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CHEMICAL ENGINEERING TRANSACTIONS Volume 21, 2010

Exergy Analysis of Palm Oil Biodiesel Production

The global search for cleaner energy sources has motivated the development of fuels
from oil crops (soybean, sunflower, rapeseed, castor, coconut, palm, etc.), with special
importance of biodiesel from African Palm, due to its high yields (5900 l/ha) and
decrease of emissions of vehicles (mainly carbon monoxide and volatile hydrocarbons).
One of the most important disadvantages of biodiesel is a lower energy output than
fossil fuels and consequently requires greater quantities of energy to be consumed in
order to produce the same energy unit. To evaluate the efficiency of biodiesel
production from palm oil in this work the methodology of exergy analysis was applied.
In this case biodiesel production process includes tree steps: 1. the pre-treatment
performed to hydrolyze triglycerides presented in palm oil, 2. the esterification to fatty
acids using sulfuric acid as catalyst, 3 the separation and purification stage. To evaluate
the energetic and exergetic efficiency at each stage of the process the thermodynamic
analysis was applied, and was found that the largest exergy losses were occasioned by
absence of energy flows integration. Additionally, the methodology developed in this
work could be employed as a tool to achieve more efficient use of energy in the biofuel
industry, also as an instrument for comparison to other biodiesel production processes
from renewable resources (soybean, castor, etc.). This work was supported by the Ibero-
American Program on Science and Technology for Development (CYTED) project
306RTO279 “New technologies for biofuels production” UNESCO codes 330303,
332205, 530603, 330999 and the Colombian Department of Science, Technology and
Innovation COLCIENCIAS, projects CT 475-2007 and CT 272-2008.)

1. Introduction
Nowadays, biodiesel is frequently considered to be a more ecological friendly type of
fuel compared to oil and others fossil fuels because biodiesel have many advantages in
terms of environmental sustainability. Even with the many positive characteristics of
biodiesel, there are also inconveniences to these energy sources. One of the most
important is a lower energy output than fossil fuels and consequently requires greater
quantities of energy to be consumed in order to produce the same energy unit.
Therefore the evaluation of the efficiency of biodiesel production from palm oil is very
important task to assure the sustainability of this process. To solve this problem, in this
work the methodology of exergy analysis was applied.

Please cite this article as: Jaimes W., Acevedo P. and Kafarov V., (2010), Exergy analysis of palm oil biodiesel production, Chemical
Engineering Transactions, 21, 1345-1350 DOI: 10.3303/CET1021225
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According to Dincer and Rosen (2007), energy analysis is the traditional method of
assessing the way energy is used in some physical or chemical process with transfer
and/or conversion of energy. This usually entails performing energy balances, which are
based on the first law of thermodynamic (FLT), and evaluating energy efficiencies.
However, an energy balance provides no information on the degradation of energy or
resources during a process and does not quantify the usefulness or quality of the energy
and mass stream of system and exiting as products and wastes.
The exergy method of analysis overcomes the limitations of the FLT. The concept of
exergy is based on both the FLT and the Second Law Thermodynamic (SLT). Exergy
analysis clearly indicates the locations of energy degradation in a process and can
therefore lead to improved operation or technology, also can quantify the quality of heat
in a waste stream. A main aim of exergy analysis is to identify meaningful (exergy)
efficiencies and the causes and true magnitudes of exergy losses. But, the exergy of a
system depends on the Reference Standard Environment (RSE) and a bad choice of
RSE would lead to erroneous results.
The total exergy involves the physical, chemical, kinetic and potential exergy and
exergy transfer accompanying heat, equation 1, but for some exergy analysis the
potential and kinetic are negligible and the results are valid.
The total exergy is:

(1)

1.1 Metodology
This work was made following a series of guidelines, to determine the Reference
Standard Environment (RSE), the exergy of mass and energy flows and calculate the
exergy efficiencies of process and each unit, based on suggestions of Dincer and Rosen
(2007) and others authors Sorin et al (1998), Talens et. al (2007), Koroneos et. al
(2003), Wall (1988).
At the first stage, the process was simulated to obtain information about the operation
variables as temperature, pressure and flows for each stage of the process and some
properties as enthalpy entropy about this stream, by the principles of conservation of
mass and energy (FLT), equation 2 and 3 respectively.
Principle of conservation of mass:

(2)
The first law of thermodynamics:

(3)
But, but the process was conducted at steady state then the FLT is:

