NWO/CW Project Nr. 700.54.

653

Continuous Biodiesel Production

Reactive Distillation Makes It Happen
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
STW Dutch Technology Foundation
NWO/CW Project Nr. 700.54.653

Entrainer-Based Reactive Distillation

for Synthesis of Fatty Acids Esters

k
n
a
h
T !
you

Cognis, Oleon, Sulzer and Uniquema

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Biodiesel = green energy

Emission type

CO2 Light

B20 = 20% biodiesel

B20

B100

Biodiesel = mono-alkyl esters of fatty

acids
Total unburned hydrocarbons
20%
67%
Safe,monoxide
renewable,
Carbon
(CO) non-toxic, biodegradable
12%
48%
16%
79%
Carbon dioxide (CO2)
Raw materials: vegetable oils, fat, recycled
grease
Particulate matter
12%
47%
Positive
life
cycle
energy
balance
Nitrogen oxides (NOx)
+2%
+10%
20% 100%
Sulphur
oxides
(SOx) impact
Positive
social
Polycyclic Aromatic Hydrocarbons (PAH)
13%
80%
Less emissions than regular petroleum
diesel
Nitrated PAH's (nPAH)

Biomass

50%

CO2

90%

Biodiesel

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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

Active, selective, stable

Easy to use
Available on industrial scale
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Applications

O
CH3

CH3
CH3

Cosmetics

Food

Why fatty esters?

Food industry
Pharmaceuticals
Cosmetics
Plasticizers
Bio-detergents
Pharmaceuticals

Bio-diesel

Bio-stuff
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Industrial key players

STEARINERIE-DUBOIS

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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

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

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Fatty acids & alcohols

Saturated fatty acids: CH3-(CH2)n-COOH
Lauric acid
Myristic acid
Palmitic acid
Stearic acid
Arachidic acid

(n=10)
(n=12)
(n=14)
(n=16)
(n=18)

Aliphatic alcohols:
Methanol
Ethanol
Propanol

2-Ethyl hexanol

Unsaturated fatty acids

Palmitoleic acid:
Oleic acid:

CH3(CH2)5CH=CH(CH2)7COOH
CH3(CH2)7CH=CH(CH2)7COOH
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Reaction pathways
REACTANTS
Fatty Acid

Alcohol

esterification

dehydration

etherification

Fatty Ester
Main product

Excess of alcohol

Ether

Water

Alkene

Secondary products

Water removal by distillation

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Reaction mechanism
Catalyst
H

RCOOH + ROH RCOOR + H2O

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'

Similar mechanism for hetero- and homogeneous catalysis.

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Surface hydrophobicity
Water tolerant.
Not enough acid sites.

C
O

OH

H+

hydrophobic surface with isolated acid site

H+

OH

C
H+

OH

H+

OH

Proper trade-off
hydrophobicity-acidity.
Good catalytic activity.

hydrophobic surface with adjacent acid site

H 2O

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

hydrophilic surface/ numerous acid sites

Influence of surface hydrophobicity on catalytic activity.

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Solid acid catalysts

Zeolites and clays
Beta, Y, MOR, ZSM-5

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
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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]

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

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Zeolites structure

*BEA Beta, tetragonal

MFI ZSM-5, orthorhombic

Diffusion
limitations ?!

MOR Mordenite, orthorhombic

12.82
3.06

CH3

2-ethylhexyl dodecanoate

7.78

O
O

CH3

4.86

CH3

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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

Similar activity for esterification with 1-propanol and methanol.

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Experiments + Simulations
Integration of experimental results with simulations of the
reactive distillation (RD) setup, in AspenTech AspenPlus
Distillate

RD column sections

Reflux
a

a.

Rectifying section (water)

b.

Recovery of alcohol

Feeds

c.

Reaction zone

Alcohol

d.

Recovery of fatty acid

e.

Stripping section (ester)

Fatty acid

Recycle
e
Biodiesel

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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

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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

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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 %

Feed ratio 1:1

Methanol
Evaporator
Ester 99.9 %

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Effect of reflux ratio

Fatty acid

Partial alcohol conversion

Highest reaction rate

Fatty acid

Total alcohol conversion

Highest
reaction rate

Alcohol

Total acid conversion

Alcohol

Total acid conversion

Maximum reaction rate is located in the centre

of RD column for an optimum reflux ratio
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Entrainer-based RD flowsheet
100

Feasible process. High purity products >99.9%

Acid conversion, %

Entrainer
Make up

No entrainer

99

98
100

Decanter

Fatty acid

With entrainer

Stripper

150

200

250

Catalyst loading, kg/m

300
3

Steam
Water

Alcohol

Evaporator

Biodiesel

Reactive distillation column

Enhanced mass transfer and reduced catalyst loading when entrainer is used.
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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

Liquid mole fraction

Reaction

Lauric acid

450

400

350

0
0

10

15
Stage

20

25

30

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10 15 20 25
Stage
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Reactive distillation advantages

No external recycles
Reduced investment costs
Reduced energy consumption
Increased process controllability

Reaction

Separation

Equilibrium shifted to products

Enhanced overall rates
Improved selectivity

Break azeotropes
Handle difficult separations

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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
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