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Chemical Engineering and Processing 52 (2012) 4754

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Chemical Engineering and Processing:


Process Intensication
journal homepage: www.elsevier.com/locate/cep

Biodiesel process intensication in a very simple microchannel device


E. Santacesaria , M. Di Serio, R. Tesser, R. Turco, M. Tortorelli, V. Russo
Department of Chemistry of the University of Naples Federico II, Complesso Universitario Monte S. Angelo, Via Cintia 4, IT 80126 Naples, Italy

a r t i c l e i n f o a b s t r a c t

Article history: Biodiesel is normally obtained by transesterication of triglycerides with methanol in the presence of an
Received 11 July 2011 alkaline catalyst. The reaction, performed in stirred tank reactors, requires 12 h of reaction time. As the
Received in revised form reactants are immiscible, the reaction rate can be affected by mass transfer limitation. We have recently
24 November 2011
shown, that all methods favoring local micromixing can give place to high performances. At this purpose,
Accepted 2 December 2011
we have recently developed a very simple laboratory device for testing the behavior of the mentioned
Available online 20 December 2011
reaction in microchannels of different sizes. This device is simply a tubular reactor lled with stainless
steel spheres of different diameters. By opportunely changing the spheres diameters it is possible to
Keywords:
Biodiesel
obtain microchannels in a range of 3001000 m. However, in these reactors the void portion of the
Transesterication reactor is low and the productivity per volume is low, too. It is possible to obtain better results in terms
Process intensication of productivity by lling the tubular reactor with stainless steel wool, being in this case the void fraction
Microreactor about 0.9. In this paper, the performances obtained with this type of reactor are reported together with
Static mixer a discussion on the reaction mechanism in view of the future development of a kinetic biphasic model.
Kinetics 2011 Elsevier B.V. All rights reserved.

1. Introduction proposed, therefore, for the process intensication (PI) of two-


phase reactions occurring at liquidliquid interface (e.g. 1-pentene
Biodiesel is normally produced in industry by reacting vegetable epoxidation [14], transesterication reaction [15]). It would be use-
oils with methanol in the presence of a homogeneous catalyst ful for better modeling microreactors, to develop reactor systems
such as NaOH, KOH or related alkoxides, at 3070 C and atmo- able to give a rapid response about the effectiveness of microchan-
spheric pressure. Many papers have been published on the kinetics nels for a given two phase liquidliquid reaction. In a recently
of the transesterication reaction but data reported are often in published paper [16] we proposed the use of a microchannel device
disagreement and in some cases are clearly affected by mass trans- to test the process intensication effects on a reaction. This device
fer limitation [17]. The reagents are immiscible liquids and the was simply a tubular reactor lled with stainless steel spheres of
interphase plays an important role. All the published works report- different sizes in which the smaller spheres (0.39 mm of diam-
ing experimental data are related to batch reactors. In a recently eter) are perfectly allocated in the void volume existing in the
published paper and patent [8,9] we have shown that a very high framework created by the bigger ones (2.5 mm of diameter). In
productivity (2000 kg/(day L)) can be obtained by performing the this way, microchannels with a size of about 300 m were created
transesterication reaction in a continuous corrugated plates heat and the device can be understood, for the uid dynamic behavior
exchanger reactor (CP-HEX reactor) in a range of temperatures and mass transfer performances, as a microreactor. The proposed
between 60 and 100 C. The high performances are due to a very device ideally represents a connection between a traditional tubu-
active local micromixing occurring when high liquid ow rates lar packed bed reactor and the microreactors having in common
were fed in such type of reactors. Starting from these observa- the microchannel structure. However, we have shown, by using
tions, we can conclude that it is possible to strongly enhance the a CP-HEX reactor, that for liquidliquid biphasic reactions like
mass-transfer rate in the methanoloil transesterication reac- methanolsoybean oil transesterication, mass transfer rate can
tion also by using other reactors favoring the development of greatly be increased also by favoring an intense local turbulence.
a high liquidliquid interphase such as, for example, microreac- This effect can also be obtained by using a static mixer system.
tors or static mixers. Microsystems with microchannels of sizes Many different devices of this type have been proposed in the lit-
less than 300 m allow to improve mass, heat and momentum erature [17]. However, is not simple to decide what type of device
transfer very much [1013]. The use of microreactors is often could be more suitable for a given reaction. Again an ideal sys-
tem could be useful for orienting the choice. At this purpose, in
a recent work [18] we proposed the use of three different tubular
Corresponding author. reactors respectively containing spheres of uniform size (2.5 mm of
E-mail addresses: elio.santacesaria@unina.it, elisanta@unina.it (E. Santacesaria). diameter) having microchannels of about 1000 m, spheres of two

