Proceedings of IMECE2007

2007 ASME International Mechanical Engineering Congress and Exposition

November 11-15, 2007, Seattle, Washington, USA

IMECE2007-43502

SIMULATION OF A BIODIESEL CONTINUOUS PRODUCTION PROCESS

USING HYSYS®
Jaime García, Jorge Giraldo, Antonio Bula
Mechanical Engineering Department
Universidad del Norte
Kilómetro 5, Antigua Vía Pto Colombia
Barranquilla, Colombia
abula@uninorte.edu.co

Adrián Ávila
Mechanical Engineering Department
Universidad Pontificia Bolivariana
Monteria, Colombia
adrian.avila@upbmonteria.edu.co

ABSTRACT the analytic models of the chemical processes can be developed

Elements of Chemical Process Engineering were used in
this research to design and simulate two continuous
transesterification processes for the production of biodiesel
from palm oil, using the chemical simulator, HYSYS®. This
design specified the operating conditions of all the equipment
required for the continuous production of biodiesel using
ethanol and methanol as alcohols. The palm oil was modeled as
a mixture of the triglycerides that compose it in greater
proportion, estimating the chemical properties of the substances
that take part in the transesterification reaction, with group
contributions and group interactions theories. Finally, the
quality specifications for biodiesel obtained in both simulations
were analyzed to verify the fulfillment of the properties
required by ASTM (American Society for Testing and
Materials) and EN (European Norms) standards.
INTRODUCTION
The biodiesel production process from palm oil is an issue
that has seen a lot of research in the last years, because of the
need to seek alternatives to fossil fuels or by-products of the
petroleum, due to the instability of the oil price and also, by the
continuous search of reducing the quantity of contaminants
which are emitted to the environment.
For the development of a biodiesel production plant from
palm oil, it is necessary to analyze the different processes
carried out in the production, as for equipment required,
quantity of raw materials, consumption of energy, etc. Although
manually, this mechanism does not permit a simple
generalization of processes, neither to treat the variables
without having to rewrite the complete model. As an alternative
for the solution, commercial simulators of chemical processes
have been developed and they are able to analyze all the
variables of the processes and even, carry out an optimization
and economic evaluation of the plant.
The main purpose of this investigation was to simulate a
plant of continuous biodiesel production from palm oil with the
aid of the software HYSYS®, using ethanol and methanol as
alcohols, and also to analyze the quality specifications of the
final biodiesel obtained in the simulations.
BACKGROUND
Under the specific conditions of production: palm oil –
ethanol – KOH, there are no similar studies developed;
nevertheless, the investigations carried out on the production of
biodiesel on a worldwide basis, there are differences when the
origin of the oil used is brought into consideration. Haas [1]
considered waste cooking oils in the study and concluded that
the utilization of these oils implies half of the costs of raw
materials and contributes to solve the problem of the waste of
virgin vegetable oils. As for catalysts, diverse chemical
substances have been used: sodium hydroxide (NaOH) and
potassium hydroxide (KOH). The use of ethanol has been
borne in the fact of its smaller degree of contamination, the
possibility to obtain it 100% from natural sources. Furthermore,

