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Energy xxx (2014) 1e15

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Energy
journal homepage: www.elsevier.com/locate/energy

Process intensification in biodiesel production with energy reduction


by pinch analysis
Valentin Pleşu b, Joan Subirana Puigcasas a, Guillem Benet Surroca a, Jordi Bonet a, b,
Alexandra E. Bonet Ruiz a, b, *, Alexandru Tuluc b, Joan Llorens a
a
University of Barcelona, Department of Chemical Engineering, 1, Martí i Franqu
es Street, E-08028 Barcelona, Spain
b
University POLITEHNICA of Bucharest, Centre for Technology Transfer in Process Industries (CTTPI), 1, Gh. Polizu Street, RO-011061 Bucharest, Romania

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

Article history: The overall process of biodiesel synthesis from vegetable oil and methanol is spontaneous according to
Received 28 January 2014 Gibbs energy values. Therefore, a classical process scheme consisting of reactor followed by distillation
Received in revised form columns train is grouped in a single hybrid reactive extraction column. Minimum energy consumption is
30 October 2014
calculated using Pinch Analysis, taking into account the minimum energy thermodynamically required
Accepted 5 November 2014
Available online xxx
by process units, e.g. distillation. Process Integration decreases dramatically the minimum energy re-
quirements. Using Pinch Analysis, a useful tool is provided to calculate the minimum energy re-
quirements of alternative processes, the effect of inclusion of the distillation column is to be underlined.
Keywords:
Energy efficiency
The intensified process provides biodiesel and glycerol valorisation with very low energy consumption.
Energy conservation A conceptual design of hybrid reactive extraction column useful for several input oils and fats is pro-
Heat engine posed, considering first pure triglycerides as raw materials and then complex mixtures of triglycerides as
Pinch analysis in real oil compositions.
Short chain fatty acids © 2014 Elsevier Ltd. All rights reserved.
Biodiesel additives

1. Introduction consumption [2]. The transesterification of vegetable oil with


methanol is thermodynamically spontaneous unlike mixing. The
Biodiesel is one of the main products of the European bio- temperature and excess of methanol are more useful to favour
refineries. In European Union, Directive 2009/28/EC require that phase mixing than to displace the reaction equilibrium towards
every year the production of biofuels increases with the aim that by biodiesel formation [3]. This statement is in agreement with
2020, 10% of transportation fuels to be biofuels. Most of the UE car experimental results, when mixing is produced by ultrasounds [4],
engines are diesel and therefore biodiesel plays a crucial role. The or in supercritical conditions [5], or when using reactors that pro-
classical scheme to produce biodiesel including a reactor followed vide an intensive mixing [6]. All these techniques require an excess
by a train of distillation columns to purify the products and to of methanol. Our research team has recently proposed a novel
recover non-reacted methanol, requires a high-energy demand [1]. overall intensified process for triolein transesterification without
Great improvements on biodiesel process are required to compete the need of methanol excess, using a hybrid reactive extraction
with the mature petro-diesel process. Combining in the same unit column that produces pure biodiesel and glycerol [7]. Both re-
reaction and separation as a technique of process intensification actants flow in counter-current, which is more efficient than other
proved to be an effective way to reduce the energy requirements for flow configurations such as cross-flow [8]. Methanol is partially
many processes. Gibbs energy provides a valuable guide to identify soluble in FAME (fatty acid methyl ester) [9], consequently can be
when process intensification is advantageous. In case of biodiesel recovered in the non-reactive section, using glycerol as extractive
synthesis, the overall intensified process does not require energy agent. Without the use of the non-reactive section, an excess of
methanol is required [10]. The capital costs and risks become lower
as the number of process units decreases due to the intensification
[11].
* Corresponding author. University POLITEHNICA of Bucharest, Centre for Tech-
nology Transfer in Process Industries (CTTPI), 1, Gh. Polizu Street, RO-011061
Several oils can be used as raw material for biodiesel: waste
Bucharest, Romania. Tel.: þ40 21 4023916; fax: þ40 21 3185900. vegetable cooking oils [12], algae oil [13], fish oil [14], Sapindus
E-mail address: a_bonet@chim.upb.ro (A.E. Bonet Ruiz). mukorossi kernel oil [15], Canola or Camelina oil [16], Karanja [17],

http://dx.doi.org/10.1016/j.energy.2014.11.013
0360-5442/© 2014 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Pleşu V, et al., Process intensification in biodiesel production with energy reduction by pinch analysis, Energy
(2014), http://dx.doi.org/10.1016/j.energy.2014.11.013
2 V. Pleşu et al. / Energy xxx (2014) 1e15

Table 1 Table 3
Some biodiesel compositions limited by legislation. Mass percent of fatty acid for several kinds of oils.

% wt EN 14214 ASTM D6751-08 FFA Jatropha curcas oil Algae oil

Ester >96.5 Tolypoghrix Spirogyra Spirulina


Water <500 mg/kg <0.05% vol
C 7:0
Impurities <24 mg/kg
C 8:0
Linolenic methyl ester <12
C 14:0 5.8 6.4 0.23
Methanol <0.2 <0.2
C 16:0 14.2 31.8 25.2 46.07
Monoglycerides <0.8
C 16:1 4.7 5.4 1.26
Diglycerides <0.2
C 16:2 2.4 3.8 3.38
Triglycerides <0.2
C 18:0 7.0 2.7 4.5 1.41
Free Glycerine <0.02 <0.02
C 18:1 44.7 23.4 33.3 5.23
Total Glycerine <0.25 <0.24
C 18:2 32.8 8.6 10.8 17.43
C18:3 8.4 0.7 8.87
Others 1.3 12.2 9.9 16.12
rubber seeds oil [18], castor oil [19], etc. Algae oil is considered a
good oil source for biodiesel. To produce 50% of the fuel required in
USA, an agriculture area equivalent to 24% of the USA fields should calculated with the aid of Pinch Analysis is a great stimulus to
be dedicated to palm oil production meanwhile only 3% would be achieve efficient process conceptual designs. Although the meth-
required using microalgae [20]. Algae oil can be collected with low odology of taking into account the distillation column energy re-
energy requirements by CO2 media acidification, low-power pulsed quirements in the Pinch Analysis was well established [25], the
electromagnetic field and static mixer turbulences to break the calculation of the minimum energy requirements of a distillation
membrane and posterior decantation to separate oil, water and column, in a simple way, based on thermodynamic principles, was
cellular membranes [21]. However, palm oil is used as base case in not described until recently [26]. The minimum energy require-
Aspen Plus® documentation providing the composition of palm oil. ment of a system is calculated taking into account the maximum
The catalyst considered in the Aspen Plus® example is homoge- heat exchangeable, fulfilling the second thermodynamic law and
neous. However, important advances are reported in literature considering the distillation columns as heat engines that provide
concerning application of heterogeneous catalysts, e.g. MgeZn separation instead of work. At our knowledge, this approach to
mixed metal oxide catalysts [22], acidic ionic liquid immobilized on calculate the minimum energy requirements of a process has not
poly divinylbenzene [23], hydrotalcite as basic catalyst [24] or sugar been yet reported before in literature. This paper proposes to verify
catalyst [8]. Furthermore, it is evaluated the suitability of the hybrid if classical process integration could compete with the proposed
reactive extraction column for several pure triglycerides, fat and intensified process from energy point of view. In some cases, the
oils. The number of required reactive and non-reactive stages energy savings for process intensification and the process inte-
required for a hybrid extraction column able to treat several kinds gration are reported to be similar, e.g. the energy requirements for
of oils and fats is also determined. The UE and USA legislation methanol and glycerol recovery can be decreased with 27% by using
related to biodiesel composition is taken into account (Table 1). The a divided wall column [27] or 23% with an appropriate heat ex-
effect of presence of free fatty acids, as well as the potential for change network [28].
glycerol revalorization is not the scope of the present study. This Therefore, a comparison between the hybrid reactive extraction
allows providing more details about the biodiesel synthesis. The column and the classical scheme is required to verify the potential
study focuses on aspects such as comparison between classical and of the novel intensified process. The novel process is evaluated
intensified process for biodiesel synthesis from minimum energy using several triglycerides and oils, i.e. to be close to real situations
point of view. from this point of view.
When alternative processes are available, the process with
lower energy requirements, typically, is more efficient and prefer- 2. Material and method
able because it provides lower operation costs, higher energy
conservation and lower environmental impact. However, the en- Biodiesel synthesis from palm oil using a classical process
ergy requirements comparison between processes is not an easy scheme available as example in AspenPlus® version 8.2 is used as
task because it depends on how well it is optimized and how base case, providing palm oil composition (Table 2). Thermody-
process integration is made. The minimum energy consumption namic data and kinetics are ready implemented in AspenPlus® v8.2