0255-2701/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2011.12.001
48 E. Santacesaria et al. / Chemical Engineering and Processing 52 (2012) 4754

Fig. 1. Scheme of the laboratory-scale plant used for the kinetic experiments. The picture indeed shows the stainless steel ribbon wool employed for lling the reactor.

different sizes of respectively 2.5 and 1 mm of diameters having 2.2. Analytical method
microchannels of about 500 m and two different sizes of respec-
tively 2.5 and 0.39 mm of diameters having microchannels of about The FAME (fatty acid methyl esters) yields, were determined
300 m, for studying the methanolsoybean oil transesterication by using 1 H NMR technique (GEMINI 200 Mz), measuring the area
reaction. Surprisingly, in some cases, the performances obtained of the H NMR signal related to methoxylic (A1, single signal at
were so high that none of the kinetic models proposed by the liter- = 3.7 ppm) and methylenic groups (A2, triplet signal = 2.3 ppm),
ature, derived from runs performed in batch conditions, is suitable respectively. The FAME yields can be calculated by using the fol-
to describe the observed kinetic behavior. As mentioned before, lowing equation:
these reactors could be useful as laboratory reactors for orienting  2 A1 
on the choice of the static mixer or for modeling microreactors yieldFAME = 100 (1)
but are not useful for industrial purpose being the productivity, 3 A2
for reactor volume unity, relatively low. However, by lling the
The 1 H NMR spectra were obtained with GEMINI-200 equipment
reactor with stainless steel wool it is possible to obtain a much
in deuterated chloroform [19].
higher void fraction accompanied by an increase of the produc-
In all the cases the conversion values were conrmed by
tivity that renders the reactor interesting for industrial purpose.
gas-chromatographic analysis [UNI 10946:2001], using a gas
The performances obtained with such reactor are reported in this
chromatograph (Perkin-Elmer model Clarus 500), equipped with
paper. A simplied version of a pseudo-homogeneous monopha-
a ame ionization detector (FID), an on-column injector, and
sic kinetic model, proposed in the literature for the description of
employing a FS-HP5 column (10 m X0.32 mm, I.D. 0.1 m lm).
batch runs [5,6] has been used for the description of our continu-
Before analysis, the samples were derivatizated by BSTFA (N,O-bis
ous runs but the obtained results are unsatisfactory. According to
(trimethylsilyl) triuoroacetamide with trimethylchlorosilane). As
us the pseudo-homogeneous mono-phasic kinetic model is unsuit-
internal standards, methyl-heptadecanoate was used for methyl
able to describe the behavior of continuous reactors characterized
ester and 1,2,4 butantriol was used for glycerol. The uid dynamic
by intense micromixing or by the presence of microchannels. For
tests have been performed analyzing the samples by UVvisible
this purpose, a discussion on the nature of the catalyst, the reaction
measurements.
mechanism, the evolution of the composition of the two immisci-
ble phases with the conversion will be reported as starting point
for the development of a biphasic model that will be our next 2.3. Reactor setup and kinetic runs
challenge.
The used reactor is a stainless steel cylindrical tube of 20 cm
length and 12.7 mm (1/2 ) of external diameter with an internal
2. Experimental diameter of 10 mm. The internal void volume of the reactor was
15.7 cm3 . A stainless steel ribbon wool, like the one shown in Fig. 1,
2.1. Reagents has been used for lling the reactor by compressing it as much as
possible. After the lling a void fraction of 0.89 has been directly
Soybean oil used in the runs was purchased in a local food-store measured. The described reactors have then been used to perform
(the fatty acid composition of the used soybean oil, determined the reaction in a laboratory plant schemed in Fig. 1.
by gas chromatographic analysis, was: (%, w/w): palmitic = 11, Kinetic runs have been carried out by feeding to the reactor two
stearic = 4, oleic = 23, linoleic = 56, linolenic = 5, others = 1). All other different liquid ows one of methanol containing the dissolved cat-
employed reagents (when not specied) were supplied by Aldrich alyst (KOH, normally 1 or 2 wt.% with respect to the oil) and another
at the highest level of purity available and were used as received of rened soybean oil. The oil was preheated at the reaction tem-
without further purication. perature, whereas methanol was fed at room temperature.
E. Santacesaria et al. / Chemical Engineering and Processing 52 (2012) 4754 49

