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Biodiesel by Catalytic Reactive Distillation Powered by Metal Oxides

Anton A. Kiss,*
,,
Alexandre C. Dimian,*
,,
and Gadi Rothenberg*
,,
Van t Hoff Institute for Molecular Sciences, UniVersity of Amsterdam, Nieuwe Achtergracht 166,
1018 WV Amsterdam, The Netherlands, Akzo Nobel Chemicals B.V., Velperweg 76, Arnhem, The
Netherlands, and Yellow Diesel B.V., Roetersstraat 35, Amsterdam, The Netherlands
ReceiVed May 24, 2007. ReVised Manuscript ReceiVed September 27, 2007
The properties and use of biodiesel as a renewable fuel as well as the problems associated with its current
production processes are outlined. A novel sustainable esterication process based on catalytic reactive distillation
is proposed. The pros and cons of manufacturing biodiesel via fatty acid esterication using metal oxide solid acid
catalysts are investigated. Finding catalysts that are active, selective, and stable under the process conditions is the
main challenge for a successful design. The best candidates are metal oxides such as niobic acid, sulfated zirconia,
sulfated titania, and sulfated tin oxide. Rigorous process simulations show that combining metal oxide catalysts
with reactive distillation technology is a feasible and advantageous solution for biodiesel production.
1. Introduction
Sustainable energy management is a major concern of the
modern society. The increasing energy demand makes the imple-
mentation of sustainable fuels a crucial issue worldwide.
1,2
Biodie-
sel has become increasingly attractive because it is made from
renewable sources and combines high performance with environ-
mental benets.
36
The idea of using vegetable oil as fuel for diesel
engines is over a century old. In fact, Rudolph Diesel himself
demonstrated the performances of his engine using peanut oil as
fuel. Unlike petroleum diesel that contains hydrocarbons, biodiesel
consists of a mixture of monoalkyl esters of long-chain fatty acids.
These are typically produced by (trans)esterication.
7
Biodiesel has several advantages over petroleumdiesel: it is safe,
renewable, nontoxic, and biodegradable; it contains no sulfur and
is a better lubricant.
4,8
Despite the chemical differences, these two
fuels have similar properties and performance parameters (Table
1).
912
Along with its technical advantages over petroleum diesel,
biodiesel brings several additional benets to the society: rural
revitalization, creation of new jobs, and less global warming.
An important characteristic of diesel fuels is the ability to
autoignite, quantied by the cetane number (cetane index).
Biodiesel not only has a higher cetane number than petroleum
diesel but also has a higher ash point, meaning better and safer
performance. Blends of biodiesel and petroleum diesel are
designated by a B followed by the vol % of biodiesel. B5
and B20, the most common blends, can be used in unmodied
diesel engines.
5
Remarkably, biodiesel is the only alternative
fuel currently available with an overall positive life-cycle energy
balance (Figure 1), producing 3.2 units of fuel product energy
per unit of fossil energy consumed, compared to barely 0.83
units for petroleum diesel.
3
The presence of oxygen in biodiesel (10%) improves
combustion and reduces CO, soot, and hydrocarbon emissions
while slightly increasing the NO
x
emissions. Figure 2 shows
the biodiesel versus petroleum diesel emissions as well as the
amount of CO
2
per distance produced by various fuels.
4,11
One
comprehensive study showed that using B20 in trucks and buses
would completely eliminate the black smoke released during
acceleration.
4
There are ve primary ways for making biodiesel: (i) direct
use and blending of vegetable oil,
7
(ii) use of microemulsions
* E-mail: tony.kiss@akzonobel-chemicals.com (A.A.K.); alexd@
science.uva.nl (A.C.D.); gadi@science.uva.nl (G.R.). Fax: +31 20 525 5604.

University of Amsterdam.

Akzo Nobel Chemicals B.V.

Yellow Diesel B.V.


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Vol. TN06-085.