Table 2
Palm oil feed composition.

Compound AspenPlus® x
identifier (Mass)

Trioleine OOO 0.0440


Trimirystine MMM 0.0042
Tripalmitine PPP 0.0551
Dipalmitine stearine PPS 0.0106
Dipalmitine oleine PPO 0.2962
Palmitine oleine Stearine POS 0.0490
Dimiristate palmitine MMP 0.0170
Dipalmitine Linoleine PPLI 0.0923
Palmitine Dioleine POO 0.2326
Palmitine Linoleine Oleine PLIO 0.0968
Dioleine Stearine OOS 0.0224
Dioleine Linoleine OOLI 0.0058
Mirystine Palmitine Linoleine MPLI 0.0220
1,3-Dipalmitine PP 0.0520
Fig. 1. Methanol and triglycerides reacting in co-current in a PFR.

Please cite this article in press as: Pleşu V, et al., Process intensification in biodiesel production with energy reduction by pinch analysis, Energy
(2014), http://dx.doi.org/10.1016/j.energy.2014.11.013
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example [29], the thermodynamic model used is UNIFAC-


DORTMUND.
Oils used as raw material provide mixtures of 33 compounds.
The triglycerides of following fatty acids are taken into account:
myristic (C14:0 M), palmitic (C16:0 P), stearic (C18:0 S), oleic (18:1
O) and linoleic (18:2 Li). The nomenclature used in this paper is the
same as the one used in AspenPlus® where “O” means Oleic acid,
“M” e Myristic acid, “P” e Palmitic acid, “Li” e Linoleic acid and “S”
e Stearic acid. The components denominated with three letters are
triglycerides and each letter represents the base fatty acid (for
example OOO is a triglyceride obtained from three oleic acid mol-
ecules, i.e. triolein). In a similar manner, the molecules denomi-
nated with two letters are diglycerides made of two fatty acids
according to the initials specified previously. The molecules like 1-
O are monoglycerides of the fatty acid indicated. Finally, compo-
nents like Methyl-O represent fatty acids methyl esters (FAMEs)
that, in this case, derive from oleic acid. Fig. 3. The increase of number of chain length decrease the biodiesel purity.
The extraction column operates at 60  C. Jatropha curcas oil [30]
and several algae oils compositions [31] are listed (Table 3). The
the influence of pure triglycerides on hybrid extraction column
composition of the different algae oils is quite similar. As a reactive
stages requirements is evaluated. Secondly, the classical process
extraction column is not implemented as an independent unit
scheme consisting of reactor section and separation section,
operation in AspenPlus®, each equilibrium reactive stage is simu-
already implemented in Aspen Plus® for palm oil, is compared to
lated combining a CSTR (continuous stirred tank reactor) and a
proposed process model. Finally, the behaviour of several types of
decanter. The thermodynamic model UNIFAC-DORTMUND is cho-
oils is evaluated, to propose column configurations and operation
sen, as it is proved to be suitable for biodiesel-related LLE (liquid-
conditions able to treat any type of oil.
eliquid equilibrium) () mixtures [32]. The reactive stages are added
one by one until all the input oil is converted to biodiesel. The novel
process is compared to the classical scheme in terms of minimum 3.1. Pure triglycerides transesterification to produce biodiesel
energy requirement, which is calculated using the Pinch Analysis,
as implemented in Sprint® software [33]. This software tool is A stoichiometric mixture of methanol and pure triglycerides of
provided by Centre for Process Integration, The University of 4 kmol/h with 0.25 kmol/h NaOH is feed to a reactor modelled as a
Manchester, as CTTIP is member of the Process Integration Research PFR (plug flow reactor), operated isothermally at 60  C. Although
Consortium. Sprint® software is a complete tool for Pinch analysis, the conversion is somewhat high, no total conversion is achieved
compared with other similar tools, available as commercial or free when methanol and triglycerides flows in co-current (Fig. 1). The
license. Distillation columns are considered as heat engines [26]. results show that some compounds react faster than others do, e.g.
trimyristin. In general, it is observed that the triglycerides reaction
3. Results rate is faster for low number of double bounds and short chain
length. Some other triglycerides, such as the tripalmitin, react
Pure triolein was previously considered as raw material [7] for slower, but reach higher conversions compared to trimyristin. The
the proposed novel process. Process simulations for several pure lowest conversions are provided for triglycerides containing long
triglycerides and mixtures of these triglycerides according to chain saturated fatty acids, e.g. O (oleine). However, some excep-
typical compositions of several oils are provided in this paper. First, tions do not fulfil this general tendency. For instance, OOLi (diolein-

Fig. 2. The increase of number of double bounds decrease the biodiesel purity.

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Fig. 4. Conversion along the column stages depending on the chain length.

linolein) has more double bounds than OOO (triolein), but con- extractive-reactive column of five equilibrium stages. The mass
version slightly higher, according to the kinetic model imple- fraction of methyl esters decreases when the number of double
mented in Aspen Plus®. bounds in the triglyceride increases (Fig. 2). The decrease of this
The reaction mixture splits in two liquid phases, and therefore a mass fraction is much influenced when the number of double
counter-current flow of reactants is feasible. It is commonly bounds is greater than three. When there are more than 16 carbon
accepted that countercurrent flow is usually more efficient than co- atoms in the chain, the ester mass fraction decreases more abruptly
current flow of reactants. The high amount of the reactant at the (Fig. 3). With 5 reactive stages, a practical total conversion is ob-
entrance displaces the other reactant to high conversions at the tained for any triglyceride and the ester mass fraction is above 90%.
exit. Nevertheless, the countercurrent flow pattern means that it The main impurity in the obtained biodiesel is due to the solubility
cannot be treated any more as a PFR but as equilibrium stages. Its of methanol in biodiesel. However, the presence of methanol in
model is closer to the reactive distillation column than to a PFR and biodiesel is not a problem as it is extracted in the non-reactive
liquid phase equilibrium becomes as important as the reaction ki- stages by glycerol.
netics. The feed is stoichiometric and the 1 kmol/h of methanol is In the case of POO (palmitin-diolein) and PPP (tripalmitin),
diluted with a glycerol stream of 1 kmol/h because glycerol is with just one stage, conversions higher than 90% are already
required as extractive agent in the non-reactive section of the attained. The triglycerides conversion and mass fraction variation
proposed process. along the number of stages, depending on carbon chain length, are
The influence of chain length and number of double bonds is presented in Figs. 4 and 5, respectively. According to these results,
determined when the reactants flow in counter-current in an five reactive stages provide enough biodiesel purity, although a

Fig. 5. Methyl esters mass fraction along the column stages depending on the chain length.