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 a legal framework in some countries has helped to develop the Therefore, the normal boiling temperature used in the
ethanol industry. simulation is the one obtained by the following expression:
Along with the technical analysis of the production of
biodiesel, some authors include an economic evaluation of the
process keeping in mind changes in raw materials and TB =
∑ N iCi + c (1)
na + b
characteristics of the processes. The presence of glycerol as
byproduct of the reaction requires an alternate analysis, Zhang
Where Ni is the number of groups of each type, Ci is the
et al. [2].
contribution of each group in [K]; a, b and c are the fitting
For the analysis of the production process of biodiesel and
parameters (a=0.6583, b=1.6868, c=84.3395); and n is the
the correlation among the different variables of the process
number of atoms in the analyzed molecule without considering
with the final yield of biodiesel, commercial simulators have
the atoms of hydrogen. Table 1 and Table 2 present the results
been used to evaluate the conditions in which the plant will
for the normal boiling point for the diolein molecule illustrated
work and based on this, estimate the operating and equipment
in Fig. 2., based on its organic groups.
costs of the process.
Table 1. Results of the contribution group theory for the diolein
molecule.
ESTIMATION OF CHEMICAL AND PHYSICAL
PROPERTIES NiCi
Groups Contribution Frecuency
Vegetable oils are organic compounds originated from
COO 636.202 2 1272.404
fruits or seeds such as sunflower, soy, palm, rapeseed, etc.
C=C 475.7958 2 951.5916
Their chemical composition is such that three fatty acids are
connected to a molecule of glycerin. In Fig. 1 the molecular OH 390.2446 1 390.2446
structure of a characteristic triglyceride is shown, tripalmitin, CH3 177.3066 2 354.6132
formed by the union of three palmitic acids in a molecule of C 266.8769 3 800.6307
glycerin. Similarly, its respective diglyceride and CH2 239.4531 28 6704.6868
monoglyceride are also shown. OH-COO 211.6814 0.022727273 4.810940909
COO-OH 211.6814 0.022727273 4.810940909
H GLYCERIN H FATTY ACIDS H COO-COO 431.099 0.022727273 9.797704545
| | |
H - C – COO – (CH2)12 - CH3 H - C – OH H - C – OH
| | |
H – C – COO - (CH2)12 - CH3 H – C – COO - (CH2)12 - CH3 H – C – OH Table 2. Temperature calculation based on the contribution group
| | | theory for the diolein molecule.
H – C – COO - (CH2)12 - CH3 H – C – COO - (CH2)12 - CH3 H – C – COO - (CH2)12 - CH3
| | |
H H H
TRIPALMITIN DIPALMITIN MONOPALMITIN a b c Atoms
0.658 1.6868 84.3395 44
Figure 1. Molecular structure of triglycerides, diglycerides and
a
monoglycerides. ΣNiCi n +b
10494 13.761738
In the simulation of chemical processes, necessary
components are not always included in the gallery of the
Tb (K) 846.590
simulators, that is why is necessary to create these compounds
from their properties. The properties estimation methods from
organic groups contribution permit to calculate the normal Tb (°C) 573.59
boiling point of a substance based on its molecular structure
and the interactions among the different organic groups that Table 3 shows the boiling temperature for the different
compose it. For the properties estimation of pure substances, components considered in the simulation, calculated according
the most used group contribution methods are the presented by to the method presented in Nanoolal et al. [4].
Cordes and Rarey [3]. In these methods, the property of a
compound is function of parameters dependent of its structure.
The method used to calculate the normal boiling point of
all the substances involved in the transesterification reaction
was the one presented by Nanoolal et al. [4]. According to this
author, the maximum error introduced in this approximation is
quite insignificant, only 10 K for the boiling temperature.

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 The known stream conditions were created: Oil, Alcohol
COO (Ethanol or Methanol) and Catalyst (KOH or NaOH). The
C=C streams of alcohol and catalyst are mixed to form the ethoxide
CH2 that enters the reactor (ERV-100 or R-1). This mixture was
OH modeled using a Mixer, equipment that simulates the mixture
of two or more streams. The simulation also includes this
equipment for the mixture of water and hydrochloric acid used
in the subsequent purification of the biodiesel.
It is necessary to specify pumps (B-1, B-2) to elevate the
pressure of the streams to the specified for the
CH3
transesterification reaction. In this case, a pressure over the
atmospheric is needed to avoid the partial evaporation of the
alcohol in the reaction, resulting in an increase of its boiling
Figure 2. Diolein molecule with its organic groups. temperature. Also the stream at the exit of the distillation tower
should enter a pump (B-3) to carry the pressure again to
Table 3. Boiling temperature of the Palm Oil components atmospheric, considering that the distillation tower works under
vacuum pressures.
Component Chemical Formula Boiling Point In the process, two heat exchangers are used, one in the
Triolein C57H104O6 952.387 °K initial phase (E-1) to elevate the temperature of the Oil stream
to the temperature stipulated for the reaction and the other (E-2
Tripalmitin C51H98O6 916.184 °K
or E-100) in the final phases of the process to cool down the
Trilinolein C57H98O6 951.838 °K stream that exits the distillation tower and guarantee favorable
Diolein C39H72O5 846.59 °K conditions for the purification.
The reaction is carried out in an equilibrium reactor. The
Dipalmitin C35H68O5 816.95°K performance of these reactors in the steady state simulation is
Dilinolein C39H68O5 846.41 °K not influenced by the volume, neither by the level of liquids.
The stream that is extracted from the reactor feeds a distillation
Monoolein C21H40O4 714.1 °K
tower, responsible for the separation of the remaining alcohol
Monopalmitin C19H38O4 694.03 °K that is undesirable in the final biodiesel.
Monolinolein C21H38O4 713.8 °K
Etthyl Oleate C20H38O2 688.25 °K
Ethyl Palmitate C18H36O2 686.5 °K
Ethyl Linoleate C20H36O2 687.92 °K