Table 1. Petroleum Diesel vs Biodiesel
fuel property diesel biodiesel
fuel standard ASTM D975 ASTM D6751
fuel composition C
10
-C
21
HC
a
C
12
-C
22
FAME
a
kinetic viscosity, mm
2
/s
(at 40 C)
1.34.1 1.96.0
specic gravity, kg/L 0.85 0.88
boiling point, C 188343 182338
ash point, C 6080 100170
cloud point, C -15 to 5 -3 to 12
pour point, C -35 to 15 -15 to 10
cetane number
(ignition quality)
4055 4865
stoichiometric
air/fuel ratio (AFR)
15 13.8
life-cycle energy
balance (energy units
produced per unit energy
consumed)
0.83/1 3.2/1
a
HC, hydrocarbons; FAME, fatty acid methyl esters.
Energy & Fuels 2008, 22, 598604 598
10.1021/ef700265y CCC: $40.75 2008 American Chemical Society
Published on Web 12/06/2007
with short-chain alcohols,
7
(iii) thermal cracking (pyrolysis) of
vegetable oils,
13,14
(iv) transesterication of triglycerides
7,14
catalyzed by bases, acids, or enzymes,
15,16
and (v) esterication
of fatty acids with alcohols, using acid catalysts (H
2
SO
4
) or
solid acids.
17,18
The current manufacturing processes, however,
have several disadvantages: shifting the equilibrium to fatty
esters by using an excess of alcohol that must be separated and
recycled, making use of homogeneous catalysts that require
neutralization (causing salt waste streams), expensive separation
of products from the reaction mixture, and high costs due to
relatively complex processes involving one to two reactors and
several separation units. Therefore, to solve these problems, we
develop a sustainable biodiesel production process based on
catalytic reactive distillation using solid acid catalysts (SACs).
19
Reactive distillation (RD) integrates reaction and separation
in one unit. This intensies mass transfer and allows in situ
energy integration while simplifying the process owsheet and
operation. However, combining the two operations is possible
only if the reactions show reasonable conversion and selectivity
data at pressures and temperatures that are compatible with the
distillation conditions.
2022
Ion-exchange resins were used
successfully in low-temperature esterication processes.
2325
Previously, we examined the applicability of a range of alcohol
types in the fatty acid esterication process and screened various
materials, such as zeolites, ion-exchange resins, heteropoly acids,
sulfated carbons, and sulfated zirconia, with potential SAC
applications.
17,18
Here, we focus on using metal oxides as
catalysts. In addition to sulfated zirconia, we have tested sulfated
titania, sulfated tin oxide, and niobic acid. We study the effects
of calcination temperature and acid concentration on the catalytic
activity and integrate the catalyst development in the process
design at an early stage. Our objective is a catalytic reactive
distillation process powered by metal oxides as green catalysts,
with the potential for making low-cost biodiesel. In this Article,
we present the key features of our approach, present experi-
mental results and rigorous process simulations, and discuss the
possible applications of this new process.
2. Experimental Section
Materials and Instrumentation. Characterization of mixed
metal oxides was performed by atomic emission spectroscopy with
inductively coupled plasma atomization (ICP-AES) on a CE
Instruments Sorptomatic 1990. NH
3
-TPD was used for the char-
acterization of acid site distribution. Sulfated zirconia (0.3 g) was
heated up to 600 C using He (30 mL min
-1
) to remove adsorbed
components. Then, the sample was cooled at room temperature and
saturated for 2 h with 100 mL min
-1
of 8200 ppm NH
3
in He as
carrier gas. Subsequently, the system was ushed with He at a ow
rate of 30 mL min
-1
for 2 h. The temperature was ramped up to
600 C at a rate of 10 C min
-1
. A thermal conductivity detector
(TCD) was used to measure the ammonia desorption prole of NH
3
.
Textural properties were established from the nitrogen adsorption
isotherm determined after degassing at 200 C under a vacuum at
510 mbar. The catalyst surface area was calculated using the BET
equation, and the pore volume was determined at a relative pressure
of 0.98. The pore size was calculated using the BarrettJoyner
Halenda (BJH) method. All process simulations were performed
using the AspenTech AspenOne 2004 engineering suite.