2.4. Fluid dynamic characterization tests possible to estimate the ND value from the slope of the curve F(t)
for  = 1, according to the following relationship [20].
The described reactor has been subjected to a uid dynamic
 dF(t)  
characterization with a stimulusresponse step test to evaluate the 1 uL
= (3)
RTD (retention time distribution). Water has been used as owing d(t/tm ) t/tm =1 2 D
medium and cobalt nitrate(II) hexahydrate, having a characteris-
The integrated function F(t) is reported below.
tic pink color, has been used in the test as a tracer. A solution of
  
known concentration (C0 ) of the tracer was sent to the reactor at
1 1 uL 1 (t/tm )
time = 0; from this time samples have been periodically withdrawn F(t) = 1 erf
(4)
from the outgoing ow in order to record the step response. Then, 2 2 D t/tm
the samples have been analyzed by an UVvisible spectrophotome-
ter, monitoring the absorbance of cobalt nitrate at 511 nm. The tests where erf is the error function dened as follows:
 x
have been repeated at different ow rates. An HPLC pump was used 2 2
for regulating the cobalt solution ow rate. erf(x) = ey dy (5)
 0

For the mentioned reactor ND numbers resulted respectively 0.036


3. Results and discussion and 0.042, in correspondence of 5.6 and 8.3 cm3 /min of liquid ow.
The literature ndings conrm that the ND values estimated are
3.1. Results of the uid dynamic tests very close to the ones expected for the static mixers 1/ND = Pe = 70L
[21] (where L stands for the length of the reactor expressed in
By reading the ex of the sigmoidal function that best t the meters): in this way, it is possible to calculate a ND = 0.07 for a
experimental data it was possible to determine the mean residence reactor of 0.2 m length. It is important to underline that in the
time and from these values, to estimate the empty volume of the described systems the local turbulence is not given mainly by the
reactor. The value obtained was 13.93 cm3 conrming a void frac- ow-rate, but by the static elements that guarantee an intimate
tion of 0.89. The dead volume at the exit of the reactor was 0.32 cm3 mixing between the two immiscible phases because the formation
that is small with respect to the reactor void volume. The results of eddies.
of this characterization are shown in Fig. 2, where the dimen-
sionless tracer concentrations F(C/C0 ), are plotted as a function of 3.2. Methanolsoybean oil transesterication runs
the dimensionless time  (t/tm , where tm is the mean residence
time) for two different volumetric ow rates of respectively 5.6 The typical experimental conditions of most of the runs per-
and 8.3 cm3 /min. C0 is the inlet solution concentration and C is the formed, using the reactor described in the previous sections, are
outlet measured concentration. molar ratio methanol/soybean oil = 6:1 considering for soybean oil
Then, the uid dynamic experimental data can be treated by an average molecular weight of 885 g/mol, a KOH catalyst concen-
mathematical regression analysis using a single parameter func- tration of 1 or 2 wt.% referred to the oil and a temperature of 60 C.
tion; the parameter is known as the axial dispersion number (ND ), To examine the effect of the presence of a packed bed, a rst run
normally indicated as the reciprocal of the Peclet number (Pe), was performed with the empty reactor using a total ow rate of
dened by the following expression. 8.33 cm3 /min. The esters yield obtained in this case was 3%. This
value can be compared with the much higher values obtained in
1 D the presence of a packed bed.
ND = = (2)
Pe uL Some experimental runs were performed xing the tempera-
ture (60 C) and the catalyst concentration (1 wt.% KOH referred to
where u is the uid linear velocity (m/s) calculated from the volu- the oil) in order to study the effect of the residence time on the
metric ow rate and the section of the empty reactor, D is the axial methylester yield (entries 113 of Table 1). It must be observed,
dispersion coefcient (m2 /s) and L the length of reactor (m). It is rst of all, that the presence of the packed bed gives place to a very
strong increase of the conversion due to the static mixing effect.
Then, it must be pointed out that, by increasing the residence time,
the yield in methylesters increases until a maximum is reached, a
further increase of the residence time gives place to a decrease of
1.0
D/uL=0 the yield. This behavior can be better appreciated by plotting the
yields as a function of the residence time, as reported in Fig. 3. The
0.8 low value of the yield, obtained at the highest residence time, is
D/uL=0.042
D/uL=0.036 very probably due to a less active micromixing having as a conse-
3
quence the reduction of the interfacial area and the effect of the
F(t)=C/C0

0.6 5.6 cm /min mass transfer limitations, while, the decrease of the yield observed
3
8.3 cm /min at the lowest residence time seems the normal behavior of a sys-
0.4 tem working in a chemical regime. Several runs have then been
performed by using 2% of KOH catalyst (entries 1418 of Table 1).
The corresponding yields are again reported in Fig. 3. It is interesting
0.2 to observe that the increase of the catalyst amount produces a very
high yields conrming our previous observations by using other
different static mixers [18] in which the phenomenon was much
0.0
more pronounced with respect to the system studied in this work.
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
Such large increase in the yields, by increasing the amount of used
=t/tm
catalyst, was unexpected and as it will be seen later, this behavior
Fig. 2. F function plot against the dimensionless time for the reactor uid-dynamic
cannot be described by using a monophasic pseudo-homogeneous
characterization. kinetic model, normally, adopted in the literature for describing
50 E. Santacesaria et al. / Chemical Engineering and Processing 52 (2012) 4754

Table 1
List of the experimental runs performed at 60 C with 1 wt.% (referred to the oil) of KOH catalyst (entries 113) and 2 wt.% of catalyst (entries 1418).