Please cite this article in press as: Pleşu V, et al., Process intensification in biodiesel production with energy reduction by pinch analysis, Energy
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Fig. 8. Influence of the extractive agent flow rate on methanol content in final
biodiesel.

the stoichiometric mixture (3 kmol/h methanol: 1 kmol/h MMM


(trimyristin)), the conversion presents a sudden small increase that
is not observed any more at higher ratios of methanol. This fact is
not a problem and a stoichiometric feed mixture is recommended
to be used industrially. However, the process simulation consid-
ering a high number of compounds and reactions requires a small
excess of methanol to assure the mathematical convergence. The
convergence of PPS (dipalmitin-stearin) has not been attained with
stoichiometric methanol. When the ratio is 3.1 kmol/kmol PPS,
mass fraction of methyl esters 99.68% is obtained.
Another important parameter is the glycerol flow rate for
methanol extraction from the final biodiesel in the extraction sec-
Fig. 6. Non-reactive section stages required to decrease the amount of methanol below tion. The minimum mass flow rate percent of glycerol/triglyceride
the specification. for methanol extraction depends on the kind of triglyceride used
(Fig. 8). MMM (trimystirine) requires the highest amount: a flow
rate of 7% of glycerol with respect to biodiesel. The flow rate of
non-reactive extraction section is required to remove methanol extraction glycerol also influences the amount of monoglycerides,
from biodiesel. diglycerides and triglycerides present in biodiesel. There is a glyc-
According to the EN 14214, the methanol content in biodiesel erol flow rate that minimizes the amount of monoglycerides in
must be under 0.2% (Table 1). Fig. 6 shows that with 9 non-reactive biodiesel but there is a wide interval where the legislation is ful-
extraction stages the methanol content in biodiesel decreases to filled (Fig. 9). Therefore, the mass flow rate of glycerol should be
values under the legal limit allowed, independently of the triglyc- between 9 and 13% related to the biodiesel flow rate. In the process
eride used. However, there is not a big difference related to the simulations, the amount of glycerol is fixed to 0.8 kmol glycerol/
number of stages required for each triglyceride, kmol feed oil and therefore the mass percent of glycerol/biodiesel is
e.g.trimyristin requires the lowest number of stages e 8 stages. not constant but within the indicated range. Finally, the mass
Hence, with a hybrid reactive extraction column with 5 reactive fraction of methyl esthers is calculated. Most of the triglycerides
stages and 9 non-reactive stages, a total conversion of methanol reach a mass fraction of methyl esthers higher than required by the
and any triglyceride stoichiometric mixture to glycerol and bio- legislation (Fig. 10). Nevertheless, the palmito-dioleo-glycerol
diesel is attained. An excess of methanol does not influence much
the conversion. This fact is observed for MMM (trimystirine) in
Fig. 7. However, when methanol quantity increases slightly above

Fig. 9. Influence of the extractive agent flow rate on monoglycerides content in final
Fig. 7. Influence of methanol excess on biodiesel purity. biodiesel.

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Fig. 12. Influence of number of double bonds on the energy requirements.

Results previously presented show that the counter-current


flow is able to attain a total reactant conversion to pure biodiesel
Fig. 10. Influence of the extractive agent flow rate on methyl ester fraction in final
biodiesel. and glycerol when an enough number of equilibrium stages are
used, without an excess of methanol. Therefore, the next section
compares the classical scheme for biodiesel production with the
(POO) has not reached enough conversion, although it can be novel proposed scheme.
solved adding reactive stages. The simulations are performed
following the minimum equilibrium stages required but, as the rule 3.2. Palm oil transesterification, comparison between the classical
of thumb for the distillation columns, at least 40% more equilibrium and intensified process
stages would be advisable for an industrial implementation. An
excess of equilibrium stages increases the investment cost, while a The classical process scheme for biodiesel synthesis is composed
deficit of equilibrium stages, once the column is constructed, pro- of a reactor followed by a separation section with several distilla-
duces biodiesel out of specifications that could not be improved tion columns (Fig. 14). The flowrate of palm oil entering the process
only changing the operation variables. The above results show that is of 1.28 kmol/h. The classical scheme has a first distillation column
a reasonable number of equilibrium stages allows the production of to recover part of the non-reacted methanol in high excess. A LLExt
biodiesel, fulfilling the legislation. (liquideliquid extraction) column with water separates glycerol
The kinetic model implemented in AspenPlus® used is based from non-polar phase, the non-polar phase in a second distillation
on the homogeneous NaOH basic catalyst. Although there are column is split in non-reacted oil to be recycled and pure biodiesel.
some other models available in the literature, e.g. heterogeneous, In a third column, glycerol is purified. The distillation columns
the same catalyst has been used for an easiest comparison be- operate at low pressure, e.g. 0.2 bar. There are also several heat
tween the classical process and the intensified process. Fig. 11 exchangers, e.g. HX1 for reactor feed, HX2 for extraction column
shows that the minimum amount of catalyst required for OOO feed and B2 for the oil recycled. A single hybrid reactive extraction
(triolein) is 0.07 kmol/h for feed flow rate 4 kmol/h. In the pro- column can replace the classical scheme (Fig. 15a). As the reactive
cess simulations, a flowrate of 0.25 kmol/h has been used, extraction column is not implemented in AspenPlus®, the flow-
following a ratio similar to the one provided in the classical sheet shown in Fig. 15b is considered to be equivalent. A CSRT
scheme of AspenPlus. (continuous stirred tank) model is considered for reaction section
Assuming the feed at 60  C, energy is required to ensure reaction and a decanter simulates the LiquideLiquid Equilibrium for each
and mixing enthalpies. It is obvious that it is very low. Energy reactive equilibrium stage. The stream GLI (glycerol) þ MeOH
requirement increases for compounds with large number double (methanol) is the internal column stream of the polar phase from
bounds (>4) (Fig. 12) and passes through a minimum around 16 the extractive to the reactive region; the main components are
carbon chain length (Fig. 13). glycerol that dragged methanol from the non-polar phase. The
temperature of the inlet stream GLYCERIN (extractive agent) is
60  C because is a recirculation from the glycerol produced (S2).

Fig. 11. Influence of the catalyst amount. Fig. 13. Influence of chain length on the energy requirements.