26
Procedure for Fatty Acid Esterication. The experimental
results are presented on the use of solid catalysts in esterication
of dodecanoic acid (C
12
H
24
O
2
) with methanol (CH
4
O), propanol
(C
3
H
8
O), or 2-ethylhexanol (C
8
H
18
O). Reactions were performed
using a system of six parallel reactors (100 mL)sSTEM Omni-
Reacto Station 6100, with modular design and interchangeable
heating blocks, glassware, and reux heads. Reaction progress was
monitored by gas chromatography (GC). GC analysis was per-
formed using an InterScience GC-8000 gas chromatograph with a
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2006, 40, 141150.
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Aspen Technology Inc.: Cambridge, U.K., 2004.
Figure 1. Life cycle of diesel vs biodiesel as an environmentally friendly
fuel. The CO
2
cycle is closed for biodiesel but not for diesel.
Figure 2. Biodiesel vs petroleum diesel emissions (top). Comparison
of CO
2
emissions for most common fuels (bottom).
Biodiesel by Catalytic ReactiVe Distillation Energy & Fuels, Vol. 22, No. 1, 2008 599
DB-1 capillary column (30 m0.21 mm). GC conditions: isotherm
at 40 C (2 min), ramp at 20 C min
-1
to 240 C, isotherm at 240
C (4 min). The injector and detector temperatures were set at 240
C. Reaction proles were measured for both noncatalyzed and
catalyzed reactions, at several temperatures exceeding 100 C
(below 100 C and in the absence of mixing, the liquids separate
before equilibrium is reached). The catalyst concentration in the
reaction mixture was varied from 0 to 5 wt %. The initial alcohol/
acid molar ratio used was varied from 1:1 up to 5:1. Table 2 shows
the matrix of experimental conditions.
Double-distilled water was used in all experiments. Unless
otherwise noted, chemicals were purchased from commercial
companies and were used as received. Dodecanoic acid 98 wt %
(GC), methanol, propanol, and 2-ethylhexanol 99+ wt % were
supplied by Aldrich, zirconil chloride octahydrate 98+ wt % by
Acros Organics, 25 wt % NH
3
solution and H
2
SO
4
97% from
Merck. Niobic acid (HY-340, Nb
2
O
5
nH
2
O) was provided by
Companhia Brasileira de Metalurgia e Minerao-CBMM. The
sulfated metal oxides were prepared according to literature recipes.
2732
Procedure for Preparation of Metal Oxides. The sulfated metal
oxides (zirconia, titania, and tin oxide) were synthesized using a
two-step method. The rst step consists of hydroxylation of
zirconium, titanium, and tin complexes. The second step is the
sulfonation with H
2
SO
4
followed by calcination in air at various
temperatures. Example: Sulfated tin oxide. Sn(OH)
4
was prepared
by adding a 25% aqueous NH
3
solution to an aqueous solution of
SnCl
4
(Aldrich, >99%, 50 g in 500 mL) until the pH reached 910.
The precipitate was ltered, washed, and then suspended in a 100
mL aqueous solution of 4% CH
3
COONH
4
. The precipitate was
ltered, washed, and dried for 16 h at 140 C. Then, 1 N H
2
SO
4
(15 mL of H
2
SO
4
per 1 g of Sn(OH)
4
) was added to prepare SO
4
2-
/
SnO
2
and the precipitate was ltered, washed, and dried for 16 h
at 140 C, and calcined in air for 4 h.
Testing for Catalyst Leaching. The leaching of catalyst was
studied in an organic and an aqueous phase. First, a sample of fresh
sulfated zirconia catalyst (0.33 g) was stirred with water (50 mL)
while measuring the pH development in time. After 24 h, the acidity
was measured by titration with KOH. The suspension was then
ltered and treated with a BaCl
2
solution to test for SO
4
2-
ions. In
a second experiment, the catalyst was added to an equimolar mixture
of reactants. After 3 h at 140 C, the catalyst was recovered from
the reaction mixture, dried at 120 C, and nally stirred in 50 mL
of water. The pH was measured and the suspension titrated with a
diluted solution of KOH after 24 h. Sulfate ions in the suspension
were determined qualitatively with BaCl
2
(at 140 C, the reaction
mixture does not split into two liquid phases because the water
evaporates). In a third experiment, the same procedure was repeated
at 100 C when the reaction mixture segregates and a separate
aqueous phase is formed.
