC column
Dodecanoic acid Water ≥ 99.9 %
Feed ratio 1:1
Methanol
Evaporator
Ester ≥ 99.9 %
Effect of reflux ratio
Partial alcohol conversion Total alcohol conversion

Fatty acid Highest reaction rate Fatty acid
Highest
reaction rate
Alcohol Alcohol
Total acid conversion Total acid conversion
Maximum reaction rate is located in the centre

of RD column for an optimum reflux ratio
Entrainer-based RD flowsheet
Feasible process. High purity products >99.9% 100
With entrainer
%
Acid conversion,
99 No entrainer
Entrainer
Make up 98
Decanter
100 150 200 250 300
Stripper
Fatty acid Catalyst loading, kg/m3
Steam
Water
Alcohol Evaporator
Biodiesel
Reactive distillation column
Enhanced mass transfer and reduced catalyst loading when entrainer is used.
RDC profiles
Liquid composition and temperature profiles
1 Separation zone Reaction zone Separation Reaction

500
K
0.8
Liquid mole fraction
450
Temperature,
0.6 Water n-Propyl laurate
1-Propanol
0.4 n-Propyl acetate Lauric acid 400
0.2
0 350
0 5 10 15 20 25 30 0 5 10 15 20 25
Stage Stage
Reactive distillation – advantages
• No external recycles
• Reduced investment costs
• Reduced energy consumption
• Increased process controllability
Reaction Separation
• Equilibrium shifted to products
• Enhanced overall rates • Break azeotropes
• Improved selectivity • Handle difficult separations
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


Continuous Biodiesel Production

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NWO/CW Project Nr. 700.54.

Continuous Biodiesel Productionction

Tony KISS, A.C. Dimian, G. Rothenberg, F. Omota

NWO/CW Project Nr. 700.54.653

Cognis, Oleon, Sulzer and Uniquema

Emission type B20 = 20% biodiesel B20 B100

CarbonSafe,monoxiderenewable,(CO) non-toxic, biodegradable–12%–48%

Continuous biodiesel production process

Long life Easy to use

Why fatty esters?

• Reduced investment costs Make up

• Reduced energy consumption Fatty acid

• Enhanced overall rates Fatty ester

The key to success is an active & selective solid acid catalystcatalyst..

Unsaturated fatty acids

Fatty Acid Alcohol

Fatty Ester Ether Water Alkene

Main product Secondary products

Excess of alcohol Water removal by distillation

Similar mechanism for hetero- and homogeneous catalysis.

hydrophobic surface with isolated acid site

Water sensitive. H2O H2O H2O H2O

Influence of surface hydrophobicity on catalytic activity.

Oxides, sulphates Acid catalyst

Composite materials CH3-(CH2)10-COOC8H15 + H2O

Organic resins are not thermo-stable. Zeolites have low activity.

*BEA – Beta, tetragonal MFI – ZSM-5, orthorhombic

MOR – Mordenite, orthorhombic

2-ethylhexyl dodecanoate CH3

40 Non-catalyzed 1.2% min

Similar activity for esterification with 1-propanol and methanol.

n-Propyl dodecanoate Tb=302 ºC

Methyl dodecanoate Tb=267 ºC

One liquid phase • T > 100ºC VLE

Feasible RD process. 0.4

High purity products.

Dodecanoic acid Water ≥ 99.9 %

Feed ratio 1:1

Partial alcohol conversion Total alcohol conversion

Maximum reaction rate is located in the centre

1 Separation zone Reaction zone Separation Reaction

GREEN ENERGY Biodiesel

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