Resources, Conservation and Recycling 51 (2007) 397407

Exergy analysis applied to biodiesel production

Laura Talens
a,
, Gara Villalba
a
, Xavier Gabarrell
a,b
a
SosteniPra UAB-IRTA. Environmental Science and Technology Institute (ICTA),
Edici Cn, Universitat Aut ` onoma de Barcelona (UAB),
08193 Bellaterra (Cerdanyola del Vall es), Barcelona, Spain
b
Department of Chemical Engineering, Universitat Aut ` onoma de Barcelona (UAB),
08193 Bellaterra (Cerdanyola del Vall es), Barcelona, Spain
Received 16 June 2006; received in revised form 16 October 2006; accepted 18 October 2006
Available online 21 November 2006
Abstract
In our aim to decrease the consumption of materials and energy and promote the use of renewable
resources, such as biofuels, rises the need to measure materials and energy uxes. This paper suggests
the use of Exergy Flow Analysis (ExFA) as an environmental assessment tool to account wastes and
emissions, determine the exergetic efciency, compare substitutes and other types of energy sources:
all useful in dening environmental and economical policies for resource use. In order to illustrate
how ExFA is used, it is applied to the process of biodiesel production. The results show that the
production process has a low exergy loss (492 MJ). The exergy loss is reduced by using potassium
hydroxide and sulphuric acid as process catalysts and it can be further minimised by improving the
quality of the used cooking oil.
2006 Elsevier B.V. All rights reserved.
Keywords: Exergy analysis; Exergetic efciency; Environmental assessment; Renewable resources; Biodiesel
1. Introduction
The study of renewable resources is a promising and mandatory eld of research in our
strife to achieve a more sustainable way of living. In 2003, the European Commission pre-
sented the directive 2003/96/EC on the promotion of the use of biofuels or other renewable

Corresponding author. Tel.: +34 93581 2503; fax: +34 93581 3331.
E-mail address: laura.talens@uab.es (L. Talens).
0921-3449/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.resconrec.2006.10.008
398 L. Talens et al. / Resources, Conservation and Recycling 51 (2007) 397407
fuels for transport. In this directive, EU member countries set the goal of increasing the
production of renewable energy to a minimum of 12% of the total domestic energy con-
sumption by the year 2010. The directive established an amount of 5.75% of biofuels by
the year 2010 (Parliament, 2003). Thus, as we expect the use of biodiesel to increase, it is
important to have a means of evaluating these renewable resources of energy. An accurate
comparison among the impacts is rather difcult due to the lack of a unique unit of mea-
surement. This makes it difcult if not impossible to compare among renewable resources,
for example wind and biomass energy production.
Exergy Flow Analysis (ExFA) accounts for all energy and material requirements in
the same units. The concept of exergy accounting has been applied in the past to study
the production processes and account wastes and gas emissions (Ayres, 1998; Wall, 1977;
Ayres and Ayres, 1999). This work applies this exergy concept to the production process of
renewable resources. Since previous exergy analysis have done extensive introductions to
the concept of exergy (Ayres and Ayres, 1999; Szargut et al., 1988; Baumg artner, 2002), we
will limit ourselves to the basic denition. Exergy is the amount of work obtainable when
some matter is brought to a state of thermodynamic equilibrium. As the systemapproaches
equilibrium, the exergy approaches zero. For example the iron ore extracted from the earth
has an exergy of 252 MJ, however as it is upgraded in the steel production process, its exergy
content increases to 6750 MJ (Ayres et al., 2001).
The exergy of an isolated system is a variable not conserved; it can be gained, lost,
accumulated or even stored. In processes, exergy is lost mostly as low temperature heat as
well as in chemically and physically reactive materials. This unutilized exergy normally
interacts with its surroundings and can drive to undesirable environmental processes in
non equilibrium situations that can cause environmental harm. So, exergy can be under-
stood as well as the potential of a material for causing harm (Ayres, 1998). The exergy
content of a natural resource input can be interpreted as a measure of its quality or
potential usefulness, or its ability to perform useful work (Ayres and Ayres, 1999). Con-
sequently, exergy can measure resource quality as well as quantity and is applicable for
both materials and energy. The following work will illustrate how exergy analysis can be
used to evaluate the production process of renewable resources by evaluating biodiesel
production.
2. Exergy ow analysis
The methodology consists of four steps. The rst step is to establish the system bounda-
ries by drawing a ow diagram of the industrial process under study, determining which
inputs/outputs stages and by-products are part of the system. In dening systemboundaries,
factors such as fuel and energy carriers, trace inputs/outputs and pre-treatment stages must
be taken into account before drawing a process ow diagram.
Secondly, the process is broken down into operation units to study each one indepen-
dently. An operation unit is dened as a unit of the process with a set of working conditions
specic to the reaction such as evaporation, separation and acidulation. The working condi-
tions dened for each operation unit are the residence time, pressure, temperature, catalyst,
product yield, time and utilities, which are interrelated and modifying one alters the others.
L. Talens et al. / Resources, Conservation and Recycling 51 (2007) 397407 399
Examining each unit independently can help identify opportunities for technical improve-
ments. In addition, they can be reused in other studies.
Then, based on the material balance principle, the in and out ows are balanced for each
process unit. After that, all process streams are normalized to 1 ton of main product in order
to facilitate comparisons.
Finally, the exergy of pure substances, mixtures and utilities is calculated. The total
exergy of the system is equal to the chemical exergy of material and the exergy of utilities
(Szargut et al., 1988). The standard exergy of many compounds can be found in Szargut
et al. or in the Appendix B and Appendix C in Accounting for Resources 2 (Ayres and
Ayres, 1999). When not available, the chemical exergy content of any pure substance can
be computed by the approximate Eq. (1) (Ayres and Ayres, 1999; Szargut et al., 1988).
B
ch
= G
Fo
+

