Biodiesel Plant Optimisation Study by using

Aspen-HYSYS® Process Simulator

ALEXANDRU TULUC1, PETRICA IANCU1*, VALENTIN PLESU1, JORDI BONET-RUIZ2, GRIGORE BOZGA1, GHEORGHE BUMBAC1
1
University Politehnica of Bucharest, Centre for Technology Transfer in Process Industries, Department of Chemical and
Biochemical Engineering, 1, Gh. Polizu Str., 011061, Bucharest, Romania
2
University of Barcelona, Department of Chemical Engineering, Martí I Franquès, núm. 1, Planta 6, E-08028 Barcelona, Spain

The work presents a simulation and optimisation study for biodiesel synthesis process, based on rapeseed
oil transesterification with methanol in homogeneous catalysis (KOH catalyst). All necessary calculations
are performed with Aspen HYSYS® 8.3 process simulator. For the transesterification reaction, after a thorough
investigation, two perfectly mixed reactors in series are considered, insuring a triglyceride conversion
corresponding to biodiesel standards as EN14214 conditions for biodiesel purity. The optimisation study is
performed based on economic type objective function representing main costs associated to the
transesterification step of the process, for a fixed production. Decision variables are the volume of each
transesterification reactor, the methanol to triglycerides ratio, the temperature of each reactor and the three
phase separator temperature. The restrictions consider limit for total reactors volume, limit for reactors
temperature, three phase separator temperature interval, minimum methyl oleate mass fraction, and
maximum methanol content of biodiesel. The results reveal that the minimum production cost, in the
optimisation problem so formulated, is 14% lower than the reference case. This is achieved considering
higher methanol to oil ratio (e.g. limited however by methanol recycling cost), each reactor temperature
close to maximum limit, and three separation temperature close to the lower limit. The results are dependent
on the quality of kinetic model. Aspen HYSYS® is appropriate instrument to solve flowsheet optimisation.

Keywords: biodiesel plant, kinetic models, transesterification, process simulation,

cost objective function, flowsheet optimisation

Biodiesel is an alternative renewable fuel with rapid
worldwide development especially in last two decades.
Chemically, biodiesel is a mixture of fatty acids alkyl esters,
obtained by the transesterification of triglycerides with light
alcohols, usually methanol or ethanol. The reactions below
represent transesterification with methanol.
(1)
(2)
(3)
Those reactions highly dominated by chemical
equilibrium. As source of triglycerides usually there are
vegetable oils and animal fats as most important [3]. The
reaction takes place in the presence of basic or acid
catalysts, in homogenous or heterogeneous medium [4,
7]. Usually, industrial scale processes are applied with
basic homogenous catalysis, as high conversion in
relatively short time is achieved [5, 7, 9, 12]. Typical basic
catalysts are alkaline hydroxides (NaOH, KOH) or
methoxides (CH 3ONa) in the case of homogenous
catalysis. Calcium oxide, hydrotalcites or sodium silicate
are typical heterogeneous catalysts [4], [10]. Acid catalysts
give relatively poor performance, especially regarding the
amount of time needed to achieve reasonable triglyceride
conversion [15, 16].
The main disadvantages of the homogenous catalysis
are: catalyst recovery is not possible and the equipment
should be corrosion resistant, which involve expensive
materials. In addition, the catalyst removal from the
reaction mixture is not a simple issue.
Industrial scale biodiesel processes are typically setup
in continuous stirred tank reactors, achieving triglycerides
conversion higher than 99.3%. An important process
parameter is the molar ratio between the two reactants
(methanol: tryglicerides). Conventional processes use
molar ratios between 6:1 and 10:1. As the reactions are
slightly exotermic, reaction temperature is relatively low,
usually in the range of 60°C to 80°C. The transesterification
reaction is performed in at least two reactors in series, to
achieve high conversion.
Four different transesterification processes using virgin
canola oil and waste cooking oil as raw materials are
compared in [15] and [16]: alkali-catalyzed process, using
virgin canola oil as raw material; alkali-catalysed process
using waste cooking oil as raw material (including a
pretreatment unit for free fatty acids removal); acid
catalysed process using waste cooking oil as raw material;
the fourth process has same conditions as third process,
the modification consists in hexane or petroleum ether as
a solvent in FAME separation step. The authors compared
the techno-economic performance of four processes, using
Aspen HYSYS® process simulator, and concluded [17] that
the alkali catalysed process using virgin oil (first process)
gives the lowest capital cost.
A techno-economic analysis for a biodiesel synthesis
process was performed also in [1], with the aim to
investigate the influence of critical profitability indicators
on production capacity. The authors concluded that the
raw materials cost accounts for 75 % of the production
cost for small plants, and it is possible to increase up to 90
% for large plants.