3. Results
An industrial solid acid esterication catalyst must fulll
several conditions that seem trivial on the laboratory scale. It
should have high activity and selectivity, as byproducts are likely
to render the process uneconomical, and it should be water-
tolerant and stable at relatively high temperatures, which are
required for increased reaction rates. Additionally, it must be a
readily available and inexpensive material. Considering these
conditions and previous literature reports, we investigated metal
oxides with strong Brnsted acid sites and high thermal stability
(up to 200250 C). The literature study shows a large range
of SACs available: zeolites,
33,34
ion-exchange resins,
3537
het-
eropoly acids,
38,39
carbon-based catalysts,
18,38
sulfated metal
oxides,
27,4046
and niobium-based catalysts.
4749
On the basis of
the literature reviews and our previous experimental screening,
17,18
we focused on metal oxide catalysts based on Zr, Ti, Sn, and
Nb.
Fatty acid esterication using solid acids is not yet well
established in industry, as it is much more difcult to nd a
suitable SAC for long-chain acid esterication compared to
shorter acids such as acetic acid. In contrast to liquid acids that
possess well-dened acid properties, SACs may contain a variety
of acid sites.
19,50,51
Usually, SACs are categorized by their
Brnsted or Lewis acidity, the strength and number of sites,
and the textural properties of the support.
52
A water-tolerant
catalyst is required, since the nonideal mixture may segregate
into an organic and an aqueous phase that may easily deactivate
the catalyst.
33
In a typical reaction, equivalent amounts of dodecanoic acid
and 2-ethylhexanol were reacted at 160 C in the presence of 1
wt % solid acid catalyst (eq 1). We dene the percentage
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Table 2. Matrix of Experimental Conditions
catalyst
catalyst
amount (wt %)
temperature
(C)
reactant
ratio
a
H
2
SO
4
0 (noncatalyzed) 120 1:1
Amberlyst-15 0.5
b
130 2:1
Cs
2.5
H
0.5
PW
12
O
40
1 140 3:1
Nb
2
O
5
5H
2
O (HY-340) 2 150 5:1
ZrO
2
/SO
4
2-
(SZ) 3 160
b
TiO
2
/SO
4
2-
(STi) 5
b
180
b
SnO
2
/SO
4
2-
(SSn) 10
b
a
The reactant ratio is expressed as the initial molar ratio of alcohol
to acid.
b
These experiments were performed only for sulfated zirconia
(SZ) or noncatalyzed reaction.
600 Energy & Fuels, Vol. 22, No. 1, 2008 Kiss et al.
fractional conversion as X %) 100{1 - ([acid]
nal
/[acid]
initial
)}
and normalize the amount of catalyst to the total amount of
reactants, that is, W
cat
% ) M
cat
/(M
acid
+ M
alcohol
). Using metal
oxides as catalysts, no byproducts were observed by GC
analysis. For all of the catalysts described here, the selectivity
was assessed by testing the formation of side products in a
suspension of catalyst in alcohol (e.g., sulfated zirconia in pure
2-ethylhexanol) under reux for 24 h. No ethers or dehydration
products were detected by GC analysis.
Figure 3 shows the reaction proles for the noncatalyzed
esterication of dodecanoic acid with 2-ethylhexanol and
methanol, respectively. This background reaction should be kept
in mind when comparing the efciency of the various solid
catalysts.
Zirconia compounds are well-known for their industrial
applications in a variety of processes.
30,5355
Zirconia can be
modied with sulfate ions to form a superacidic catalyst,
depending on the treatment conditions.