(4)
This stage was performed with the ASPEN HYSYS industrial process simulator. The
simulation of the production of biodiesel was made in three stages: The hydrolysis of
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triglycerides from palm oil, this reaction was made to conditions extremes of
temperature and pressure, 290 °C and 20 MPa with molar ratio water/oil of 60 as
proposed Saka and Minami (2006) in their work.
Then the heterogeneous esterification of fatty acids was considered, this stage was
simulated in a PFR reactor with conditions proposed by Lopez et al. (2008), using
zirconia sulfated catalyst because this catalyst was very active in the transesterification
of soybean and esterification of fatty acids reactions, also the conversions were 98 %
and 92 % for methanolysis and ethanolysis respectively according to Garcia (2008) and
Kumar (2008). The molar ratio ethanol/acid was 100 and the kinetic model for
heterogeneous reactions was Langmuir-Hinshelwood-Hougen-Watson (LHHW) type,
Dossin et al (2009), Balakosa and Chuang (1995), Altıokka and Ödes (2009). The third
step was the simulation of separation systems to purify the biodiesel according to the
ASTM international standards and ethanol was recovered by an azeotropic distillation
column using glycerol at the conditions suggested by Uyazan et al. (2005).
For exergy analysis, first was defined the RSE standard in 25 °C and 1 atm and these
conditions were assessed standard enthalpy and entropy of each current to calculate the
physic exergy by equation 4, also, the chemical standard exergy was evaluate with the
equation 5, both suggested by Ayres et. al (1999) and were defined as the maximum
work that can be extracted when that chemical is transformed by successive reactions
into de reference species in the standard state of the temperature and pressure.

(5)

(6)
Where ΔG°f is the Gibbs energy of formation of the target compound, b°ch is the
chemical exergy of the target compound per mole, b°ch,el is the chemical exergy of the
compound element and nel, is the number of atoms of the element in the compound.
Next, calculate the irreversibility rate of all streams of the process by the equation 7
(7)

2. Result
The simulation of the biodiesel production plant is shown in Figure 1. The above
mentioned three stages in which was divided this process and all flows are also shown
in this scheme. The hydrolysis reactor date: inlet flows 8806 kg/h of palm oil and 12760
kg/h of water, outlet flows 979 kg/h of glycerol and 15240 kg/h of fatty acids. The
esterification reactor date: inlet flows 15240 kg/h of fatty acids and 17960 kg/h of
ethanol (1475 kg/h of fresh ethanol and the rest recycled ethanol). In general, the
process inlet flows: 8806 kg/h of palm oil and 1475 kg/h of ethanol and outlet flows:
9145 kg/h, 1014 kg/h and 121 kg/h of biodiesel, glycerol and water respectively.
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Figure 1: Simulation of Biodiesel production from Palm Oil and using heterogeneous
acid catalyst in Aspen Hysys 2006.5 and ethanol with solvent

The irreversibility rates for all equipments were evaluated and 75.8 % the exergy
efficiency for the hydrolysis reactor and 82.4 % for esterification reactor were obtained.
Total exergy losses of the 10 heat exchangers were 25121 MJ/h, for 5 pumps 15527
MJ/h, for 8 valves 15646 MJ/h, and for 4 distillation columns 48405 MJ/h. respectively.
The table 1 shows efficiencies and exergy losses for some equipment used in this
process.

Table 1 Efficiencies and Irreversibility for some Process Equipment of the Biodiesel
Production
Equipment Efficiencies kJ/h
Pump B1 37 % 618,825
Pump B2 68 % 85,282
Pump B5 67 % 30,571
Heat Exchanger E - 100 98 % 11,300,722
Heat Exchanger E - 101 77 % 20,908,468
Heat Exchanger E - 104 77 % 476,542
Valve VLV - 100 96 % 1,663,487
Valve VLV - 102 82 % 796,848
Valve VLV - 103 28 % 12,936,787
Reactor CRV - 100 80 % 1,095,737
Reactor PFR - 100 98 % 519,170
Column T - 100 25 % 2,645,845
Column T - 101 69 % 5,215,243

The figure 2 shows a general diagram of the process which specifies the mainstream
and physical exergy.
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Figure 2: This diagram represent the general distribution of physic exergy in the
Biodiesel production.

3. Conclusions
The exergy analysis is powerful tool for evaluation of efficiency and sustainability of
biodiesel production processes.
With application of exergy analysis the irreversibility of the overall process was
estimated (106,739 MJ/h) with the impact of separation and purification system about
42 % of total loses.
The exergy analysis also shows that energy integration is needed to reduce energy
losses and to make the process more sustainable.

Acknowledgements
The authors thank to Colombian Department of Science, Technology and Innovation
COLCIENCIAS, to the collaboration projects CT 475-2007 and CT 272-2008 and
Ibero-American Program on Science and Technology for Development (CYTED)
project 306RTO279 “New technologies for biofuels production” UNESCO codes
330303, 332205, 530603, 330999

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