* email: p_iancu@chim.upb.ro

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An economic analysis of a biodiesel production plant
was reported in [6]. The raw material for the trans-
esterification process was soybean oil. The predicted
biodiesel cost was 0.4 euro/L and the major contributor to
this cost was also the cost of the oil feedstock, which
accounted for 88% of the total estimated production cost.
The transesterification of soybean oil in alkali based
catalysis was reported in [14]. The reaction temperature
was 60°C and the molar ratio between methanol and oil
was 6:1. Following the economic analysis performed by
the authors, break-even cost for biodiesel was 0.53 euro/L.
Another economic analysis for an alkali based
transesterification plant was reported in [10]. The reaction
temperature was considered 60°C, and the molar ratio
methanol to oil was 6:1. The methanol and water were
removed by vacuum distillation from the biodiesel product.
The estimated biodiesel cost was 0.47 euro/L.
The main studies investigating the economics of
biodiesel synthesis processes, based on computer
simulations are presented in table 1.
In spite of the significant number of simulation studies,
overall biodiesel plant optimisation is less considered in
the open literature. The aim of this work is to evaluate the
main process parameters value, minimizing the cost of
biodiesel production, and to analyze the potential of Aspen-
HYSYS® process simulator for flowsheet optimisation.
Reaction kinetics
Because the transesterification reaction is reversible and
slightly exothermal the equilibrium conversion of
triglycerides is favoured by low temperatures and high
methanol excess.
In order to simulate the transesterification reactor, an
indispensable information is regarding the process kinetics.
One of the first studies regarding the kinetics of the
transesterification reaction was carried out by [8]. The
reaction conditions were: temperature 30-70°C, molar
reaction 6:1, catalyst concentration 0.2% (based on oil
mass) and the raw material was soybean oil.
566 http://www.revistadechimie.ro
Table 1
SIMULATION AND ECONOMIC
STUDIES REGARDING BIODIESEL
SYNTHESIS PROCESSES
Brassica Carinata oil transesterification kinetics was
studied in [11], for following conditions : temperature 25°C
to 65°C, molar ratio methanol to oil 6:1, basic catalyst
concentration 0.5-1.5% KOH (based on oil mass).
Soybean oil transesterification in the presence of BuONa
or sulfuric acid as catalysts were reported in [5]. They
concluded that the basic catalysis was the most indicated
for this kind of reaction. The study was performed in
following conditions : temperature between 20 and 60°C,
reactants molar ratio methanol to oil 6:1, and catalysts
concentration was 1% (based on oil mass).
Sunflower oil transesterification of with methanol kinetic
analysis, in the presence of NaOH as catalyst was reported
in [2]. The kinetic model was developed for following
conditions: temperature 20 and 60°C, methanol to oil molar
ratio 6:1, and catalyst concentration in the interval 0.25-
1% NaOH (based on oil mass).
Based on the reaction mechanism, the majority of
published kinetic models consider second order reaction
rates in molar concentrations (the form 4 to 6), neglecting
the partial solubility of reactants and the non-ideal
behaviour of the reaction medium. The kinetic parameters
published in various studies are presented in table 2.
(4)
(5)
(6)
It the above kinetic models, reaction rate constants are
arrhenius form:
(7)
Table 2
KINETIC PARAMETERS FOR
VARIOUS BIODIESEL SYNTHESIS
STUDIES
REV. CHIM. (Bucharest) ♦ 66 ♦ No. 4 ♦ 2015
Process description
One of the most important issues regarding trans-
esterification of vegetable oils with an alcohol is the
immiscibility of the reactants. Thus, to achieve high
triglyceride conversions, reactants advanced contacting
(intensive mixing) is required. Two types of reactors are
most accessible and commonly used in practice, the
mechanically stirred autoclave, and the tubular reactor. The
mechanical stirred autoclave has the advantage of a very
good reactants mixing, but the required reaction volume
necessary to achieve high conversions is relatively large.
The tubular reactor presents the advantage of a lower
volume necessary to achieve high levels of conversion (due
to low intensity of axial mixing), but intimate reactants
contacting is difficult to be achieved.
To achieve good reactants contacting and high
conversions, in reasonable reaction volumes, a series of
two or more stirred reactors appears to be a suitable
solution. In this work, a flowsheet for the biodiesel
synthesis process, having the structure presented in figure
3 is considered. The raw material streams are mixed in a
static blender, heated at reaction temperature and pumped
in the first reactor autoclave type of the series, at pressure
2 bar, with pump P-100. The effluent of the last reactor of
the series is heated, flashed and fed to three phase
separator D-100. Three streams are obtained : ester phase,
glycerol phase and methanol vapours. As methanol is