i
N
i
b
i
(1)
G
Fo
, standard Gibbs free energy of formation of the substance [J/kg]; b
i
, chemical exergy
of the ith pure element of the substance [J/kg]; N
i
, molar fraction of the ith pure element of
the compound.
The Gibbs free energy of formation is available for most chemical compounds in standard
reference sources for a large number of chemicals. If not available, it is determined by
methodologies as the Shomate equation (Technology, 2005) and the Van Krevelen-Chermin
equation (Perry and Chilton, 1973). The chemical exergy of the ith pure element of the
substance b
i
is determined by using the standard chemical exergy of elements given in
Appendix B and C in Accounting for resources 2 (Ayres and Ayres, 1999).
Since mixtures preserve their chemical properties, the chemical exergy of mixtures is
dened as the sumof the chemical exergy of substances forming the mixture plus the exergy
loss due to the mixing of the substances (Eq. (2)).
B
chmixture
=

i
N
i
b
i
+RT
0
y
i
ln y
i
(2)
b
i
, chemical exergy of the ith substance [J/kg]; N
i
, molar fraction of the ith substance; R
Gas law constant [J/kgK]; T
0
Temperature [K]; y
i
, Mole fraction of the ith substance.
Utilities in chemical engineering are dened as the set of gas, electricity, vapor, coke and
other energy sources that supply the energy needed to carry out the process at the optimum
reaction conditions. Although there is information available on energy consumption per
process unit, the normal procedure is to account the overall utility consumption as a general
value for the process. Usually, in order to account energy sources in exergy units (Joules),
exergy conversion coefcients are dened. In the case of fuels (coal, fuel oil and natural
gas), the exergy content is estimated by multiplying the net heating value by an appropriate
coefcient (Ayres et al., 2001). This coefcient can be used to estimate the chemical exergy
content of any fuel from its heating value or enthalpy. The exergy coefcient of electricity
is assumed to be equal to 1.00, so 1 kJ of electrical energy corresponds to an exergy ow
of 1 kJ (Ayres et al., 2001). When calculating the exergy of the process steam, the ther-
mal exergy b
th
is accounted by its two components, the physical and the chemical exergy
400 L. Talens et al. / Resources, Conservation and Recycling 51 (2007) 397407
(Eq. (3)) (Szargut et al., 1988).
b
th
= b
ch
+b
ph
(3)
The chemical exergy b
ch
of steam (528 kJ/kg) is taken from Table I of the appendix of
Exergy analysis of thermal, chemical, and metallurgical processes (Szargut et al., 1988). In
general, the physical exergy b
ph
is dened by Eq. (4), where values for specic enthalpies
and entropies are obtained from steam tables (Rogers and Mayhew, 1964).
b
ph
= (H H
0
) T
0
(S S
0
) (4)
h, specic enthalpy of steam[J/kg]; h
0
, specic enthalpy of saturated liquid water at ambient
temperature [J/kg]; s, specic entropy of steam [J/kgK]; s
0
, specic entropy of saturated
liquid water at ambient temperature [J/kgK]; T
0
, ambient temperature [K].
The exergy of each process stream is calculated, to obtain an exergy ow diagram of
the process which allows identifying material and energy losses, detecting areas needing
technological improvements, measuring the potential reactivity and quality and comparing
the production of biodiesel with other energy sources.
3. Application to biodiesel
3.1. Biodiesel production
Biodiesel is a renewable fuel producedfromvegetable oils suchas rapeseedandsunower