SIMULATION OF THE BIODIESEL PRODUCTION

PROCESS
To begin the simulation of the production process of
biodiesel in HYSYS®, it is necessary to define the Fluid
Package which controls and determines the thermodynamic
model used for the development of the calculations used for all
the properties of the streams. For non-polar compounds or
slightly polar, equations of state such as Peng Robinson or SRK
(Soave Redlich Kwong) are appropriate; nevertheless, in highly
polar ideal mixtures, models of activity like NRTL (Non
Random Two Liquid) or UNIQUAC (Universal Quasi
Chemical) can produce better results. According to
investigations carried out, the NRTL fluid package is
appropriate for the simulation; however, its selection presented
some inconveniences in the final phases of the process, for
which UNIQUAC fluid package was then chosen, as suggested
in some investigations, Zhang et al. [2] and Narváez et al [5],
adjusting favorably to the conditions of the process.
Figure 3. Mass flow of glycerol vs. Mass flow of water, used in the
purification of biodiesel.
The purification of the biodiesel implies withdrawing the
excess of glycerol, catalyst and soaps in the stream, by adding
water to wash the biodiesel. The quantity of necessary water to
remove the maximum quantity of glycerol was analyzed using
the Databook, a tool that HYSYS® includes for the behavior
analysis of some variables with regard to other in the process.
For this case, the water mass flow was analyzed in order to
extract the maximum mass flow of glycerol. Although the ideal
scenario would be to withdraw all the glycerol, it is not
technically feasible. Therefore, a flow of water is chosen that
guarantee an adequate extraction of glycerol, Fig. 3.

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 Figure 4. Process flowsheet for the biodiesel production process with ethanol.

Figure 5. Process flowsheet for the biodiesel production process with methanol.

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 The remaining catalyst in the biodiesel stream should be possible to state that the behavior of the reaction kinetics will
separated to avoid soap formation along with undesirable remain the same.
substances that degrade the biodiesel obtained. This is why 1N
hydrochloric acid is used in the reaction, to guarantee that the Table 5. Global reaction conversion percentages comparison.
catalyst conversion percentage is near to 100% by dragging the
KCl product of the neutralization reaction. This process not Triglyceride % Mass 30°C 40°C 50°C 60°C
only consists of the addition of acid to transform the catalyst Tripalmitin 43% 56.24 56.02 54.58 52.43
Triolein 45% 93.82 95.35 95.81 95.52
used in the reaction, but its goal is also to achieve a neutral pH Trilinolein 12% 90.58 89.33 89.06 89.56
in the biodiesel obtained.
Finally a separation column is used (X-100) to evaporate Global Simulation 77.27 77.72 77.27 76.28
the water product of the washing phase and the neutralization Global Ávila 77.70 87.81 88.20 87.97
reaction. In the same way that the values for pressures and Percentage Error 0.6% 11.5% 12.4% 13.3%
temperatures in the distillation tower were determined, the
values in this column are introduced so that the stream of final Table 6. Yields (kg/hr) for the biodiesel production process
biodiesel stays below the degradation temperature along with
the specification of the variables that want be separated, for this Ethanol Methanol
case alcohol and water. Palm Oil 3000 3000
Alcohol 976.28 1302.74
The continuous process flowsheet using ethanol is shown Catalyst 12.69 13.03
in Figure 4. This diagram includes equipment, flow and energy Glycerol 872.3 1393.98
streams for the designed process explained above. A simulation Biodiesel 3160.37 3027.1
using methanol as feedstock was also carried out and the
resultant process flowsheet diagram is shown in Figure 5.

RESULTS AND DISCUSSION

The results are intimately related to the quality
specifications of the biodiesel according to the ASTM D6751
[6] or the EN14214 [7]. In Table 4, the specifications of the
biodiesel obtained in the simulations are shown. These results
were obtained directly from the simulation, excepting the
corresponding to density (15°C) and total glycerol, which are
found according to the standards D6584 [8] and EN 14214[7].

Table 4. Quality specifications of the biodiesel obtained.