Run Qoil (cm3 /min) QMeOH (cm3 /min) Qtot (cm3 /min) Residence time (min) Yields (%)

1 35.77 9.227 45.00 0.31 39.80


2 31.00 7.997 39.00 0.36 57.08
3 25.04 6.459 31.50 0.44 81.88
4 14.31 3.690 18.00 0.77 80.31
5 9.80 2.526 12.33 1.13 76.83
6 6.60 1.730 8.33 1.67 83.24
7 5.50 1.400 6.90 2.02 80.43
8 4.40 1.150 5.55 2.51 83.82
9 2.40 0.615 3.02 4.62 84.08
10 3.69 0.951 4.64 3.00 76.90
11 2.77 0.714 3.48 4.00 74.91
12 2.21 0.571 2.78 5.01 73.64
13 1.10 0.287 1.39 10.04 67.10
14 11.070 2.860 13.930 1.00 81.02
15 5.537 1.428 6.965 2.00 88.63
16 3.698 0.951 4.649 3.00 97.05
17 2.768 0.714 3.482 4.00 93.71
18 2.210 0.571 2.781 5.01 85.21

batch runs. The scattering of the experimental data reported in order to describe the evolution with time of reagents and products,
Fig. 3 is probably due to small differences in the pre-xed ow rates in a batch reactor, three kinetic expressions, containing also the
having this factor a strong inuence on the methyl ester yields. equilibrium terms, are necessary, that is, we need to know three
kinetic parameters and related activation energies, three equi-
3.3. Kinetic interpretation of the runs librium constants and related enthalpy change parameters. The
kinetic laws suggested by the literature, for the three mentioned
The experimental data collected have been interpreted by reactions, are pseudo-second order laws with equilibrium. This
adopting the monophasic kinetic model already published in the approach, works reasonably well to describe the runs performed in
literature. This model had been elaborated on the basis of runs batch conditions, for which many experimental points as a function
performed in batch laboratory reactors by considering, as a rst of time are available, but the extrapolation of the same kinetics and
approximation, a pseudo-homogeneous reaction system in kinetic parameters to the description of few experimental data, obtained
regime [2,5,6]. Therefore, the concentration of each reagent and cat- in a continuous reactor, is problematic for the large number of
alyst has been calculated considering the total volume of the two parameters that must be introduced. For this reason, we have devel-
phases. As known, the reaction occurs in three different consecutive oped a simplied mathematical model [18] with the aim to reduce
steps, according to scheme (6): signicantly the number of kinetic parameters but describing the
experimental data, reported in literature, with a satisfactory accu-
1) T + A D + E racy. Such model has then been applied to the experimental data
2) D + A M + E (6) collected in the previous section of this paper. This mathematical
3) M + A G + E model takes into account the simplied reaction scheme (6), where
ki (i = 1, 2 and 3) and Keq are respectively the kinetic and equilibrium
where T represents the triglycerides, D the diglycerides, M the
constants for the three reactions in series.
monoglycerides, G glycerol, A methanol and E the methylesters. In
The mathematical model is based on the following assumptions:

2% KOH
- The system is considered as a pseudo-homogeneous (single
100
phase).
90 - The equilibrium constant is assumed the same for all the three
reactive steps independently of the temperature being the reac-
80
tion approximately athermic.
70 - A linear correlation has been assumed between the three different
kinetic constants, that is: k2 = 2k1 and k3 = 3k1 . This assumption
60 is reasonable, considering the reaction mechanism, that is, when
1% KOH
Yield (%)

50 the catalyst CH3 O attacks an ester group of the triglyceride, its


relative concentration, referred to the number of available esters,
40 is half than in the presence of a diglyceride molecule and one
third in the presence of a monoglyceride. It is now possible to
30
write the reaction rate expressions for each step, expressed in
20 [mol L1 min1 ], as it follows:
KOH 1% wt
10 KOH 2% wt
 
0 1
r1 = k1 [Cat][T][A] [Cat][D][E] (7)
0 1 2 3 4 5 6 7 8 9 10 11 Keq
Residence time (minutes)
 
Fig. 3. Performances of the reactor lled with ribbon steel wool, at 60 C, in the 1
presence of 1% or 2% of KOH catalyst. Dashed lines correspond to the simulation of r2 = 2k1 [Cat][D][A] [Cat][M][E] (8)
Keq
the runs with the monophasic kinetic model [5,6,18].
E. Santacesaria et al. / Chemical Engineering and Processing 52 (2012) 4754 51

Table 2 d[G] r3
Kinetic and equilibrium parameters obtained by mathematical regression on the = (19)
dV Q
experimental data, performed in batch conditions, reported in the literature [5,6].