32
In our experiments,
sulfated zirconia (SZ) outperformed other solid acid catalysts
(Figure 4, left). SZ showed good thermal stability as well as
high activity and selectivity for the esterication of fatty acids
with a variety of alcohols ranging from 2-ethylhexanol to
methanol. By increasing the amount of catalyst, the reaction
rate, hence conversion after a certain time, can be further
increased (Figure 4, right). Thus, sulfated zirconia is suitable
for RD applications where high activity is required in a short
time.
The concentration of the H
2
SO
4
used for sulfated zirconia
preparation did not affect the catalytic activity. Conversely, the
calcination temperature has a tremendous effect: the optimal
calcination temperature was 600700 C (Figure 5, left). In a
separate set of experiments, we tested the catalyst reusability
and robustness. After ve consecutive runs, the activity dropped
to 90% of the original value and (importantly) remained
constant thereafter. Recalcination of the used catalyst restored
its original activity. Considering the promising results with
sulfated zirconia, we tested also the applicability of sulfated
titania and tin oxide. These catalysts performed slightly better
than SZ, showing a several percent increase in acid conversion
(Figure 5, right). However, SZ is cheaper and readily available
on the industrial scale. The catalytic activity of SZ can be
enhanced by preparing it from using a chlorosulfonic acid
precursor dissolved in an organic solvent, instead of the
conventional H
2
SO
4
impregnation.
32
Other metals, such as iron,
can also be added to enhance the activity.
53
The catalyst characterization results are given in Table 3. The
values are in very good agreement with literature data.
40,56
As
expected, higher sulfur content corresponds to higher acidity
of the catalyst and consequently higher catalytic activity. In
addition, the pore size plays an important role as the reactants
and the products must be able to t inside the catalyst to take
full advantage of the total surface area available. The pore sizes
of metal oxides are sufciently large (>2 nm) to facilitate the
mass transfer into and from the catalyst pores. This compensates
for their lower acidity compared to other solid acids.
17,18
The leaching of catalyst was studied in an organic and an
aqueous phase. From the leaching tests, it can be concluded
that sulfated zirconia is not deactivated by leaching of sulfate
groups when water is present in the organic phase, but it is
easily deactivated in pure water or aqueous phase. Other solid
acid catalysts are also deactivated by the presence of water or
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Figure 3. Esterication of dodecanoic acid with 2-ethylhexanol (left)
and methanol (right), noncatalyzed reaction at different temperatures.
Figure 4. Esterication of dodecanoic acid with 2-ethylhexanol (left)
at 130 C using liquid and solid acid catalysts (2 wt %); (right)
noncatalyzed and catalyzed (0.510 wt % SZ catalyst) reaction proles.
(1)
Figure 5. Reaction proles for the esterication of dodecanoic acid
with 2-ethylhexanol: (left) using sulfated zirconia catalyst calcined at
400800 C; (right) using sulfated zirconia, titania, and tin oxide
catalysts.
Table 3. Catalyst Characterization
catalyst sample
surface
area (m
2
/g)
pore
volume
(cm
3
/g)
pore diameter
max/mean/
calcd (nm)
sulfur
content (%)
Cs
2.5
H
0.5
PW
12
O
40
163 0.135 2/5.5/3 N/A
Nb
2
O
5
(HY-340) 176 0.162 //3.7 N/A
ZrO
2
/SO
4
2-
/650 C 118 0.098 4.8/7.8/7.5 2.3
TiO
2
/SO
4
2-
/550 C 129 0.134 4.1/4.3/4.2 2.1
SnO
2
/SO
4
2-
/650 C 100 0.102 3.8/4.1/4.1 2.6
Biodiesel by Catalytic ReactiVe Distillation Energy & Fuels, Vol. 22, No. 1, 2008 601
in an aqueous phase. There are several methods to prevent
aqueous phase formation and leaching of acid sites: (1) using
an excess of one reactant, (2) working at low conversions, and
(3) increasing the temperature to a value exceeding the boiling
point of water, preserving the catalyst activity and driving the
reaction to completion.