Please cite this article in press as: Pleşu V, et al., Process intensification in biodiesel production with energy reduction by pinch analysis, Energy
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Fig. 14. Example of biodiesel synthesis provided by AspenPlus® 8.2.

The reactants, oil and methanol, flow in counter-current in the extractive agent flow rate could be 0.077 kg glycerol/kg palm oil
reactive extraction column section. Methanol is the lowest density which is in the range defined previously for pure triglycerides with
compound, glycerol is the highest density compound, and therefore 14 theoretical stages (5 reactive þ 9 non-reactive). The 5 reactive
the polar phase methanol-glycerol flows downwards, as the reac- stages at the lower part of the column are used to achieve the
tion proceeds and becomes richer in glycerol. Methanol is fed at the complete palm oil conversion, and the 9 non-reactive stages at the
top of the reactive section and glycerol is collected at the bottom of upper part is used to separate the biodiesel from methanol by
the reactive section. On the other hand, the vegetable oil is fed at extraction with glycerol.
the bottom of the reactive section and impurified FAME is collected Fig. 18 shows the composition profile for the polar phase. The
at the top of the non-reactive section. Methanol is partially soluble main components of this phase are methanol and glycerol, the
in FAME and therefore a non-reactive extraction section at the latter flowing from the top to the bottom, also having the higher
upper part of the column is required to extract it from the obtained density. MeOH increases its composition from top to bottom of
biodiesel, using glycerol as extraction agent. This is obtained by non-reactive section (from stage 14 to stage 5). In agreement with
recycling part of the glycerol product stream collected in the bot- reaction scheme, MeOH reacts with glycerides forming FAME and
tom of the column. The numbering of column stages is performed glycerol in the reactive section (from stage 5 to stage 1), as illus-
from bottom to top. trated in Fig. 18.
Fig. 16 shows the evolution of the composition versus the Fig. 19 shows the composition profile for the non-polar phase. In
number of reactive stages in a reactive extraction section, keeping the first stage, most of the triglycerides are converted to mono-
constant the number of non-reactive stages. For simplicity pur- glycerides, which react to biodiesel in the second stage. Although in
poses, the compounds are grouped in biodiesel, triglycerides, di- the first stage the composition of biodiesel is lower, in the second
glycerides and monoglycerides without representing in the figure stage the mass fraction is higher than 0.9 and remains constant
the type of fatty acid present. Biodiesel is the main component. through the reactive phase. Between stages 3e6, methanol con-
Although an almost total conversion is achieved using only few centration passes through a maximum, enabling high conversion.
stages, the biodiesel stream purity is limited due to the methanol Between stages 6e14, which are non-reactive, methanol concen-
feed in counter-current. Nevertheless, the main aim of reactive tration decreases until the desired value, under 0.2%. In the
stages is to convert the vegetable oil to biodiesel (99% in this extractive phase, the biodiesel composition rises to achieve the
system). required value (99.6%). As mentioned previously, for simplicity, the
A conversion of 99.2% of palm oil to biodiesel can be achieved in compounds used in the simulation are presented in Figs. 16e19
5 reactive stages. Notice that a column with 5 reactive stages pro- lumped as triglycerides, diglycerides, monoglycerides, biodiesel,
vides biodiesel containing 16% methanol. This quantity can be glycerol and methanol. However, in Table 4 detailed composition
decreased to the allowed quantity of 0.2% in mass of methanol, for the input and output streams of the reactive extraction column
according to the European standards EN14214, by increasing the are presented. In Table 4, raw materials (oil and MeOH) are fed at
number of extraction stages or flow rate of extractive agent. The 25  C. Reactive extraction column operates at 60  C. Appropriate
relation between minimum glycerol flowrate and the number of utilities are used to provide this condition.
non-reactive stages allowing to obtain limiting MeOH concentra- The purity of biodiesel collected is 99.6% and the purity of
tion is shown in Fig. 17, obtained in AspenPlus®. glycerol is 88.2%. The purity of glycerol is limited by the presence of
An acceptable result is obtained for 9 non-reactive stages (99.6% a slight excess of 6.7% methanol in the feed, otherwise mathe-
of biodiesel purity as established in EU) for glycerol flow rate of matical convergence is not achieved due to the great quantity of
0.89 kmol/h for an imposed palm oil flow rate of 1.28 kmol/h. The compounds present in palm oil.
number of reactive and non-reactive stages is in agreement with Running the economic analysis in AspenPlus® with the default
the previously calculated values for pure triglycerides. A convenient settings for the classical scheme, for a biodiesel flow rate of 1051 kg/

Please cite this article in press as: Pleşu V, et al., Process intensification in biodiesel production with energy reduction by pinch analysis, Energy
(2014), http://dx.doi.org/10.1016/j.energy.2014.11.013
8 V. Pleşu et al. / Energy xxx (2014) 1e15

Fig. 15. Hybrid reactive-extraction column: (a) proposed process scheme and (b) simulation flowsheet.

h, the capital costs are of about 9,111,180 USD. For the intensified purify biodiesel and to recirculate the non-reacted oil and GLYCOL
process, the capital costs calculated in AspenPlus® are of to purify the glycerol) and one for methanol recovery (MEOHCOL)
1,951,360 USD Therefore, the capital cost for the classical process is which is recirculated to the reaction stage. In addition, an extrac-
4.6 times higher than for the intensified process. Nevertheless, tion column (WASHCOL) to separate the polar and non-polar
these values suggest that the intensified process is more advanta- phases using water is considered and a second reactor is needed
geous from economic point of view. to neutralize with H3PO4 the NaOH catalyst present in the polar
phase using. The product Na3PO4 is commonly used as fertilizer. In
3.3. Comparison of the minimum energy requirements for the Table 5, distillation columns specifications are given.
intensified process with the classical scheme Distillation columns operate at high temperature and low
pressure, involving important energy consumption, due to low
The classical scheme proposed in AspenPlus® example requires volatility of glycerol and FAME, as revealed in Table 6. However, the
3 distillation columns, two for the product purification (ESTCOL to extraction column WASHCOL operates adiabatically at 1 bar.

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Fig. 18. Composition profile for the polar phase.


Fig. 16. Composition results of the reactive phase simulation.