Run T ( C) KOH (wt.%) Oil k1 (L2 /(mol2 min)) Keq d[E] r1 + r2 + r3


= (20)
1 25 1 Brassica 1.02 3.86 dV Q
2 35 0.5 Sunower 2.69 3.31
3 65 1 Sunower 9.5 3.50
d[A] r1 r2 r3
= (21)
dV Q
 
1
r3 = 3k1 [Cat][M][A] [Cat][G][E] (9) Q is the overall volumetric ow rate given by the sum of the
Keq
volumetric ow rates of both oil and methanol sent to the reac-
The mass balance equations for each component, expressed in tor. Setting the values of the reactor inlet concentrations, the
[mol L1 min1 ], for a batch reaction system, can be written as fol- kinetic runs performed in the reactor can be simulated with the
lows: developed kinetic model and related parameters by using the soft-
d[T] ware Berkeley-Madonna v.8.0 setting a fourth-order RungeKutta
= r1 (10) algorithm in order to integrate the differential equations. The sim-
dt
ulation results are reported in Fig. 3. From this gure it is possible
d[D] to see that the monophasic pseudo-homogeneous model is not able
= r1 r2 (11)
dt to describe continuous runs, conrming some previous observation
d[M] made by using the same reactor lled with stainless steel spheres
= r2 r3 (12) of different sizes. In some cases the obtained yields are higher than
dt
the one foreseen by the model, in other cases are lower probably
d[G]
= r3 (13) for the intervention of mass transfer limitations. Another important
dt observation is that simply by changing the amount of catalyst from
d[E] 1 to 2% the apparent equilibrium value changes very much, from
= r1 + r2 + r3 (14)
dt about 82 to 97%. The change of the apparent equilibrium value with
the amount of catalyst has been observed also in the batch runs [5,6]
d[A]
= r1 r2 r3 (15) with the same trend, that is, the equilibrium value increases with
dt
the catalyst amount. This means that other more complex equilib-
In order to test the goodness of the model described above, some ria both physical and chemical are involved in the reaction system
experimental data reported by the literature have been used for not contemplated by the monophasic kinetic model. Two aspects
determining, by regression the kinetic parameters of the simplied must be considered for a correct interpretation of the experimen-
model [5,6]. The kinetic runs considered according to the authors tal data: the reaction mechanism and the partition, or distribution
would not be limited by mass-transfer phenomena. The best kinetic coefcients, between the polar and apolar phases of reactants, cat-
parameters obtained by regression are reported in Table 2. alytic species and products. By using ChemCAD 6.2 software with
This monophasic pseudo-homogeneous model reproduces sat- UNIFAC LLE model [22] it is possible to estimate the composition
isfactorily all the kinetic runs performed in batch conditions by of the biphasic system as a function of the conversion (see Fig. 4).
Aracil et al. [5,6] as shown in a previous work [18]. The kinetic First of all, an important aspect is that the volume ratio between
parameters are independent of the type of used oil (Brassica, Sun- the polar and apolar phase dramatically decreases by increasing the
ower) and from the runs made on Brassica and Sunower we conversion from about 0.17 to a minimum of 0.13 at 0.5 of conver-
can obtain one value of the activation energy for all the three sion, then increases at 0.16 but changing completely the nature of
occurring reactions. By concluding a model with only 3 param- both the polar and apolar phase (see compositions in Fig. 4). All
eters is equivalent, for the accuracy in the simulation of all the these changes occur inside the described continuous tubular reac-
batch runs, to the model proposed in the literature containing 12 tors from the inlet to the outlet. The monophasic simplied kinetics
parameters. In this simplied model, only one activation energy has been assumed as a rst attempt to evaluate the evolution of the
has been considered for the three reactions of the scheme (6). This overall composition with the conversion, then the partition of the
activation energy, obtained by mathematical regression analysis, different species has been evaluated by using ChemCAD 6.2 soft-
resulted 10.67 1.94 kcal/mol, while, the best value for the pre- ware, setting the UNIFAC LLE model [22], to build the diagram of
exponential factor is ln(k0 ) = 18.2 3.1 (k0 = L2 /(mol2 min)) related Fig. 4. Then, it is interesting to observe in Fig. 4 that monoglyc-
to the rst reaction of scheme (6). As mentioned before a correla- erides are partitioned between the two phases and reach, in the
tion has been imposed between the kinetic constants of the three polar phase, a maximum molar concentration of 1% but in corre-
reactions of scheme (6) so contributing to reduce the number of spondence there is not a signicant production of glycerol. This
kinetic parameters. At last, by mathematical regression analysis means that very probably the catalyst, initially potassium methox-
also the equilibrium constant has been determined and resulted ide, is mainly distributed in the form of mono and diglyceroxide and
Keq = 3.52 0.05. that the successive transesterication steps occur preeminently in
The kinetic parameters can then be used to elaborate the exper- the oil phase. This explain why the reaction rate rapidly slow down
imental data obtained in our continuous reactor by writing the at high conversion, because, the catalyst come back as glyceroxide
following mass balance equations: anion in the polar phase. Initially, we have a polar phase contain-
d[T] r1 ing methanol and very few amount of dissolved triglycerides. KOH
= (16) dissolved in methanol gives the reaction:
dV Q
d[D] r1 r2
= (17) K+ OH + CH3 OH K+ CH3 O + H2 O (22)
dV Q
d[M] r2 r3 Then, methoxide anion CH3 O reacts with triglycerides in the polar
= (18)
dV Q phase or more probably at the interphase giving place to methyl
52 E. Santacesaria et al. / Chemical Engineering and Processing 52 (2012) 4754