favouring the reciprocal miscibility of glycerol and fatty
acid esters, the glycerol separation is promoted by
diminishing methanol concentration in the liquid mixture.
So, for good separation of glycerol product, methanol and
glycerol have to be simultaneously separated from the
mixture. Preliminary calculations shown that an adequate
separation of methanol from liquid phases is insured at
temperature 90°C and a pressure of 0.5 bar in three phase
separator D-100.
Methanol vapour stream from D-100 is condensed in
heat exchanger E-102 and recycled to feed point with pump
P-101. The glycerol stream resulted from three phase
separator D-100 contains the base catalyst which should
be neutralized with a mineral acid (HCl aqueous solution)
in the reactor CSTR-102, and further fed to the rectifying
column T-101 for methanol advanced separation. The raw
glycerol stream resulted from the bottoms of this column
is further purified and valorised in different ways (this step
is not considered in this work). Similarly, the biodiesel
product stream resulted from the separator D-100 is fed to
rectification column T-100 for advanced methanol
separation. To avoid thermal degradation of heavy
components (glycerol and fatty acid esters respectively),
it is necessary to operate rectification columns at low
pressure (0.5 bar), so that the bottoms temperature of these
rectification columns to be lower than 170°C.
Process simulation
A first step of the study consists in a process simulation
at conventional values of operating and constructive
parameters, considering a rapeseed oil transesterification
plant with the capacity of 100,000 t/year. The process is
simulated using Aspen HYSYSÒ v8.3 process simulator. To
simplify the process calculations, the following
assumptions are considered:
- triglyceride content in oil raw material is considered as
pure triolein;
REV. CHIM. (Bucharest) ♦ 66 ♦ No. 4 ♦ 2015 http://www.revistadechimie.ro
- mixing in the two autoclave reactors is considered to
be ideal (Continuous-Stirred Tank Reactor, CSTR).
The thermodynamic model selected to describe the
behaviour of different mixtures involved in the simulation
is NRTL (liquid phase) and ideal (vapour phase) [17].
Previous studies revealed that this model seems to be most
suitable for glycerides transesterification process [15]. The
missing binary coefficients are estimated using UNIFAC
group contribution method. Among the three kinetic
models presented above (table 2), the study published in
[2] is considered as the most appropriate for simulation of
selected process.
One of the most important restrictions of biodiesel
synthesis process is product purity. In agreement with
European Standard EN14214, glycerides concentration in
biodiesel has to be smaller than 0.2 wt % for triglycerides,
0.2 wt % for diglycerides, and 0.7% for monoglycerides.
This purity can be achieved for very high triglyceride
conversion in the reaction section (at least 99.3%). Lower
triglyceride conversion involves expensive separation of
fatty acid methyl esters and unreacted glycerides [16].
A study is carried out to decide the number of reactors
required to achieve high triglycerides conversion. Four plant
configurations are studied, with the transesterification step
performed, alternatively, either in one CSTR reactor or in a
series of two, three or four reactors. Simulation results are
presented in table 3 and figure 1. It is to notice a strong
decrease of total reaction volume with the number of
reactor units to achieve same conversion. This is the result
of the average transesterification rate increase with the
number of reaction stages. Nevertheless, two reactors are
selected to perform the transesterification step, due to
increase of operation and investment expenses associated
with increased number of reactors. All the reaction
conditions are kept constant (methanol flowrate 126 kmol/
h, reaction temperature 65°C, three phase separator
temperature 90°C, for a triglycerides conversion 99.3%).
Following this study two reactors configuration is chosen,
because it has the highest influence on the overall reaction
volume, and there is also relatively simple to implement.
The total reaction volume and its distribution amongst
the two CSTR units considered in the simulation are given
in table 4.
The effluent from the second reactor is heated up to
90°C, then flashed to 0.5 bar pressure, then separated in
three phase separator D-100. The glycerol stream is fed in
CSTR-102, where the catalyst is neutralized with
hydrochloric acid (20% aqueous solution). The separation
of methanol-glycerol mixture is achieved in rectification
column T-101 (4 theoretical trays - NTT). The methanol
contained in biodiesel stream is also separated in T-100
rectification column (with 4 theoretical trays). The bottom
temperature for both rectification columns is maintained
Table 3
REACTOR VOLUME (METHANOL FLOWRATE 126 KMOL/H ,
REACTION TEMPERATURE 65°C, DECANTER OPERATING
TEMPERATURE 90°C, TRIGLYCERIDES CONVERSION 99.3%)
Table 4
REFERENCE WORKING CONDITIONS (FOR
TRIGLYCERIDES CONVERSION 99.3 %)
567