stream composition modification (separation task). The energy


The use of heat exchanger HX2 is irrelevant because only in- required for this purpose is calculated with equations given below
creases the temperature with 1  C and its energy consumption is (enthalpy of mixing is assumed negligible):
insignificant. One unclear aspect of this system is the recirculation
of non-reacted oil that leaves the distillation column ESTCOL at 0 Tc $DSsep
Qr ¼ þ l$D (1)
338  C, later is cooled to 25  C in the heat exchanger B2 and finally h
is heated again to the reaction temperature of 60  C. Therefore,
when comparing different processes, it is important to assess 2 P  X  3
rational use of energy. In this respect, Pinch Analysis is very useful ðD þ BÞ$ xfeed
i $ln xfeed
i  D$ xdistil
i $ln xdistil
i 
DSsep ¼ R$4 P  5
methodology. The streams are heated to 60  C before entering the B$ xresidue $ln xresidue
i i
reactor and then the effluents are feed to distillation columns at the
corresponding boiling point. Process scheme output streams are (2)
cooled to 35  C. In this respect Pinch Analysis is used. In Table 7 and
Fig. 20, data extraction results are presented, for hot and cold Tr  Tc
process streams. h¼ (3)
Tr
Fig. 21 shows the Composite Curves for the classic process
considering only the streams, without taking into account the The minimum energy requirements are shown in Table 8. These
distillation columns. A DTmin ¼ 40  C is necessary to obtain a pro- values are introduced in the heat cascade of Pinch Analysis. The
cess integration problem. The heat utility target is small, 8.35 kW reboiler duty has the same sign as a cold stream because it con-
due to the output distillation column streams at high temperature. sumes energy. The same value is used for the condenser duty, but
Cold utility is as well relatively small, 47.1 kW. But, energy con- with the opposite sign. The column duties are introduced in the
sumption of distillation columns is very important, as presented in cascade at the reboiler and condenser temperatures, respectively.
Table 6. The energy of process streams considered above is just a At our knowledge, it is the first time that the minimum energy
small part of flowsheet heat requirements, therefore the columns requirements of a process are determined based on the second law
must be also considered in process integration study. Following of thermodynamics, taking into account the operation units
recent results [8], it is possible to calculate the minimum energy requirements.
consumption of a distillation column, for consideration into the The minimum energy consumption is lower than a simple sum
Pinch Analysis. Fulfilling the second thermodynamic law, the of the units' energy requirements shown in Table 6, as the
distillation column acts as a heat engine, which exchanges energy distillation columns can be energy integrated. The energy
between a cold and a hot focus (condenser and reboiler) to ensure

Fig. 17. Minimum glycerol flowrate to obtain MeOH legal composition in biodiesel
versus number of non-reactive stages. Fig. 19. Composition profile for the non-polar phase.

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Table 4
Detailed composition for the input and output streams.

Stream OIL MEOH GLY FAME GLYPR GLY þ MEOH

x (mass)
METHANOL 0.92707 0.00052 0.06613 0.50941
OOO 0.04699 0.00000 0.00000 0.00000
MMM 0.00366 0.00000 0.00000 0.00000
METHYL-O 0.38932 0.00002 0.00033
GLYCEROL 1.0000 0.00019 0.88242 0.48095
NaOH 0.07293 0.00000 0.04749 0.00786
PPP 0.05366 0.00001 0.00000 0.00000
METHYL-P 0.48103 0.00000 0.00075
PPS 0.01068 0.00000 0.00000 0.00000
PPO 0.29774 0.00001 0.00000 0.00000
POS 0.05091 0.00000 0.00000 0.00000
MMP 0.01540 0.00000 0.00000 0.00000
PPLI 0.09256 0.00000 0.00000 0.00000
POO 0.24112 0.00001 0.00000 0.00000
PLIO 0.10011 0.00000 0.00000 0.00000
OOS 0.02398 0.00000 0.00000 0.00000
OOLI 0.00618 0.00000 0.00000 0.00000
MPLI 0.02132 0.00000 0.00000 0.00000
METHYL-M 0.01993 0.00001 0.00007
METHYL-S 0.02934 0.00000 0.00002
METHY-LI 0.07655 0.00001 0.00009
1-M 0.00005 0.00009 0.00003
1-P 0.00123 0.00355 0.00030
1-S 0.00009 0.00001 0.00001
1-O 0.00123 0.00025 0.00016
1-LI 0.00025 0.00003 0.00002
MM 0.00000 0.00000 0.00000
PP 0.03568 0.00005 0.00000 0.00000
OO 0.00004 0.00000 0.00000
PO 0.00009 0.00000 0.00000
PLI 0.00002 0.00000 0.00000
MP 0.00000 0.00000 0.00000
PS 0.00001 0.00000 0.00000
OS 0.00001 0.00000 0.00000
LIO 0.00001 0.00000 0.00000
MLI 0.00000 0.00000 0.00000
Total Flow kg/h 1059 146 82 1062 225 171
SUMMARY x (mass)
Triglycerides 0.96432 0.00004 0.00000 0.00000
Diglycerides 0.03568 0.00022 0.00000 0.00000
Monoglycerides 0.00285 0.00393 0.00052
FAME 0.99617 0.00004 0.00126
Methanol 0.92707 0.00052 0.06613 0.50941
Glycerol 1.0000 0.00019 0.88242 0.48095
NaOH 0.07293 0.04748 0.00786

requirement to operate at low pressure is not considered. reboilers and hot streams in condensers. The very small increase
Applying the Pinch Analysis and taking into account the mini- of temperature must be positive for the reboilers, which are
mum energy requirement for the distillation columns, the hot considered as a cold stream, and negative for the condensers. As
minimum energy requirement of the system is of 28.0 kW. The the reaction is exothermic, the reactor is considered as a hot
minimum duties (condenser and reboiler duties) calculated for stream. Stream data introduced in Sprint® is shown in Fig. 22. The
the columns in Table 8 are considering a very small temperature Composite Curves taking into account the irreversibilities in
difference between the reboiler and condenser and the respective
heating and cooling fluids according to minimize the irrevers- Table 6
ibility. For better real values, the temperature of the units should Energy consumption of process equipment.
be shifted as it was made for the process streams, to take into
Equipment Type Heat (kW)
account the irreversibilities in condenser and in reboiler. The
Heat requirement MEOHCOL Reboiler 118.0
temperature shift is performed automatically when the data is
GLYCOL Reboiler 283.8
introduced in Sprint®. A very small corresponding difference of ESTCOL Reboiler 374.4
temperature (0.1  C) is used to consider the cold stream in HX1 Heat exchanger 22.0
REACTOR Reactor 15.3
TOTAL 813.5
Table 5 Heat to eliminate MEOHCOL Condenser 122.0
Distillation columns specifications. GLYCOL Condenser 261.2
ESTCOL Condenser 304.7
Name Stages Reflux ratio Pressure (bar) Treboiler ( C) Tcondenser ( C)
HX2 Heat Exchanger 0.1
MEOHCOL 7 2 0.2 59.2 28.8 B2 Heat Exchanger 9.8
GLYCOL 6 2 0.4 262.2 70.9 NEUTR Reactor 1.5
ESTCOL 6 0.95 0.1 338 148.3 TOTAL ¡699.3

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Table 7
Data extraction: hot and cold process streams for classical process scheme.