0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
1,0 0,025
0,9
0,8 Polar Phase 0,020Left y axis
0,7 Methanol
0,6 0,015 Glycerol
0,5
Component molar fraction (X)i

0,4 0,010
Right y axis
0,3 Triglycerides
0,2 0,005 Methylesters
0,1 Monoglycerides
0,0 0,000 Diglycerides
1,0 0,05
0,9
0,8
Apolar Phase 0,04 Left y axis
0,7 Triglycerides
0,6 0,03 Methylesters
0,5
Diglycerides
0,4 0,02
0,3 Right y axis
0,2 0,01 Glycerol
0,1 Methanol
0,0 0,00 Monoglycerides
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
Conversion Degree

Fig. 4. Plot of molar fractions against the conversion degree related to the triglycerides for each component involved in the transesterication reaction. The upper section of
the diagram is related to the polar phase, the downer to theapolar phase. The right axis of both the section is related to: methanol and glycerol for the polar phase, triglycerides
and methylesters for the apolar phase. The simulation has been performed by using ChemCAD 6.2 software, setting the UNIFAC LLE model [22].

ester and diglyceroxide anion [23] according to the following reac-


tion:

(23)

Diglyceroxide anion migrates in the apolar phase and promotes


further transesterication steps. As suggested by Dijkstra et al. [23],
diglyceroxide anion reacts with triglyceride molecules giving an
enolate intermediate and a molecule of diglyceride:

(24)

Then the enolate reacts with methanol dissolved in the apolar phase
to give methylester and a new diglyceroxide anion:

(25)

With the same mechanism is formed the monoglyceroxide anion,


glycerol and glyceroxide in successive steps. Following reaction
(22) a simplied scheme of the reaction mechanism is reported
below: M + D E
D +M (32)

CH3 O + T D + E (26)

M + M E
M+M (33)
D +T E
T +D (27)

E
M + CH3 OH G + E (34)
E
T + CH3 OH D + E (28)

D + D E G + T E
T +G (35)
D +D (29)

E G + D E
D +G (36)
D + CH3 OH M + E (30)

M + T E
T +M (31) G + M E
M+G (37)
E. Santacesaria et al. / Chemical Engineering and Processing 52 (2012) 4754 53

