Received: 23 February 2018 Revised: 28 March 2019 Accepted: 29 April 2019

DOI: 10.1002/ep.13264

SUSTAINABLE ENERGY

Simulation process of biodiesel production plant

Abozar Salehi1 | Abdolreza Karbassi1 | Barat Ghobadian2 | Amir Ghasemi1 |

Amir Doustgani3

1
School of Environment, College of
Engineering, University of Tehran, Tehran, Iran
2
Department of Mechanics of Biosystems
Engineering, Tarbiat Modares University,
Tehran, Iran
3
Department of Chemical Engineering, College
of Engineering, University of Zanjan,
Zanjan, Iran
Correspondence
Abdolreza Karbassi, School of Environment,
College of Engineering, University of Tehran,
Tehran, Iran.
Email: akarbasi@ut.ac.ir
Abstract
The increasing global demands for fossil fuels have resulted in the release of large
quantity of pollutants and reduction of the available resources. Owing to this fact,
alternatives to fossil fuels, like biodiesel, are essential for the survival of the existing
resources and the decrease of environmental contamination. In the current study,
the technical assessment of five continuous biodiesel production processes was
designed and simulated with the Aspen Plus v8.6 software. In order to convert virgin
vegetable oil (VVO) as well as waste cooking oil (WCO) to biodiesel, alkali-catalyzed
and acid-catalyzed processes were utilized in the first three processes. In the fourth
and fifth processes, the two-step supercritical methanol method (noncatalytic) and
the acid-catalyzed process were adopted by hexane extraction to transform the
WCO to biodiesel. According to the technical assessment, the two-step supercritical
methanol process has the lowest number of operating units; however, it has the low-
est purity of FAME (98.47%). The highest purity of glycerol (99.98%) and FAME
(99.7%) belong to Processes 3 and 1, respectively. As a result, the homogeneous acid
catalytic process of WCO and the two-step supercritical methanol process are the
best choices in terms of technical evaluation among all the examined processes.

KEYWORDS
Aspen plus, biodiesel, simulation process, transesterification, waste cooking oil

1 | I N T RO D UC T I O N biodiesel. Therefore, it can be concluded that biodiesel is considered as

Energy, which is mainly supplied by renewable and fossil resources, exists
in various forms, including chemical, thermal, nuclear, and so forth.1-3 Fos-
sil fuels as major energy sources currently supply most of the world's
energy demands. Satisfying these demands results in the increased
amount of combustion products, which causes environmental problems.4
In order to tackle this issue, alternative energy sources like biodiesel can
be used. Biodiesel, as an environmentally friendly fuel, whose characteris-
5
tics are similar to those of conventional or fossil diesel, can reduce the
amount of UHC, CO2, CO, Sox, and PM from engine exhaust. As an exam-
ple, biodiesel can reduce carbon dioxide emissions by 78%.6 However,
only a small amount of nitrogen oxides is produced, which may decreased
7,8
by adjusting fuel injection timing. Proper lubrication, high flash point,
high cetane number, and CFPP are among the other advantages of using
an appropriate alternative to diesel.9 The first generation of commercially
produced biodiesel is essentially derived from edible oil such as palm, soy-
bean, canola, and rapeseed.10 While the continued use of biodiesel can
reduce greenhouse gas emissions and increase security of energy supply,
in the long term, it endangers the supply of edible oil, increases its price,
and consequently, expands poverty. In order to overcome the mentioned
problems, the second-generation biodiesel, which is manufactured from
nonedible oil, can be used.11
It is worth mentioning that, viscosity of vegetable oil is 10–17 times
higher than diesel.12,13 Accordingly, numerous strategies, including trans-
esterification, microemulsion, pyrolysis, and catalytic cracking have been
suggested to reduce viscosity.14 Among these strategies, trans-
esterification technique has expanded rapidly due to its high efficiency,
low cost, user-friendly technology as well as appropriate quality of fuel.15