seed oils, and also from used cooking oil (UCO). UCO is a mixture with high content of
tri-, di- and monoacylglycerides, from here on referred to as glycerides, and Free Fatty
Acids (FFA) (Mittelbach, 2004; Knothe et al., 2005). The reaction between glycerides and
short chain alcohols, such as methanol and ethanol, yields glycerol and fatty acids methyl
esters, better known as biodiesel. The production of biodiesel is based on a two-step process.
The rst step is the preesterication of FFA and glycerides with an alcohol using an acid
catalyst, such as sulfuric acid or phosphoric acid. The ester phase containing methyl esters
and glycerides settles in the reactor and the unreacted FFA is fed to a separate tank. The
secondstepis the transestericationof the glycerides withalcohol inthe presence of analkali
catalyst (potassium hydroxide or sodium hydroxide) or an alkoxide (metoxide or etoxide).
The reaction mixture settles and separates into an ester phase and a glycerol phase. The ester
phase contains glycerides, methyl esters and methanol which are puried by distillation
to obtain the nal biodiesel. The remaining unreacted glycerides are reintroduced in the
transesterication reactor together with traces of esters which allow for a better mixture of
the alcohol and oil phases. The glycerol phase which contains glycerol, water and methanol,
is fed into a buffer tank which also contains the glycerol phase from the transesterication
reactor. Once the two glycerol phases are well mixed, they are fed into an acidulation tank
where FFA from the preesterication are added until having an alkaline pH to avoid the
formation of soaps and emulsions. The remaining unreacted FFA is sent again into a FFA
buffer tank to be reused in the preesterication reactor. The glycerol phase is neutralized
and distilled to recuperate glycerol and methanol to be reused within the system. By this
L. Talens et al. / Resources, Conservation and Recycling 51 (2007) 397407 401
two step process, the transesterication takes place at moderate conditions and the biodiesel
conversion reaches its highest rate, above 95% (Mittelbach, 2004).
3.2. Application of ExFA to biodiesel production
Detailed composition of inputs and outputs of the process and the working conditions are
required in order to ensure the accuracy of the results. Two studies were carried out simulta-
neously, an exergy analysis based on published data and an exergy analysis of the biodiesel
production plant BIOCAT(BIOCATis a ctitious name to protect company condentiality).
In dening the system, the pre-treatment of UCO is left out since the pre-treatment
stages are normally done off site by external companies. Therefore, the system includes the
production of biodiesel by the transesterication of UCO, the production of process glycerol
and fertilizer as by-products and the methanol recovery. The biodiesel ow diagram is
divided in 14 operation units where each unit operates at determined temperature, pressure
and mixing rate/settling rate. Each operation units is studied as an isolated system using
exergy to account both materials and energy. The BIOCAT ow diagram does not differ
much from the theoretical process. The only signicant difference is the input ow of
BIOCAT, which has a fraction of non-reacting compounds.
Most operation units are non-reaction operations, so the chemical composition of the
in and out ows does not change. The two principal reactions are the preesterication
and transesterication. The overall process occurs at atmosphere pressure and temperature
range 2585