where T, triglyceride; D, diglyceride; M, monoglyceride; E, methyl the reacting oil phase. This explains the difference in the activity
ester; D , diglyceroxide anion; M , monoglyceroxide anion; G , observed by using different devices (stirred batch reactors, static
glyceroxide anion; E
T , enolate form of triglyceride; ED , enolate form mixers reactors, structured reactors etc.). It is clear that a more
of diglyceride; E M , enolate form of monoglyceride. We have 13 sophisticated biphasic model is required to describe the behav-
reactions involving the catalyst with 8 different anionic species. ior of continuous reactors characterized by the presence of local
Methoxide and glyceroxide are conned in the polar phase, while micromixing or microchannels and this will be our next research
the other species are mainly dissolved in the apolar phase. An challenge.
increase of the catalyst concentration from 1 to 2% of KOH strongly
affects the equilibrium of the anions population and the con-
Acknowledgements
version dramatically increased as a consequence. This aspect has
been observed also in batch runs, that is, the plateau of the yield
Thanks are due to EC VII Framework Programme CP-IP 228853-
increases by increasing the amount of used catalyst [5,6]. In con-
2 COPIRIDE and to MIPAF (Italian Ministry of Agricultural, Food
clusion, many different experimental observations need to be more
and Forest Policies) Project AGROPROM New technologies for
clearly explained, in particular the strong increase of the conversion
the production of biodiesel from waste oil and fats sources D.M.
observed by using: (i) an inert lling material of opportune shape
246/2007 (23/10/2007) and 16912/7303/10 (23/7/2010) for the
and size or other static mixer systems [8,9,18,24,25]; (ii) microreac-
nancial support.
tors or other devices promoting biodiesel synthesis intensication
[24,2629]; and (iii) doubling the amount of used catalyst. As a mat-
ter of fact, while, in a well mixed batch reactor a nearly complete Appendix A. List of symbols
conversion, apparently in chemical regime, is obtained in about
10 min, by using opportune static mixers [8,9,18,24,25], microre-
actors [24,26,27] or other devices [24,28,29] the same result can be A1 methoxylic groups single signal at = 3.7 ppm
achieved in few seconds. This behavior suggests the intervention A2 methylenic groups triplet signal = 2.3 ppm
of a chemical reaction of the methoxide anions with triglycerides D axial dispersion coefcient (m2 /s)
initially occurring at the interface followed by the successive reac- d diameter (m)
tion occurring in the oil phase in which di and mono-glycerolates F dimensionless tracer concentration (C/C0 ) where C and C0
anions acting as catalyst without problem of mass transfer. The are respectively the actual and the initial concentrations
initial mentioned reaction (26) depends on the interfacial area and Keq equilibrium constant
would have as limit the surface area of two contacting liquid mono- ki kinetic constant
layers. This picture would explain the apparent contradiction of the L reactors length (m)
kinetic runs, performed in batch conditions, that seem not affected ND dispersion number
by mass transfer limitation, because, increasing the stirring rate a Pe Peclet number, dened as the inverse of the dispersion
plateau in the reaction rate is obtained. This simply means that by number
increasing the stirring rate is favored the birth of new smaller drops Q overall volumetric ow rate (cm3 /min)
by breaking but also the formation of new bigger drops by collision. Rep particles Reynolds number
In this case, it is not the mass transfer that limits the reaction rate ri reaction rate (mol L1 min1 )
but the kinetic of reaction (26) dependent on the interfacial area. ui axial velocity (m/s)
In order to give a quantitative description of all the described sys- A methanol
tems it is necessary to develop a new more reliable biphasic kinetic Cat catalyst
model based on the mechanism reported above. The development D diglycerides
of such a biphasic model will be the subject of our next work in the E methylesters
eld. G glycerol
M monoglycerides
T triglycerides
4. Conclusions void fraction
 viscosity (Pa s)
We have shown that a tubular reactor lled with stainless steel  density (kg/m3 )
ribbon wool can usefully be used to obtain very high conversions,  residence time (min)
in a very short residence times, at 60 C, with a methanol/oil ratio
equal to 6 conrming the performances already observed in the
References
literature by using static mixers or microreactors. This reaction
is characterized by the presence of two immiscible liquid reac- [1] B. Freedman, R.O. Buttereld, E.H. Pryde, Transesterication kinetics of soybean
tants and the attempt to describe the obtained performances with oil, J. Am. Oil Chem. Soc. 63 (1986) 13751380.
a pseudo-homogeneous kinetic model derived from the literature [2] H. Noureddini, D. Zhu, Kinetics of transesterication of soybean oil, J. Am. Oil
Chem. Soc. 74 (1997) 14571463.
completely failed. In the presence of an intense local micromix- [3] D. Darnoko, M. Cheryan, Kinetics of palm oil transesterication in a batch reac-
ing or very narrow microchannels the transesterication reaction tor, J. Am. Oil Chem. Soc. 77 (2000) 12631267.
rates are much faster than the ones predicted by the mentioned [4] K. Komers, F. Skopal, R. Stloukal, J. Machek, Kinetics and mechanism of the
KOH-catalyzed methanolysis of rapeseed oil for biodiesel production, Eur. J.
kinetic model. We attributed this behavior to the development of a Lipid Sci. Technol. 104 (2002) 728737.
very high interfacial area affecting the reaction between methox- [5] G. Vicente, M. Martinez, J. Aracil, A. Esteban, Kinetics of sunower oil methanol-
ide anion and triglycerides molecules, because, this reaction very ysis, Ind. Eng. Chem. Res. 44 (2005) 54475454.
[6] G. Vicente, M. Martinez, J. Aracil, Kinetics of Brassica carinata oil methanolysis,
probably occurs at the liquidliquid interface. The true catalyst is
Energy Fuels 20 (2006) 17221726.
formed in situ being a mixture of di and mono-glycerolates. This [7] O.S. Stamenkovic, Z.B. Todorovic, M.L. Lazic, V.B. Veljkovic, D.U. Skal, Kinetics of
means that by increasing the initial interface area the methoxide sunower oil methanolysis at low temperatures, Bioresour. Technol. 99 (2008)
disappearing rate increases, too, and the limit to this rate corre- 11311140.
[8] E. Santacesaria, M. Di Serio, R. Tesser, L. Casale, D. Verde, R. Turco, A. Bertola,
sponds to the surface contact of two liquid monolayers. The mass Use of a corrugated plates heat exchanger reactor for obtaining biodiesel with
transfer limitation is related only to the methanol demand to feed very high productivity, Energy Fuels 23 (2009) 52065212.
54 E. Santacesaria et al. / Chemical Engineering and Processing 52 (2012) 4754