Environ Prog Sustainable Energy. 2019;e13264. wileyonlinelibrary.com/journal/ep © 2019 American Institute of Chemical Engineers 1 of 12
https://doi.org/10.1002/ep.13264
2 of 12
Transesterification refers to the chemical reaction between oil (vegetable
oil or animal fat) and alcohol (such as methanol) in the presence of a cata-
lyst (alkali, acid, or enzyme) to produce biodiesel (methyl ester) and
glycerol.16
In recent years, researchers have conducted numerous studies on
simulation and design of biodiesel plants by the HYSYS and the Aspen
Plus software.17-25
From 2005 to 2016, global energy demand in the transportation
sector rose by an average of 2% annually, which accounts for 28% of
total energy consumption and 23% of greenhouse gas emissions.26
The road transport sector accounts for 93% of the energy consump-
tion.27,28 4% of the global energy demand in the transport sector is
29
supplied by biofuels. In Iran, 1.5 million tons of edible oil is con-
sumed annually. In total, about 300,000 tons of WCO is produced,
which represents a significant biodiesel production potential.30 It
should be pointed out that production of biodiesel from various mate-
rials have been studied by some researchers.31,32
The purpose of the present study was to simulate the biodiesel
production plant using fresh vegetable oil and WCO with the ASPEN
PLUS V8.6 simulator software.
2 | METHODOLOGY
The simulation process mainly involves the definition of chemical mate-
rials, choice of thermodynamic model, determination of the plant capac-
ity, flowsheet of the simulation process using the required unit
operations, and definition of input conditions (flow, temperature, pres-
sure, and other conditions). Palm oil is selected as the raw material in both
VVO and WCO. Triglyceride with triolein 90 wt% (C57H104O6), free fatty
acid in WCO by oleic acid (C18H34O2) 10 wt%, as well as methyl oleate or
oleic acid methyl ester (C19H36O2) are introduced as a biodiesel (FAME)
in the Aspen Plus simulator. In addition, glycerin (C3H8O3) is a by-product
of the process. Phosphoric acid and calcium oxide are used as neutralizing
agents for sodium hydroxide and sulfuric acid catalysts.
Given that, there are high polar materials such as CH3OH and
glycerin. NRTL model is utilized to determine the coefficients of activ-
ity of materials. Moreover, in the forth process, based on the use of
supercritical methanol, the RK-ASPEN thermodynamic model is
selected to predict the activity coefficients of the material in the liquid
phase. For those materials such as CH3OH-C19H36O2, C3H8O3-
C19H36O2, and H2SO4 with any other substance, whose coefficients
of interaction parameters are not available, it is estimated that retrieve
parameters module found in the software tools menu can be used.
Vapor pressure, evaporation heat, ideal gas heat capacity, molar
volume, viscosity, and surface tension of the liquid are the most signif-
icant properties that should be determined.
Given that the number of cultural and industrial restaurants and self-
service centers in Tehran province is 20 thousand units, and each unit
produces 1 kg of frying oil daily, 7,300 tons of restaurant WCO is col-
lected annually. If the conversion efficiency of oil to biodiesel is estimated
as 96%, it will require a plant with a capacity of about 7,200 tons per year.
SALEHI ET AL.
Of course, in this calculation, the kitchen waste oil at residential, commer-
cial, educational, and military centers is ignored.
3 | PROCESS DESIGN
Five continuous acid and alkaline catalyst processes were designed
and simulated using the ASPEN PLUS V8.6 software. The number of
theoretical stages and the reflux ratio for glycerin and biodiesel distil-
lation and methanol recycling towers are the same for all processes.17
3.1 | The alkali catalysis of VVO (Process 1)
The temperature, pressure, mass fraction of catalyst and trans-
esterification reaction time, and the conversion factor of the reactor
are derived from Zhang et al research.17 The sodium hydroxide, water
and phosphoric acid mass flowrates, as well as the methanol to the oil
molar ratio are obtained with this simulation.
3.1.1 | Transesterification unit
Figure 1 presents the flowsheet of the continuous alkaline catalysis pro-
cess of VVO. Sodium hydroxide with a purity of 50% (stream 101 at
9.22 kg/hr) and fresh methanol (stream 100 at 153.6 kg/hr) are mixed in
MIXER-1 and then pumped by PUMP-1 to the MIXER-2. The VVO
(stream 104 at 921.7 kg/hr) is pumped to MIXER-2 by PUMP-2, where it
is mixed with recycled methanol with a purity of 95.6% (stream 109 at
221 kg/hr) and stream 103, then heated by HEATER-1 to 60
C.
In the reactor R-CSTR, the transesterification reaction with a
methanol to oil molar ratio of 4:61 methanol to oil molar ratio of 4:61
and 1 wt% NaOH (based on oil) is carried out at 60
C and 400 kPa for
60 min. Simulation of the CSTR reactor requires kinetic formulas and
data such as constant equilibrium and activation energy. This informa-
tion is demonstrated in Tables 1 and 2 and also Equation (1). In Equa-
tion (1), the factor n is equal to zero and the concentration is in terms
of molarity.33 The stream 108 is sent from the reactor to the methanol
distillation tower T-MEOH.