Fig. 1. Total reaction
volume versus the
number of reactors
below 170°C, as long as the pressure is smaller than 0.5
bar. Table 5 summarises the performance of both
rectification columns.
The simulation study shows that a triglyceride
conversion of 99.3 % can be achieved considering two CSTR
reactors in series, having each the volume of 9 m3, operation
temperature 65°C, pressure 2 bar, catalyst concentration
of 1% KOH, based on oil flow rate, and methanol to oil
molar ratio of 9:1 in the feedstock.
Process flowsheet optimisation
Based on the simulation results previously presented,
subsequently an optimisation study is carried out for same
biodiesel plant, with capacity of 100,000 t biodiesel/year.
As the plant capacity and the triglyceride conversion (min
99.3 %) are fixed, the triglyceride feed flowrate is also fixed
and corresponds to approximately 14 kmol/h. All the
separation equipment is considered of fixed capacity, given
by the simulation study previously presented. For
optimisation the decision variables are : methanol to oil
ratio, the volume of each of biodiesel reactors (CSTR-100
and CSTR-101), and the three phase separator D100
temperature.
The objective function to be minimised is annualised
production cost (eq. 8). This represents the summation of
the amortization costs for both CSTR reactors (considering
a depreciation period of 10 years), the cost of reacted
methanol, and the energy costs for different utilities
consumed in flowsheet heat exchangers (E-100, E-101, E-
102, E-103, E-104, etc.), [13].
568 http://www.revistadechimie.ro
Table 5
METHANOL SEPARATION CONDITIONS AND PERFORMANCE IN
COLUMNS T-100 AND T-101
Fobj = Cmethanol + Cutilities + Creactors (8)
Following restrictions are considered for the optimisation
problem:
-total biodiesel reactors volume (CSTR-100 and
CSTR101) – less than 50 m3;
-reactors temperature – less than 65°C;
-three phase separator temperature from 90°C to 140°C;
-methyl oleate mass fraction in biodiesel stream >97%;
-methanol mass fraction in biodiesel stream <0.2%;
Biodiesel reactors (CSTR-100 and CSTR-101) total
volume is restricted to a maximum of 50 m3, because
higher volume can introduce mixing problems, thus
degrading oil overall conversion. The methanol flow rate
has the highest impact on the objective function, so the
limits are less restrictive. Biodiesel synthesis temperature
is limited to 65oC, considering literature reported data (Table
1), to avoid secondary saponification reactions [9]. Three
phase separator temperature is chosen with regard to the
degree of methanol separation required. Higher
temperatures have the disadvantage of higher overall costs,
but at lower temperatures (below 90°C) the separation of
methanol is week, and high content of methanol
determines that biodiesel - glycerol liquid mixture becomes
homogenous, and two liquid phases cannot be separated.
Biodiesel stream concentration restrictions observe the
provisions of European Standard for biodiesel purity.
Prices for raw materials and utilities are presented in
table 6. Vegetable oil is the most expensive raw material
used in the transesterification process. Although methanol
has a higher unit price than oil, its contribution for the overall
process cost is small (the methanol net flow rate is much
smaller as compared to oil flowrate). Vegetable oil is the
most expensive raw material used in the transesterification
process. AspenHYSYS® process simulator has a number of
different methods implemented in its optimisation toolbox.
In this work, the Box method appeared the most suitable.
Fig. 2 Triglycerides
transesterification process
flowsheet
REV. CHIM. (Bucharest) ♦ 66 ♦ No. 4 ♦ 2015
 Table 6
METHANOL AND UTILITIES COSTS
Results and discussions
As the optimisation problem previously formulated is
characterized by four independent variables (methanol to