[9] E. Santacesaria, M. Di Serio, R. Tesser, R. Turco, D. Verde, L. Casale, Reactor for [19] G. Gelbard, O. Bres, R.M. Vargas, F. Vielfaure, U.F. Schuchardt, 1 H nuclear mag-
immiscible liquid reagents, PCT application assigned to MYTHEN SpA Co WO netic resonance determination of the yield of the transesterication of rapeseed
2010/073216. oil with methanol, J. Am. Oil Chem. Soc. 72 (1995) 12391241.
[10] H. Lowe, W. Ehrfeld, State-of-the-art in microreaction technology: con- [20] C.G. Hill, An Introduction to Chemical Engineering Kinetic and Reactor Design,
cepts, manufacturing and applications, Electrochim. Acta 44 (1999) John Wiley & Sons, 1977, 404 pp.
36793689. [21] E.B. Nauman, Chemical Reactor Design, Optimization, and Scaleup, McGraw-
[11] V. Hessel, S. Hardt, H. Lowe, Chemical Micro Process Engineering, Wiley-VCH, Hill, 2001.
Weinheim, Germany, 2004. [22] Chemical Process Simulator Chem CAD 6.2, by Chemstations (2009).
[12] V. Hessel, A. Renken, J.T. Shouten, J. Micro, Process Engineering, Wiley-VCH, [23] A.J. Dijkstra, E.R. Toke, P. Kolonits, K. Recseg, K. Kovar, L. Poppe, The base-
Weinheim, Germany, 2009. catalyzed, low-temperature interesterication mechanism revisited, Eur. J.
[13] Catalogue Chemical Process Technology, Institute for Mikrotechnik (IMM), Lipid Sci. Technol. 107 (2005) 912921.
5/2009. [24] Z. Qiu, L. Zhao, L. Weatherley, Process intensication technologies in continuous
[14] Y.S.S. Wan, J.L.H. Chau, K.L. Yeung, A. Gavriilidis, 1-Pentene epoxidation in cat- biodiesel production, Chem. Eng. Process. 49 (2010) 323330.
alytic microfabricated reactors, J. Catal. 223 (2004) 241249. [25] X. Yu, Z. Wen, Y. Lin, S.-T. Tu, Z. Wang, J. Yan, Intensication of biodiesel syn-
[15] G.N. Jovanic, B.K. Paul, J. Parker, A. Al-Dhubabian, Microreac- thesis using metal foam reactors, Fuel 89 (2010) 34503456.
tor process for making biodiesel, PCT No. WO2007142983, Dec. [26] J. Sun, J. Ju, L. Ji, L. Zhang, N. Xu, Synthesis of biodiesel in capillary microreactors,
13, 2007. Ind. Eng. Chem. Res. 47 (5) (2008) 13981403.
[16] E. Santacesaria, R. Tesser, M. Di Serio, V. Russo, R. Turco, A new simple [27] Z. Wen, X. Yu, S.-T. Tu, J. Yan, E. Dahlquist, Intensication of biodiesel syn-
microchannel device to test process intensication, Ind. Eng. Chem. Res. 50 thesis using zigzag micro-channel reactors, Bioresour. Technol. 100 (2009)
(5) (2011) 25692575. 30543060.
[17] L. Kiwi-Minsker, A. Renken, Microstructured reactors for catalytic reactions, [28] C. Laeur, H. Bouknight Jr., H. Bouknight Sr., System for creating a biofuel, US
Catal. Today 110 (2005) 214. 2008/7,452,515 B1.
[18] E. Santacesaria, M. Di Serio, R. Tesser, M. Tortorelli, R. Turco, V. Russo, A simple [29] M.B. Boucher, C. Weed, N.E. Leadbeater, B.A. Wilhite, J.D. Stuart, R.S. Parnas,
device to test biodiesel process intensication, Chem. Eng. Process.: Process Pilot scale two-phase continuous ow biodiesel production via novel laminar
Intens. (2011), doi:10.1016/j.cep.2011.05.023. ow reactor-separator, Energy Fuels 23 (2009) 27502756.