Applying Reactive Distillation to Biodiesel Synthesis.
Reactive distillation is a valuable process intensication tech-
nique that can be applied successfully to the manufacture of
biodiesel, since the reactions leading to the end-product are
controlled by the chemical equilibrium. This is particularly
advantageous in esterication-type processes, when the feed
has a high content in fatty acids. This is the case with waste
fats (cooking oil, yellow grease, tallow, etc.) or with fatty acids
obtained by a hydrolysis prestep, as in a supercritical process.
By combining reaction and separation into a single unit, one
can shift the reaction equilibrium toward the key product (ester)
by continuous removal of byproduct (water), instead of using
an excess of reactant. The secondary reactions (etherication
or dehydration) can be avoided by using a selective solid catalyst
such as sulfated metal oxides. The process based on RD does
not produce waste salt streams.
Figure 6 shows a RD process for FAME manufacturing based
on reactive distillation. The reactive distillation column consists
of a core reactive zone completed by rectifying and stripping
separation sections, whose extent depends on the separation
behavior of the reaction mixture. Since methanol and water are
much more volatile than the ester and acid, these will separate
easily in the top such that no supplementary rectifying zone is
needed. Similarly, no stripping zone is necessary. In this way,
the reactive zone can cover practically the whole column.
The operating pressure deserves particular attention. This
determines the reaction temperature, which should be compatible
with the catalytic activity. For mixed oxides, the convenient
temperature is in the range 130-150 C when methanol is used
as the alcohol. This corresponds to a pressure of 6-10 bar. In
addition, the reboiler temperature should not exceed the limit
imposed by the thermostability of the product, usually 200 C.
This constraint can be fullled by letting a certain amount of
methanol in the bottoms, which is further recovered and recycled
by a simple ash.
The top stream from the RDC contains water and alcohol in
a proportion dictated by the reux policy. When methanol is
used, Omota et al.
42,43
demonstrated that a large excess is not
necessary, the column being operated optimally at a low alcohol
reux, or even at reux with fatty acid when water can be
separated directly by decanting. In this case, the column operates
rather as a reactive absorber. This result was conrmed later
experimentally.
23
However, the operation should be safer with
a small excess of alcohol, 1020%, such to cope with feed
variability. The excess of methanol can be recovered by simple
stripping with vapor distillate, which is recycled to the bottom
of the RDC column.
When using ethanol and propanols, the formation of water
azeotrope is inevitable. This aspect can be handled conveniently
by using a suitable entrainer, such as cyclohexane. Note that
water can be separated directly by decanting in the reux drum
when using a high-boiler alcohol, such as 2-ethylhexanol. The
solubility of alcohol in water is so small that quantitative
separation can be achieved.
24
This property can be advanta-
geously exploited by so-called dual esterication, with light and
heavy alcohol. Employing methanol and 2-ethylhexanol allows
the quantitative removal of water on top. The column can be
operated near the atmospheric pressure while keeping the
temperature prole at 130 C. Since 2-ethylhexanol is typically
a waste alcohol from the manufacturing of butanols, this process
makes sense from an economic viewpoint.
Reactive distillation can also be used in the esterication
stage. However, there is a fundamental difference with the
esterication reaction, namely, the fact that both products, fatty
ester and glycerol, are heavies and cannot be separated by
distillation. In this case, shifting equilibrium can be ensured
only by using a large alcohol excess by internal reux, 2 times
or more the necessary stoichiometric amount. In addition, the
use of a reactive distillation offers a good environment for heat
integration: the reboiler can be driven with energy from process
waste, while the condenser can recover it as hot stream or by
raising steam, to be used for driving other operations. Note that
using a tubular reactor with external methanol recycle is a good
alternative too. Actually, two reactors with intermediate glycerol
separation are needed to shift the equilibrium to the desired
product distribution, as a low content in monoglycerides. As
result, when the feed consists of triglyceride oil containing a
high proportion of free fatty acids, a good reaction setup is a
reactive distillation column for esterication followed by two
tubular reactors for transesterication.