Stream TS TT Type CP (W/ C) DH


( C) ( C) (W)

1 MIX 1 25 60 COLD 153 5357


2 MEOH recirculated 28.8 60 COLD 98 3043
3 OIL 25 60 COLD 622 21,764
4 REACT-MEOHCOL 60 40 HOT 883 17,653
5 AQU3 50 100 COLD 221 11,052
6 EST4-ESTCOL 54 136 COLD 645 52,857
7 WATMEOH 71 35 HOT 152 5465
8 MEOHWAT 148.3 35 HOT 2 272
9 FAME 148.3 35 HOT 694 78,650
10 GLYCEROL 262.2 35 HOT 93 21,108
11 OILREC 338.01 60 HOT 35 9697

Fig. 21. Composite Curves for the classic process without considering the units, where
reboiler and condenser of distillation columns and the reactor are DTmin ¼ 40  C.
presented in Fig. 23. Then, as usual for such processes
DTmin ¼ 10  C, energy required by the units, i.e. distillation and
Table 8
reaction, are the horizontal regions of the curves. The pinch point
Minimum energy requirements of the distillation columns.
temperature is 66.1  C, but as it is shown in Fig. 23. From Sprint®
energy report hot utility target is 33 kW, cold utility target is Tc Tr h DS Dl Minimum energy
( C) ( C) (W/ C) (kW) consumption (kW)
79.3 kW, and process heat recovery is 121 kW. These values are
very low compared to the requirements of AspenPlus® base MEOHCOL 28.8 60 0.091 15.3 38.5 46.4
GLY COL 71 262.2 0.357 7.8 2.6 10.7
example without heat integration, i.e. 813.15 kW. These results
ESTCOL 148.3 338.01 0.310 1.9 0.1 2.5
underline the importance of process integration, taking into ac- REACTOR 60 7.4
count all process units.
Grand Composite Curve (Fig. 25a) indicates the potential heat
recovery inside the process (a big pocket in the hot zone, which
lowers the demand and temperature of hot utilities. Therefore, it is proposed flowsheet is a better option, considering process intensi-
possible for example to use about 25 kW hot utility with temper- fication and rational use of energy (Table 11). Furthermore, the
atures less than 150  C. Just a small amount of hot utility ~10 kW is intensified process requires a heat source of lower temperature than
needed around 300  C and a very small amount of hot utility ~3 kW the AspenPlus® base process (Fig. 25) as is shown by Grand Com-
is needed for more than 350  C. posite Curve. Minimum hot utility temperature is 70  C and
For our proposed process, the extractive stages operate at 60  C, maximum cold utility temperature is 25  C.
therefore energy should be considered to maintain constant tem-
perature (Table 9). This can be achieved using a jacketed column. 3.4. Evaluation of using the hybrid extraction column for several
Table 9 shows also that the energy is consumed mostly by the first oils
and fifth stages of the reactive zone, because oil stream and meth-
anol stream are fed at 25  C. Therefore, the non-integrated alter- The presence of FFA (free fatty acids) is not the scope of the
native process has a relatively low energy requirement 31.8 kW, present study, although it is also an important point to be consid-
compared to the basic AspenPlus® example process of 813.5 kW. It is ered as for instance J. curcas oil can contain up to 15% FFA [34]. Same
also bit lower when compared to the heat integrated AspenPlus® composition has as well as cooking oils. Excess FFAs lead to
basic process (33 kW). The composite curves of the isothermal increased catalyst requirement as well as soap formation. FFA
extraction column with heat integration of the streams (Table 10) should be esterified with an acid catalyst before being fed to the
are shown in Fig. 24. For same reasons as above, DTmin ¼ 10  C can be column. The oil compositions are approximate to triglyceride
considered. As shown in Fig. 24, in this case Composite Curves give composition (Table 12) with an equivalent amount of fatty acids
minimum hot utility requirement is 10.5 kW, minimum cold utility indicated in Table 3. The flow rate of oil fed to the process is of
is 13.6 kW, and process heat recovery is 26.2 kW. The pinch point 1 kmol/h, requiring a stoichiometric amount of methanol and
temperature for the intensified processes is 55  C. Therefore our 0.8 kmol/h glycerol.

Fig. 20. Classical process scheme with streams according to Table 7.

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12 V. Pleşu et al. / Energy xxx (2014) 1e15

Fig. 22. Data input at Sprint®. From 1 to 11 are streams, from 12 to 17 are column reboilers (R) and condensers (C) and 18 is the reactor.

Biodiesel composition obtained from J. curcas oil is presented Spirulina oil composition is assimilated to be 90% PPLi (dipal-
in Table 13. The biodiesel obtained using stoichiometric methanol mitin-linolein) and 10% OOLi. The linolenic acid content has been
ratio fulfils EN 14214-legislation provision with exception of assimilated to linoleic in the process simulation because it is not in
diglycerids and glycerol content. The excessive diglycerides AspenPlus® database. An interesting result is that the main tri-
quantity is unexpected result. The diglycerides with a high mass glyceride, which appears in biodiesel, is PPO (dipalmitoyl-oleiyl-
faction are PO and PLi. These are not directly obtained by trans- glycerol), although this triglyceride is not initially present in algae
esterification of the initial triglycerides (PPS and OOLi), but by oil. This behaviour can be explained considering a trans-
recombination. This fact can be justified by the stability of the esterification process. In this way, the main triglycerides present in
compounds, e.g. PO is the more stable compound, according to biodiesel are always PPO or PLiO, independently if they are present
the enthalpy of formation. Glycerol removal is easy by water or not, in the initial oil. Contrary to the result obtained for J. curcas
extraction. J. curcas oil has been assumed as a mixture of 77% OOLi oil, biodiesel obtained from spirulina oil do not contain significant
and 23% PPS and the percent of methyl esters is 97.77% instead of amounts of diglycerides PO and PLi. The reason is that as the OOLi is
the 99.47% obtained using OOLi alone. Therefore, the presence of only a 10% of oil composition, a higher conversion is obtained with
PPS leads to a lower conversion and a higher amount of di- fewer stages.
glycerides. A slight increase of the methanol amount, higher than Spirogyra oil is assimilated to a composition of 37.86% PLiO,
the stoichiometric one, produces an increase of methyl esters 26.28% OOO, 15.75% PPS, 12.63% PPP and 7.48% MMM. An excess of
quantity, in the same time, the mass fraction of diglycerides de- methanol to 3.5 kmol/h has been required to achieve process
creases. However, a higher number of equilibrium stages is
preferred rather than the use of a methanol excess to fulfil the
biodiesel specifications.

Fig. 23. Composite curves of the classical process. Fig. 24. Composite curve of the intensified process.

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Table 10
Data extraction: hot and cold process streams for the intensified process.

Stream T1 T2 Type CP (W/ C) DH


( C) ( C) (W)

1 OIL 25 60 COLD 584 20,438


2 MEOH 25 60 COLD 465 16,267
3 FAME 60 35 HOT 1444 36,106
4 GLYPR 60 35 COLD 147 3667

Table 11
Energy requirements for classic and intensified process alternatives (DTmin ¼ 10  C).

Energy Minimum thermodynamic Maximum


consumption energy temperature
(kW) (kW) (oC)

Classic 813.5 33 338


Intensified 31.8 10.5 60

4. Conclusions

A hybrid reactive extraction column to produce biodiesel (five


reactive stages and 9 non-reactive stages) is rigorously simulated
for several oils considering pure triglycerides or combinations of
heterogeneous triglycerides. The minimum number of equilib-
rium stages and operating parameters are studied for pure tri-
glycerides. A higher number of double bonds decreases the
conversion and requires more process energy. Unsaturated fats

Fig. 25. Grand composite curves for: a) the classic process scheme; b) intensified
process. Table 12
Oils and corresponding biodiesel compositions.