C. The catalyst ratio for the preesterication step is 1.34% of the total weight
of UCO while the alkoxide catalyst ratio for the transesterication stage is 10% of the
total weight of the UCO. Both catalyst quantities are greater than the amounts calculated
theoretically. The alcohol oil ratio used is 40:1 moles. The alcohol excess is justied for
the reversibility of the transesterication reaction; however the excess amount is also
greater than calculated theoretically. The excess of methanol is recovered in the distillation
of the glycerol (referred to in the diagram as distillation 2). The residence time in the
preesterication step is estimated at 17 min per 1 ton of biodiesel, resulting in a product
yield of 80%. For the transesterication reactor the residence time is 34 min per 1 ton of
biodiesel resulting in 98% conversion to methyl esters.A mass balance of the process is
done based on the material conservation principle. The kinetics for the preesterication,
transesterication and formation of potassium sulfate are assumed rst order. BIOCAT
provided an analysis of the esteried oils and methyl esters which is used to estimate
the UCO composition. By using the analysis data, it is assumed that 80% are glycerides,
18.82% FFA and 1.18% of unknown substances. On the other hand, an average molecular
weight for acids from glycerides and FFA (R
1
, R
2
and R
3
1
) are also assumed in order to
meet the material balance principle. Once each operation unit is independently balanced,
an overall material balance by chemical substances is calculated. The overall mass balance
is calculated for 1 ton of biodiesel produced. As a result, every substance in every process
stream is directly related to the amount of biodiesel which allows direct comparisons
within the biodiesel and glycerol and initial reactants such as the UCO and methanol.
1
R
1
, R
2
and R
3
represent the radicals of the rest of carbon chain that form the methyl esters.
402 L. Talens et al. / Resources, Conservation and Recycling 51 (2007) 397407
Exergy is calculated for chemical substances, mixtures and utilities. The total exergy
through the process is obtained by summing the total chemical exergy input/output from
substances and the exergy input/output from the utilities. In order to calculate the Gibbs
free energy of formation and chemical exergy of glycerides, FFA and biodiesel, an average
molecular weight is assumed for the acids and methyl carbon chains R
1
, R
2
and R
3
. For most
organic compounds, an approximation based on the Shomate equation and Van Krevelin-
Chermin equation, is done to calculate the Gibbs free energy of formation. The chemical
exergyof a substance is determinedbyusingthe standardchemical exergygiveninAppendix
B and Appendix C in Accounting for Resources 2 (Ayres and Ayres, 1999). For the rest of
process substances (sulfuric acid, potassium hydroxide, potassium sulfate and methanol)
the standard Gibbs free energy is taken fromdatabases and the Gibbs free energy at different
temperatures is calculated. The chemical exergy of the substance is determined by using
the standard reference exergy for each element. The chemical exergy is calculated from
the whole range of process temperature (2585

C) in order to meet the process working

parameters.
The total utilities consumed in the process are 22 kW of electricity and 577 kg of steam
(temperature 120

Candpressure 1 atm) per tonof biodiesel produced. The total exergyfrom

electricity delivered to the system is 79 MJ per ton of biodiesel produced. For calculating
the exergy of steam its two components, the physical and chemical exergies are calculated.
The physical exergy of steam is 338 MJ and the chemical exergy is 304 MJ. Thus, the total
exergy of steam is 642 MJ and the total exergy from utilities is 721 MJ per ton of biodiesel
produced.
Once the exergy of each substance is calculated in each process stream, a process ow
diagram of exergy is drawn. Fig. 1 shows the exergy ow in each stream and the type of
operations involved.
4. Results and discussion
Exergy Flow Analysis provides a way for process assessment that can be used as a
tool for identifying material wastes and energy loss, detecting areas needing technological
improvements by calculating the exergetic efciency. Exergy is also a useful indicator for
measuring material potential reactivity and quality, comparing different production pro-
cesses of product substitutes which is especially useful in comparing renewable sources of
energy.
4.1. Identifying material wastes and energy loss
The overall mass and exergy balance of BIOCAT is shown in Fig. 2. In BIOCAT, the
major exergy inputs are UCO and methanol, and the major exergy outputs are biodiesel and
glycerol. It is important to highlight that the overall process waste stream has been reduced
by the production of fertilizer (potassium sulfate) which results from the reaction of sulfu-
ric acid and potassium hydroxide, both substances used as catalysts in the preesterication
and transesterication reactors respectively. Biodiesel technologies using phosphoric acid
and sodium hydroxide as catalysts, even though their standard chemical exergies are lower
L. Talens et al. / Resources, Conservation and Recycling 51 (2007) 397407 403
F
i
g
.
1
.
B
I
O
C
A
T
e
x
e
r
g
y