Conceptual Process Design and Process Simulations. To
complement the experimental studies, we carried out a detailed
rigorous simulation study of the biodiesel production process
under reactive distillation conditions. By combining reaction
and separation into a RD unit, one can shift the reaction
equilibrium toward products by continuous removal of reac-
tion products, instead of using an excess of reactant.
23,42,43
The
secondary reactions (etherication or dehydration) can be
avoided by using a selective solid catalyst such as sulfated metal
oxides. The process based on RD has no additional separation
steps and produces no waste salt streams, as water is the only
byproduct (Figure 6). The process simulations were performed
using the AspenTech AspenOne 2004 engineering suite.
26
Analysis of physicochemical properties shows high boiling
points for acid and esters which both will go to the bottom of
the RD column (Table 4). The conversion of fatty acid to ester
should be complete, since they cannot be separated conveniently
by distillation. The UNIQUAC property model was used
(UNIFAC (Dortmund modied) can also be successfully ap-
plied
23
).
Fresh reactants were fed to the reactive distillation column
in a stoichiometric ratio. The RD column has 14 stages and
is operated at a very low reux ratio (0.010.1 kg/kg). A
higher reux ratio is detrimental, as it brings back water
byproduct into the column, hence decreasing the fatty acid
Figure 6. Reaction pathways and possible products (left). FAME
production by esterication with methanol in a reactive distillation
column (right).
602 Energy & Fuels, Vol. 22, No. 1, 2008 Kiss et al.
conversion by shifting the equilibrium back to reactants. To
reduce the amount of dodecanoic acid in the nal product,
the fatty acid is fed above and methanol below the reactive
zone (mid 8 stages), respectively. By allowing about 10%
alcohol in the bottom stream, the reboiler temperature in the
RD column can be maintained around 200 C. When an
excess of alcohol is used, the maximum reaction rate is
located at the top of the column, with total acid conversion
in the bottom but partial conversion of alcohol in the top.
For the optimal reux rate and stoichiometric reactant ratio,
the maximum reaction rate is located in the center of the
column, providing complete conversion of both reactants at
the ends of the column. The composition and temperature
proles in the reactive distillation column are shown in Figure
7. Note that the reactants are fed at the same temperature as
on the feed reactive stage.
The residence time in the column is 10 min, much less than
the retention times of 6090 min in the conventional processes
reported.
5759
Depending on the reux ratio and total production
rate of FAME, the energy requirement for such a process is
150 kcal/kg of fatty ester. At a catalyst loading of 15%, the
production of fatty ester can exceed 21.4 kg of ester kg of
catalyst
-1
h
-1
, or 3250 kg of ester/h m
3
reactor. The column
diameter is only 0.1 m for a pilot plant producing 1880 tons/
year of fatty ester.
4. Discussion
The process we propose has several advantages over con-
ventional biodiesel production processes: (1) short reaction time
and high unit productivity, (2) no excess alcohol requirements,
(3) lower capital costs due to the small size of RDC and no
need for additional separation units, and (4) no neutralization
and separation of the catalyst, as solid acids are used instead of
homogeneous catalysts. Further investigations on the process
efciency and in-depth economic analysis of the RD system
are required in order to fully establish its impact on the biodiesel
production.
In contrast to conventional reactors, the RD column has some
hydraulic constrains that limit the maximum residence time
(2060 min) of the liquid phase. That means not only increased
production rates, but also that a highly active catalyst is
required.
42,43
Adding an entrainer to the system leads to reduced
catalyst loading.
60
The reaction mechanism for the heterogeneous acid-catalyzed
esterication was reported to be similar to the homogeneously
catalyzed one.
61
However, there is a major difference concerning
the relationship between the surface hydrophobicity and the
catalysts activity.
18
Reaction pockets are created inside a
hydrophobic environment, where the fatty acid molecules can
be absorbed and react further. Hydrophobic surfaces are
preferred to avoid the covering with water of the solid acid
surface which prevents the adsorption of organic materials.