Stream: Mass flow [kg/h] Jatropha curcas Spirogyra Spirulina Tolypothryx


simulation convergence. In a similar way as J. curcas, a too high
amount of diglycerids and glycerol is present in the collected bio- FAME OIL FAME OIL FAME OIL FAME OIL
diesel. For 3.3 kmol MeOH/h, 1.50% diglycerids are collected; for METHANOL 0.4270 0 2.12 0 0.3130 0 0.2630 0
3.5 kmol MeOH/h, 1.47% diglycerids and for 4.0 kmol MeOH/h, 1.52% MMM 0 0 0 63 0 0 0 56.90
diglycerids are collected, therefore a minimum of diglycerids exists METHYL-O 449 0 157 0 43 0 188 0
GLYCEROL 0.2510 0 0.4480 0 0.2400 0 0.2350 0
between 3.3 and 4 kmol MeOH/h.
NAOH 0.0007 0 0.0006 0 0.0007 0 0.0007 0
The Tolypothis algae oil is assimilated to 7.88% MMM, 34.40% METHYL-P 116 0 290 0 466 0 348 0
PPP, 18.74% PPLi and 38.98% OOLi and it is simulated with a stoi- OOO 0 0 0 0 0.7170 0 25.40 0
chiometric reactants mixture. PPP 0 0 0 0 0.0042 0 0.0032 278
As discussed previously, more stages should be used to assure PPS 0.0226 192 0.0048 133 0 0 0 0
PPO 0 0 0.0222 328 34 0 47.90 0
total conversion and stoichiometric feed than the calculated one POO 0 0 0 0 0 0 0 0
for pure triglycerides. There are 14 (5 þ 9) necessary equilibrium POS 0 0 0 0 0 0 0 0
stages when considering pure triglycerides, but when using oils, MMP 0 0 0 0 0 0 0 0
the simulation results suggest considering a larger number of PPLI 0 0 0 0 0.0090 753 0.0043 156
POO 0 0 0 0 0 0 0 0
equilibrium stages to assure reasonable conversion. The energy
PLIO 0.3780 0 0 0 0 0 0 0
requirements are very low for all kind of oils. Most of the con- OOS 0 0 0 0 0 0 0 0
sumption is due to heating the reactant streams and to the first OOLI 0.0307 680 3.98 319 0.0001 83.60 0.0011 344
stages of the reactive section where most of the conversion takes METHYL-M 0 0 63 0 0 0 57.10 0.0000
place (Fig. 26). The lowest energy requirement is for Spirogyra METHYL-S 68 0 47 0 0 0 0 0
METHY-LI 225 0 59 0 294 0 169 0
algae oil. 1-M 0 0 0.1610 0 0 0 0.1620 0
1-P 1.80 0 9.94 0 0.9230 0 1.22 0
1-S 0.2650 0 0.1700 0 0 0 0 0
Table 9 1-O 3.12 0 6.16 0 0.1440 0 0.6460 0
Energy requirement of the alternative process. 1-LI 0.8720 0 0.1810 0 1.00 0 0.5970 0
MM 0 0 0.0010 0 0 0 0.0011 0
Extractive-reactive section Heat duty (kW)
PP 1.43 0 0.3180 0 0.0390 0 0.0393 0
Stage 1 20.4 OO 0.3980 0 125 0 0.0005 0 0.0097 0
Stage 2 7.1 PO 8.40 0 0.2370 0 0.0089 0 0.0389 0
Stage 3 2.6 PLI 2.03 0 0 0 0.0614 0 0.0355 0
Stage 4 0.4 MP 0 0 0 0 0 0 0 0
Stage 5 4.4 PS 0.0154 0 0.0372 0 0 0 0 0
Total 34.9 OS 0 0 0.0383 0 0 0 0 0
Extractive section All stages 3.1 LIO 0.1060 0 96 0 0.0067 0 0.0177 0
TOTAL system TOTAL 31.8

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14 V. Pleşu et al. / Energy xxx (2014) 1e15

Table 13 Nomenclature
Mass percent composition of biodiesel from several oils (3 kmol/h methanol is the
stoichiometric amount).
DS entropy change in the distillation column
Oil Jatropha Spirulina Spyrogira Tolypothrix DTmin pinch temperature (K)
curcas oil algae oil algae oil algae oil Qr energy required by the distillation column (kW)
Compound 3 3.3 3 3.2 3.5 3.0 Tc temperature of the distillation column condenser (K)
Methanol 0.049 0.048 0.037 0.044 0.045 0.03 Tr temperature of the distillation column reboiler (K)
Methylic 97.775 98.335 95.505 99.607 98.005 90.88 h Carnot efficiency
esters l enthalpy of vaporization for the distillate stream (kJ/
Monoglycerids 0.689 0.525 0.246 0.299 0.424 0.31
kmol)
Diglycerids 1.409 1.030 0.014 0.019 1.470 0.02
Triglycerids 0.049 0.034 4.169 0.003 0.027 8.73 R ideal gas constant (kPa m3/kmol K)
Glycerol 0.029 0.028 0.029 0.028 0.029 0.03 D distillate flow rate (kmol/s)
B bottoms flow rate (kmol/s)
xi molar composition of compound i in the corresponding
stream.
CSTR continuous stirred tank reactor
NRTL non random two liquid thermodynamic model
EU European Union
MeOH methanol
NaOH sodium hydroxide
FAME fatty acid methyl ester
FFA free fatty acids
O oleic acid (C18:1)
M myristic acid (C14:0)
P palmitic acid (C16:0)
Li linoleic acid (C18:2)
S stearic acid (C18:0)
MMM trimyristin
OOLi diolein-linolein
OOO triolein
Fig. 26. Energy requirements for the column operated isothermally at 60 C for PLIO palmitin-linolein
1 kmol/h of oil.
PPLI dipalmitin-linolein
PPP tripalmitin
PPS dipalmitin-stearin
are most benefic from health point of view but, for biodiesel POO palmitin-diolein
synthesis, they decrease the conversion and determine more POS palmitin-olein-stearin
energy consumption. Therefore, it would be recommended to PPO dipalmitin-olein
separate the unsaturated fats for human consumption and use Methyl-M methyl myristate
the saturated fats for biodiesel synthesis. The oils composed of C N:M FFA oil composition, where N is carbon chain length and
several triglycerides require larger reactive extraction column. In M is the number of double bonds, e.g. linolenic acid:
some cases, a too short column can be compensated using an C18:3.
excess of methanol. Therefore, a column with more stages would
be recommended for industrial application. However, it is ex- References
pected to attain a total conversion of stoichiometric reactants
with an acceptable number of stages. The proposed intensified [1] Plesu V, Bonet-Ruiz J, Bumbac G, Teodorescu F, Tuluc A. Modelling and
process requires just one unit and low energy consumption. For simulation for sustainable biodiesel production. In: CHISA 2012e20th Inter-
national Congress of Chemical and Process Engineering and PRES 2012-15th
instance, hot utility target for the intensified process using palm Conference PRES Conference Proceedings, Prague (Czech Republic); 2012.
oil is significantly lower than the classical process, i.e. 31.8 kW vs [2] Plesu V, Bonet J, Bonet Ruiz AE, Llorens J. Advantages of process integration
813.5 kW respectively. The main energy consumption is due to evaluated by gibbs energy: biodiesel synthesis case. In: Computer Aided
Chemical Engineering eProceedings of the 24th European Symposium on
distillation columns needed to purify products and to recover Computer Aided Process Engineering e ESCAPEvol. 24; 2014 [In press].
methanol. The Pinch Analysis, to determine the target for hot and [3] Bonet J, Plesu V, Bonet Ruiz AE, Iancu P, Llorens J. Thermodynamic study of
cold utilities required, considering the distillation columns as batch reactor biodiesel synthesis. Rev Chim 2014;65(3):358e61.
[4] Badday AS, Abdullah AZ, Lee KT. Ultrasound-assisted transesterification of
part of the whole process, is used. It is shown that the hot utility crude Jatropha oil using cesium doped heteropolyacid catalyst: interactions
target required by the classical scheme presented in AspenPlus® between process variables. Energy 2013;60:283e91.
documentation can decrease significantly to our intensified [5] Ong LK, Effendi C, Kurniawan A, Lin CX, Zhao XS, Ismadji S. Optimization of
catalyst-free production of biodiesel from Ceiba pentandra (kapok) oil with
scheme, from 33 kW to 10.5 kW.
high free fatty acid contents. Energy 2013;57:615e23.
[6] Alenezi R, Santos RCD, Raymahasay S, Leeke GA. Improved biodiesel manufacture
at low temperature and short reaction time. Renew Energy 2013;53:242e8.
Acknowledgements [7] Jurado MBG, Plesu V, Ruiz JB, Ruiz AEB, Tuluc A, Llacuna JL. Simulation of a
hybrid reactive extraction unit. Biodiesel synthesis. Chem Eng Trans 2013;33:
205e10.
The authors would like to thank the financial support of POSCCE [8] Cheng J-K, Chao C-C, Ward JD, Chien I-L. Design and control of a biodiesel
project ID 652 (Structural Funds for Development and Cohesion) production process using sugar catalyst for oil feedstock with different free
and the project CTQ2009-11465 (Ministry of Science and Innova- fatty acid concentrations. J Taiwan Inst Chem Eng 2014;45(1):76e84.
[9] Oh PP, Chong MF, Lau HLN, Chen J, Choo YM. Liquid-liquid equilibrium (LLE)
tion e Spanish Government) who provided the opportunity to study for six-component transesterification system. Clean Technol Environ
complete this research. Policy 2013;15(5):817e22.