o
w
d
i
a
g
r
a
m
f
o
r
t
h
e
p
r
o
d
u
c
t
i
o
n
o
f
1
t
o
n
b
i
o
d
i
e
s
e
l
(
M
J
)
.
404 L. Talens et al. / Resources, Conservation and Recycling 51 (2007) 397407
Fig. 2. BIOCAT simplied mass and exergy ow diagram.
(1.87 KJ/g and 1.06 kJ/g, respectively) need greater catalyst ratio thus producing higher
waste exergy streams than by BIOCAT technologies. Process glycerol is sold thereby mini-
mizing the exergy waste stream. In general, most of the unreacting substances (glycerides
and FFA) are normally stored in tanks and then reused in the process to increase the conver-
sion yield and consequently reduce the material input requirement and the waste fraction.
For example, the initial unreacted FFA are used to acidulate the glycerol phase and then
reused in the preesterication reactor to increase the methyl ester conversion yield (see
Fig. 1).
The part of exergy input that is not converted into useful exergy can be referred to as
exergy loss. The exergy loss can be calculated by an exergy balance at constant envi-
ronmental parameters of the system, where it is only necessary to know the composition
of the process inputs (including utilities) and the main products (Ayres et al., 1998). For
BIOCAT, the exergy loss is 1.46%of the total exergy output and is attributed to heat loss and
non-reacting wastes of unknown composition. The wastes are small amount of unknown
non-reacting materials (10.5 kg/ton of biodiesel produced) which are mixed in the cooking
oils and have not been separated before transesterication and consequently driven through
the process.
L. Talens et al. / Resources, Conservation and Recycling 51 (2007) 397407 405
4.2. Exergy as an environmental indicator to measure potential reactivity and quality
Exergy analysis can be used to evaluate the reactivity of substances/products and the qual-
ity of the system output. Since exergy indicates the distance from the equilibrium, it can be
a measure for potential uncontrolled reactions, by dissolution (discharge in watercourses),
evaporation (discharge to the atmosphere) or by continuing reaction to its most stable com-
pounds or until an insoluble solid is formed and deposited on the earths crust (Ayres and
Ayres, 1998). The exergy content of a substance can serve as an indicator of howlikely a sub-
stance is to react in the environment, possibly causing harm to human and other organisms.
The production of biodiesel from UCO allows recycling an industrial and domestic
waste with high exergy content. Thus, although the nal biodiesel has higher exergy than
the original UCO, the reuse of UCO minimizes a waste stream of materials and reduces
UCO environmental impact in water currents and soil. In addition, the exergy supplied by
utilities, the energy resource demand, for the biodiesel production (664 MJ/ton biodiesel)
is lower than the exergy increase of the nal product (982 MJ/ton biodiesel) which means
that the environmental impact due to utilities exergy loss is minimized.
In the case of the byproducts, the potassium sulfate has less potentiality to react and
cause harm than the potassium hydroxide and sulfuric acid (see exergy values from Fig. 2).
In addition potassium sulfate is reused as a fertilizer. Processes using phosphoric acid and
sodium hydroxide as catalysts usually react through the process to form sodium phosphate.
Sodium phosphate can also be used as fertilizer. However, the increase of phosphorous
compounds in water currents promotes the process of eutrophication, having its use conse-
quently a greater environmental impact than potassiumsulphate. The exergy analysis shows
that the process used by BIOCAT contributes to minimize not only waste streams but also
the environmental impact of the system.
The exergy embodied in a substance is also a measure of the material quality. In this
case we upgrade the quality of the UCO (30,367 MJ) to produce biodiesel (31,349 MJ).
Even though UCO could be reused in fuel engines, as are virgin oils, its lower quality and
net caloric derives in greater fuel consumption and cause motor engine problems due to
the presence of impurities. The exergy of the by-product process glycerol in BIOCAT is
3090 MJ, instead of 1914 MJ calculated theoretically, thus that it might need further upgra-
ding depending on its future use. Calculating the quality/exergy of materials is important
to characterize byproducts and wastes and design recycle networks such as eco-industrial
parks to promote closed loop systems and minimize overall resource use.
4.3. Detecting improvement areas by exergetic efciency
The exergetic efciency is dened as the ratio between the useful exergy of a process