Metal oxide catalysts have large pores (Table 3) and therefore
do not limit the diffusion of the fatty acid molecules. They do
not leach under the reaction conditions and suppress secondary
reactions such as etherication or dehydration. The sulfated
metal oxides are good catalysts, with strong acid sites and high
thermal stability.
Typical raw materials of choice are palm oil in Brazil and
Malaysia, sunower oil in France and Italy, and soybean oil in
the U.S. Table 5 lists the most common oil-producing crops.
62
Considering the land required for producing the current energy
demands, biodiesel is not able to completely replace petroleum
fuels. However, it is an excellent complementary fuel, contribut-
ing to a combined strategic approach of using alternative energy
sources.
5. Conclusions
Biodiesel can be produced by esterication of fatty acids
using solid acid catalysts. The activity and selectivity of these
catalysts is determined by the pore size, as well as by the
density of acid sides and the surface hydrophobicity. Catalysts
based on metal oxides such as niobia, zirconia, titania, and
tin oxide proved to be the best candidates. They are active
and selective. The calcination temperature is the key param-
eter in the preparation of these catalysts, as it heavily affects
the density of acid sites, and surface hydrophobicity. Our
simulations show that biodiesel can be produced by a
sustainable continuous process based on catalytic reactive
distillation. The integrated design shifts the chemical equi-
(57) Darnoko, D.; Cheryan, M. J. Am. Oil Chem. Soc. 2000, 77, 1269
1272.
(58) Noureddini, H.; Harkey, D.; Medikonduru, V. J. Am. Oil Chem.
Soc. 1998, 75, 17751783.
(59) Peterson, C.; Cook, J.; Thompson, J.; Taberski, J. Appl. Eng. Agric.
1999, 18, 511.
(60) Dimian, A. C.; Omota, F.; Bliek, A. Chem. Eng. Process. 2004,
43, 411420.
(61) Koster, R.; van der Linden, B.; Poels, E.; Bliek, A. J. Catal. 2001,
204, 333338.
(62) Tickell, J. From the fryer to the fuel tank: the complete guide to
using Vegetable oil as an alternatiVe fuel, 3rd ed.; Tickell Energy Consulting:
Tallahassee, FL, 2002.
Table 4. Normal Boiling Points of Chemical Species Involved in
the Process
chemical name
chemical
formula
M
w
(g/mol) T
b
(K) T
b
(C)
dodecanoic (lauric) acid C
12
H
24
O
2
200 571 298
methanol CH
4
O 32 338 65
2-ethylhexanol C
8
H
18
O 130 459 186
methyl dodecanoate C
13
H
26
O
2
214 540 267
2-ethylhexyl dodecanoate C
20
H
40
O
2
312 607 334
water H
2
O 18 373 100
Figure 7. Simulated proles in the reactive distillation column (RDC):
liquid composition (left) and temperature and ester generation (right).
Table 5. Oil-Producing Crops
plant latin name kg of oil/hectare
cashew nut Anacardium occidentale 148
soybean Glycine max 375
coffee Coffea arabica 386
sunower Helianthus annuus 800
peanut Arachis hypogaea 890
rapeseed Brassica napus 1000
jojoba Simmondsia chinensis 1528
brazil nut Bertholletia excelsa 2010
coconut Cocos nucifera 2260
palm oil Elaeis guineensis 5000
Biodiesel by Catalytic ReactiVe Distillation Energy & Fuels, Vol. 22, No. 1, 2008 603
librium to completion and preserves the catalyst activity, by
continuously removing the water byproduct. Manufacturing
of biodiesel by reactive distillation as a multifunctional
reactor can be applied to a variety of fatty acids and alcohols,
the actual applications depending on the feedstock at hand.
The process proposed in this work can dramatically improve
the biodiesel synthesis and reduce the number of downstream
steps.
Acknowledgment. We thank Dr. M. C. Mittelmeijer-Hazeleger
and Ing. J. Beckers for technical support.
EF700265Y
604 Energy & Fuels, Vol. 22, No. 1, 2008 Kiss et al.