Please cite this article in press as: Pleşu V, et al., Process intensification in biodiesel production with energy reduction by pinch analysis, Energy
(2014), http://dx.doi.org/10.1016/j.energy.2014.11.013
V. Pleşu et al. / Energy xxx (2014) 1e15 15

[10] Cadavid JG, Godoy-Silva RD, Narvaez PC, Camargo M, Fonteix C. Biodiesel [23] Liang X. Synthesis of biodiesel from waste oil under mild conditions using
production in a counter-current reactive extraction column: modelling, novel acidic ionic liquid immobilization on poly divinylbenzene. Energy
parametric identification and optimization. Chem Eng J 2013;228:717e23. 2013;63:103e8.
[11] Go mez GE, Ramos MA, Cadena JE, Go mez JM, Munoz F. Inherently safer design [24] Martins MI, Pires RF, Alves MJ, Hori CE, Reis MHM, Cardoso VL. Trans-
applied to the biodiesel production. Chem Eng Trans 2013;31:619e24. esterification of soybean oil for biodiesel production using hydrotalcite as
[12] Prussi M, Chiaramonti D, Recchia L, Martelli F, Guidotti F, Pari L. Alternative basic catalyst. Chem Eng Trans 2013;32:817e22.
feedstock for the biodiesel and energy production: the OVEST project. Energy [25] Kemp IC. Pinch analysis and process integration: a user guide on process
2013;58:2e8. integration for the efficient use of energy. 2nd ed. Burlington, MA: Elsevier/
[13] Iancu P, Plesu V, Velea S. Flue gas CO2 capture by microalgae in photo- Butterworth-Heinemann; 2007.
bioreactor: a sustainable technology. Chem Eng Trans 2012;29:799e804. [26] Plesu V, Bonet Ruiz AE, Bonet J, Llorens J, Iancu P. Minimum number of
[14] Bhaskar K, Nagarajan G, Sampath S. Optimization of FOME (fish oil methyl transfer units and reboiler duty for multicomponent distillation columns. Appl
esters) blend and EGR (exhaust gas recirculation) for simultaneous control of Therm Eng 2013;61:67e79.
NOx and particulate matter emissions in diesel engines. Energy 2013;62: [27] Ignat RM, Kiss AA. Energy efficient recovery of methanol and glycerol in
224e34. biodiesel production. Chem Eng Trans 2012;29:1141e6.
[15] Chakraborty M, Baruah DC. Production and characterization of biodiesel ob- [28] Palmeira JVN, Silva JM, Matos HAS. Industry energy optimization: a case study
tained from Sapindus mukorossi kernel oil. Energy 2013;60:159e67. in a biodiesel production site. Chem Eng Trans 2012;29:919e24.
[16] Miller P, Kumar A. Development of emission parameters and net energy ratio [29] Narvaez PC, Rincon SM, Sanchez FJ. Kinetics of palm oil methanolysis. J Am Oil
for renewable diesel from Canola and Camelina. Energy 2013;58:426e37. Chem Soc 2007;84:971e7.
[17] Chauhan BS, Kumar N, Cho HM, Lim HC. A study on the performance and [30] Huerga IR, Zanuttini MS, Gross MS, Querini CA. Biodiesel production from
emission of a diesel engine fueled with Karanja biodiesel and its blends. En- Jatropha curcas: integrated process optimization. Energy Convers Manag
ergy 2013;56:1e7. 2014;80:1e9.
[18] Ng WPQ, Lam HL, Yusup S. Supply network synthesis on rubber seed oil [31] Pankaj KM, Suseela R, Toppo K. Physico-chemical characterization of algal oil:
utilisation as potential biofuel feedstock. Energy 2013;55:82e8. a potential biofuel. Asian J Exp Biol Sci 2011;2:493e7.
[19] Halek F, Delavari A, Kavousi-rahim A. Production of biodiesel as a renewable [32] Hakim M, Najafabadi HA, Pazuki G, Vossoughi M. Novel approach for liquid-
energy source from castor oil. Clean Technol Environ Policy 2013;15:1063e8. liquid phase equilibrium of biodiesel (canola and sunflower) þ glycerol þ
[20] Chisti Y. Biodiesel from microalgae. Biotechnol Adv 2007;25(3):294e306. methanol. Ind Eng Chem Res 2014;53:855e64.
[21] http://www.originoil.com/pdf/OriginOil_NAA_January_2011.pdf, [accessed [33] SPRINT® software http://www.cpi.umist.ac.uk/software/products/sprint.asp
28.06.2011]. [accessed 30.06.2014].
[22] Lee HV, Taufiq-Yap YH, Hussein MZ, Yunus R. Transesterification of jatropha [34] Berchmans HJ, Hirata S. Biodiesel production from Jatropha curcas L. seed oil
oil with methanol over Mg-Zn mixed metal oxide catalysts. Energy with a high content of free fatty acids. Bioresour Technol 2008;99:1716e21.
2013;49(1):12e8.

Please cite this article in press as: Pleşu V, et al., Process intensification in biodiesel production with energy reduction by pinch analysis, Energy
(2014), http://dx.doi.org/10.1016/j.energy.2014.11.013

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