Figure 6. Influence of the temperature of reaction on the
Porperties Methanol Ethanol Limit Standard production of ethyl esters.
3
Density at 15°C (g/cm ) 0.883 0.91 0.86-0.9 EN 14214
Kinematic Viscosity at 40 °C (cSt) - 1.36 3.5-6.0 ASTM D6751
Water Content (mg/kg) 0 0 < 500 ASTM D6751 Finally the yields for the production process are shown,
Alcohol Content (% mass) 0 0.08 < 0.2 ASTM D6751 based on a plant capacity of 80 ton/day equivalent to 3000
Edters Content (% mass) 87.73 65.84 > 96.5 EN 14214
Free Glycerol (% mass) 0.27 0.39 < 0.02 ASTM D6751
kg/hr, (Table 6). According to these results, it can be observed
Total Glycerol (% mass) 1.67 4.92 0.24 ASTM D6751 that Ethanol has a greater production of biodiesel than
Methanol when palm oil is used as vegetable oil.
Based on the conversion yield obtained and the proportion
of each one of the triglycerides in the palm oil, averages of the
global conversion yield were calculated to analyze the ASSUMPTIONS
percentage error according to Ávila [9] and Ávila et al [10], For the simulations carried out, the following statements
Table 5. should be considered for future investigations:
It is also possible to take advantage of working with the - Raw materials have been considered 100% pure since the
simulation of chemical processes to analyze the influence of processes require such conditions. This condition should be
certain variables. It is observed that with a temperature of 75°C verified before using any raw materials in the process because
the maximum yield of ethyl esters can be obtained, for specific of the possibility to form parallel reactions of saponification,
conditions of mass flow, alcohol/oil molar rate and pressure, though not considered in the simulation, are actually one of the
(Fig. 6). However, it is necessary to emphasize that the kinetic most important factors to guarantee an adequate conversion of
data introduced to the simulation are completely valid for biodiesel.
temperatures between 30ºC and 60ºC, outside this range is not - The ethanol is quite hygroscopic, this is, absorbs easily
humidity from the environment. It should be guaranteed

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 complete air tightness in each one of the phases of the process.
However, in the simulation this property was not considered,
assuming the ethanol 100% pure at all times.
- The mixture of the alcohol with the catalyst is a reaction,
in which some water is produced. Such water influences, as has
already been commented, the formation of soaps during the
transesterification reaction; this effect should be kept in mind
for the subsequent purification phases of biodiesel.
- The distillation of the ethanol is azeotropic, that is, the
maximum percentage of purity that can be obtained in an
ethanol distillation process is around the 95%. For such reason,
the recovery of ethanol for its subsequent utilization in the
process is not viable until a process of alcohol drying is
defined. However, in the simulation a distillation is included
with the sole purpose of separating the remaining alcohol from
the reaction.
- The chemical properties estimation of the substances
used in the simulation, as well as the thermodynamic models
included in the simulator induce errors that should be kept in
mind in subsequent studies to analyze the influence of such
errors in the results obtained.
CONCLUSIONS
The viability of a plant comprises technological and
economic aspects. Although the technical evaluation of the
continuous production process through steady state simulations
can be understood as a starting point for the development of a
pilot plant, a dynamic simulation and subsequent economic
evaluation turns out to be indispensable to determine the
feasibility of the project, García and Giraldo [11].
ACKNOWLEDGMENTS
The authors wish to thank UREMA Research Group for
their support in the development of this investigation and Dr.
Jürgen Rarey for his help in the estimation of the chemical
compounds. The authors also want to acknowledge Dr. Marco
Sanjuan for his help in the simulation of the chemical process.
REFERENCES
[1] Haas, M., MacAloon, A., Yee, W., Foglia, T., 2006, “A
process model to estimate biodiesel production costs”.
Bioresource Technology, 97(4), pp. 671- 678.
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[2] Zhang, Y., Dubé M., Kates M., 2003, “Biodiesel
production from waste cooking oil: 1. Process design and
technological assessment”. Bioresource Technology, 89(1), pp.
1-16.
[3] Cordes, W., and Rarey, J., 2002, “A new method for the
estimation of the normal boiling point of non-electrolyte
organic compounds”. Fluid Phase Equilibria, 201(2), pp. 409-
433.
[4] Nannolal, Y., Rarey, J., Ramjugernath, D., Cordes, E.,
2004, “Estimation of pure component properties Part 1:
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[5] Narváez, P., Castañeda, L., Rincón, S., Sánchez, F.,
Torres, J., 2005, “Continuous Process for the Production of
Fatty Acid Methyl Esters in a Falling Liquid-liquid Film
Reactor”, 2nd Mercosur Congress of Chemical Engineering
and 4th Mercosur Congress on Process System Engineering,
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[6] ASTM, 2003, “Standard Specification for Biodiesel
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American Society for Testing and Materials (ASTM), D6751-
03.
[7] AENOR. 2003, “Ésteres de metilo de ácidos graos
(FAME) para motores diesel”. Asociación Española de
Normalización y Certificación (AENOR), UNE 14214. Madrid.
[8] ASTM, 2000, “Test Method for Determination of Free
and Total Glycerine in B100 Biodiesel Methyl Esters by Gas
Chromatography”, American Society for Testing and Materials
(ASTM), D6584-00.
[9] Ávila, A., 2006, “Desarrollo de la cinética química de
la reacción de transesterificación de la oleina de palma”, M.Sc.
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[10] Ávila, A., Bula, A. and Sanjuán, H, 2007, “Cinética de
la Transesterificación de la Oleica de Palma Africana con
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aceite de palma”, M.E. thesis, Universidad del Norte,
Barranquilla.
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