and the total exergy used to accomplish that process (Szargut et al., 1988). For BIOCAT, the
exergy of methyl esters (31,349 MJ) is greater than the input exergy embodied in the UCO
(30,367 MJ). The exergetic efciency calculated is 98.54%. The exergetic efciency can be
further improved by process adjustments such as optimizing the FFA ratio in the UCO, also
the content of impurities of the UCO, thereby incrementing the useful exergy (quality) of
the inputs. In general, the exergy loss due to heat loss can also be minimized by reusing
in-process heat thereby minimizing the energy supply. However in BIOCAT, the exergetic
406 L. Talens et al. / Resources, Conservation and Recycling 51 (2007) 397407
efciency of the process is high and those might not be implemented due to economical
costs or other factors.
4.4. Comparisons of processes, products substitutes and renewable resources
Recent studies aimed to compare product substitutes have focused on using the life cycle
assessment (LCA) (Gagnon et al., 2002; Rafaschieri et al., 1999; CIEMAT, 2005; Brentrup
et al., 2001). However most cradle to grave studies give results in different units (equivalent
tones of petroleum, equivalents grams of CO
2
emissions, etc . . .). Developing a database
using exergy accounting for all materials and energy in Joules provides the possibility of
performing comparisons of processes, product substitutes and renewable resources, in terms
of resource consumption, waste generation and emissions, and would also provide accurate
data for LCAs.
This section illustrates how ExFA can also be used for comparing material substitutes,
in this case diesel fuel and biodiesel. Although the best approach for comparing is to
look at both productions, the lack of data on diesel production process and component
fractions has forced to base this comparison on the exergy content of each fuel. Diesel fuel
is a complex hydrocarbon mixture from which composition analyses are hard to nd. The
available analyses are normally grouped by their boiling points, and no specied chemical
formulations are given (Agency, 1988). The exergy of 1 ton of diesel fuel is taken from
literature, 42,383 MJ (Ayres et al., 2001). The exergy of biodiesel is calculated by using
compositional method and the standard chemical exergy, given in Accounting for Resources
2, of each substance forming the biodiesel (Ayres and Ayres, 1999). Thus, the chemical
exergy of biodiesel is 31,349 MJ/ton biodiesel.
Using exergy as a measure of quality, the diesel is a greater quality fuel than biodiesel.
In fact, the net caloric value of diesel is greater than the one from biodiesel which means
that to cover the same distance, greater amount of biodiesel is needed. However, from the
emissions perspective, even though biodiesel consumption is greater, its emissions due to
combustion have less environmental impact and human health effects than diesel emissions
(Mittelbach, 2004). On the other hand, using exergy as an environmental reactivity indicator,
the diesel is more reactive to the environment than biodiesel. Thus, in case any of the fuels
were spilled in water currents or soil, diesel spills have lower degradation rates in soil
and water, thus greater environmental impact than biodiesel. In fact, statistical analysis by
Peterson et al. demonstrate that biodiesel fuels and diesel blended with biodiesel have higher
degradation rates than diesel alone (Knothe et al., 2005).
However, the most concluding result to assess the environmental impact of both is to
consider the life cycle of each. Biodiesel produced by UCO is a renewable resource that
has lower exergy consumption from its collection to production, whereas diesel is a non-
renewable resource that has greater exergy consumption fromits extraction to its production.
5. Conclusions
In conclusion, we can say that ExFA provides a tool for evaluating the environmental
burdens associated with the product, process or activity by identifying and quantifying
L. Talens et al. / Resources, Conservation and Recycling 51 (2007) 397407 407
energyandmaterials usedandwastes releasedtothe environment inthe same comprehensive
framework. ExFA is especially useful in evaluating the production of renewable resources,
since exergy provides an estimation of the resource requirement (energy and material) for a
process inJoules as illustratedinthis paper. Althoughthe methodologyhas traditionallybeen
used in the engineering sector, exergy analysis could also be used to assess the environmental
performance of system and help other industrial ecology tools such as life cycle assessment
and environmental and economical policies related to resource use.
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