oil ratio, CSTR-100 volume, CSTR-101 volume, and D-100
temperature) The process is highly nonlinear, the global
extreme proved relatively difficult to be located using Aspen
HYSYS® built-in functions. To identify the global minimum
of the objective function, an important number of
successive optimisation trials with Aspen HYSYS® are
performed with different initial values of the independent
variables. The final results are presented in table 7.
To minimize the objective function value and to keep oil
conversion above 99.3 %, the fresh methanol flowrate
decreases and, as a consequence, the reactors volume is
slightly increased. The optimum results of this problem
represent a trade-off between methanol recycling cost and
equipment costs. Lower methanol recycling cost favours
the excess of methanol (high methanol: oil ratios) and
smaller reactor volumes, and vice versa.
The optimized operating conditions shown in Table 7
correspond to reactors temperature close to maximum
limit.
Comparing with the reference case, considered in the
simulation study presented previously, the objective
function decreases by approximately 14 %, which
represents a significant reduction of production expenses.
Naturally, the correctness of these results is directly
dependent on the quality of the kinetic model used in
calculations. In this context, it is worth to underline that, in
spite of its practical importance, only few kinetic models
considering the reaction reversibility and accurate rate
temperature dependencies for transesterification of
vegetable oils in homogeneous catalysis, are accessible
in open literature.
Conclusions
One of the main steps in the biodiesel synthesis from
vegetable oils is triglyceride transesterification.
Based on a published kinetic model, the present
simulation study is evaluating the reactor volume
necessary for a series of two CSTRs, in conditions of limited
methanol recycling. Several simulations revealed the
influence of reactors number on overall reaction volume
to achieve a given total conversion. The largest volume
difference is between one reactor and a series of two
reactors. Therefore, in the remaining part of the work a
series of two reactors configuration is chosen for the
optimisation study.
An optimisation study is also performed to find optimal
solution for methanol to triglyceride ratio, the volume of
each unit of the reactor series and the temperature of three
phase separator, minimizing the cost of biodiesel
production. As stated above, the accuracy of this study is
essentially dependent on the quality of the available kinetic
model. The study showed that a decrease of 14 %
compared to reference data is achievable by flowsheet
optimisation.
The study underline the capacity of the AspenHYSYS®
process simulator to perform optimisation studies directly
in the simulation environment, on the flowsheet, even for
quite complex flowsheet as that studied in this paper.
REV. CHIM. (Bucharest) ♦ 66 ♦ No. 4 ♦ 2015 http://www.revistadechimie.ro
Table 7
OPTIMAL CONDITIONS
Acknowledgement: Authors are deeply recognising the financial
support of Structural Programme POSCCE, project ID 652.
Notations and abbreviations
·Ci – molar concentration of component i, kmol/m3;
·rj – reaction rate, kmol/(m3·h);
·Ea,i – activation energy for reaction j, kJ/kmol;
·T – reaction temperature, K;
·R – ideal gas constant, 8.31 kJ/(K·kmol);
·k0,j – preexponetial factor for reaction j, m3/(kmol·h);
Indexes :
-j = 1, 2, 3 the reactions of transesterification, presented in (1), (2),
and (3)
-i = TG, DG, MG, GL, ME, M chemical species involved in biodiesel
synthesis
Abbreviations
-TG – triglyceride
-DG – diglyceride
-MG – monoglyceride
-GL – glycerol
-ME – methyl ester of fatty acids
-M – methanol.
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