n


T E YN ai 1 1
r=k exp − C i − ðEq1Þ
T0 RT i=1 T T0
3.1.2 | Methanol recovery unit
Methanol distillation tower T-MEOH with five theoretical stages and
reflux ratio of 2, as well as a total condenser is used to separate meth-
anol and other materials appropriately. Distilled methanol (stream
109) with a purity of 95.6% is sent as a recycled input to MIXER-2. In
order to maintain the bottom product temperature (less than 150
C)
of the distillation tower, the vacuum distillation tower is selected. The
bottom product of the distillation tower (stream 110) at 53.5
C and
0.2 bar pressure is pumped by PUMP-3 to HEATER-2, heated to 60
C
and then sent to a water tower T-WASH.
SALEHI ET AL. 3 of 12

FIGURE 1 Homogeneous catalytic process of alkaline virgin vegetable oil (Process 1) [Colour figure can be viewed at wileyonlinelibrary.com]

TABLE 1 The kinetic parameters for CSTR reactor

Reaction type Reactions k (T0 = 323.15 K) E (kcal/mol)

TG ! DG 1. OOO a + methanol ! methyl-O + OOb 0.02311 13.5
DG ! TG 2. OO + methyl-O ! OOO + methanol 0.001867 10.3
DG ! MG 3. OO + methanol ! methyl-O + 1-Oc 0.10659 17.4
MG ! DG 4. Methyl-O + 1-O ! OO + methanol 0.002217 16.2
MG ! FAME 5. 1-O + methanol ! glycerol + methyl-O 0.05754 6.2
FAME ! MG 6. Glycerol + methyl-O ! methanol +1-O 0.000267 11.9
a
TG (OOO) = TRIOLEIN.
b
MG(1-O) = MONOOLEIN.
c
DG(OO) = 1,3-DIOLEIN.

3.1.3 | Water washing unit ESTER has five theoretical stages and reflux ratio of 2. The output stream
116 is discharged from the separator to the distillation tower T-ESTER.
FAME is separated from glycerin, methanol and catalyst in the washing
Operation under vacuum conditions is used in distillation tower to keep
unit. It should be stated that complete separation cannot be achieved
the temperature down. On top of the distillation tower, a partial con-
with a gravity settler. Therefore, the tower T-WASH is used in this study
denser for easy separation of FAME and methanol is applied. H2O and
with five theoretical stages. By adding 50 kg/hr of water (with a water to
MEOH are eliminated as vent gases (flow MEOH-H2O) on the top of the
oil molar ratio of 2:67) at 25
C (stream 113), FAME (stream 112) is sepa-
tower. The final FAME (909.103 kg/hr) product is obtained as the distilled
rated from glycerin, methanol, and catalyst. As a result, a liquid–liquid sep-
liquid at 150
C and 0.1 atm. Unconverted oil remains in the lower part of
arator is used to separate biodiesel from other materials. The upper flow
the distillation tower T-ESTER, so only a small amount of unrefined oil
of the separator (stream 116) containing 97.4% FAME is sent to the distil-
lation tower of the ester. In the stream 116, the total amounts of (stream waste at 14.23 kg/hr) is removed and treated as waste.

unconverted oil (triolein), methanol and water are less than 1 wt%. The
bottom stream (stream 117) is sent to the neutralizing reactor R-NEUTR
to remove the alkaline catalyst.
3.1.4 | FAME purification unit
This stage aims at achieving biodiesel in accordance with the ASTM stan-
dard specifications (more than 99.6%). The applied distillation tower T-
3.1.5 | Alkaline catalyst removal unit
In order to neutralize and remove the catalyst, the conversion reactor is
used, which does not require reaction kinetic formulas, and the reactor is
only simulated by entering the chemical reaction equation (stoichiometric
coefficients), temperature, pressure, and the conversion percentage of
the reactor.17 The stream 117 is fed to the neutralizing reactor R-NEUTR.
4 of 12 SALEHI ET AL.

In order to remove sodium hydroxide, 50 kg/hr phosphoric acid (85%) is
added to the reactor (stream 118). The entire NaOH is converted into
Na3PO4 under Equation (2), in a neutralizing reactor at 60
C and atmo-
spheric pressure. The resulting Na3PO4 (stream 119 at 1.537 kg/hr) is
removed in gravity separator SEP-2.
3 NaOH + H3 PO4 ! Na3 PO4 + 3 H2 O 100% conversion of NaOH ðEq2Þ
3.1.6 | Glycerin purification unit
The stream 120 contains 45.6 wt% of glycerol. As high-purity glycerin
(e.g., 92 wt%) is preferred, this stream is passed through the distilla-
tion tower T-GLYCEROL to remove more water and methanol.
Accordingly, glycerin purification tower is used with five theoretical
stages and the reflux ratio of 2. During distillation (stream 121), water
and methanol are removed. 89 kg/hr glycerol is obtained as a by-
product at the bottom stream.
3.2 | Homogeneous alkaline catalytic process of
WCO (Process 2)
Temperature, pressure, mass percent of catalyst and conversion per-
centage of the esterification reactor are derived from Zhang et al
research. Accordingly, the conversion reactor is used, and there is no
need for reaction kinetic formulas. The reactor is only simulated by
entering the chemical reaction equation (stoichiometric coefficients),
temperature and pressure, and the conversion percent of the reac-
tor.17 The sodium hydroxide, water and sulfuric acid, and glycerin
mass flow rates as well as the methanol to the oil molar ratio are
obtained from this simulation.
The pretreatment unit is used to address the sensitivity of the
alkaline catalytic process to the amount of acid in the WCO.
According to Figure 2, the pretreatment unit consists of three units of
esterification, glycerol washing, and methanol recovery.
3.2.1 | Esterification unit
Initially, 153.6 kg/hr of fresh methanol (stream 100) with methanol to
oil molar ratio of 4:61 is mixed with 260 kg/hr of recycled methanol
(stream S-10) and 46 kg/hr of sulfuric acid (stream 101), and then
pumped to the esterification reactor R-ESTR by Pump-1. WCO stream
contains 90 wt% triolein and 10 wt% oleic acid.
Since the alkaline catalyst is sensitive to the amount of fatty acid,
the triolein is separated from the oleic acid in the separator SEP-1.
The oleic acid stream (stream 102 at 92.17 kg/hr) containing 10% of

TABLE 2 Number of main processing units required for each process (requiring stainless steel)

Process 1 Process 2 Process 3 Process 4 Process 5

Pump 3(0) 5(4) 1(2) 2(0) 4(2)
Exchanger 2(0) 3(1) 1(1) 4(0) 2(1)
Reactor 1(1) 1(2) 0(4) 2(0) 0(4)
Separator 1(1) 2(3) 1(1) 1(0) 2(1)
Tower 3(1) 3(3) 2(1) 2(0) 4(1)
Sum 13 27 14 11 21

F I G U R E 2 Pretreatment unit alkaline catalytic process of waste cooking oil (Process 2) [Colour figure can be viewed at
wileyonlinelibrary.com]
SALEHI ET AL.
free fatty acid is heated to 70
C in a heat exchanger HEATER-1
before entering the R-ESTR reactor.
Esterification reaction is performed at 70
C, 400 kPa and metha-
nol to oil molar ratio of 4:61. According to Equation (3), in the esterifi-
cation reactor R-ESTR, all of the free fatty acid is converted into
METHY-01 in the presence of a H2SO4 catalyst.
MEOH + OLEIC− 01 ! METHY−01 + H2 O 100%conversion of OLEIC−01
ðEq3Þ
Then, to remove the water, the outlet flow of the reactor (stream
S-4) enters the separator SEP-2. After complete removal of water, the
stream S-5 is cooled down to 25
C, and eventually the outflow of the
COOLER from PUMP-3 is sent to the glycerin tower T-EXTRA-1 to
remove sulfuric acid.
3.2.2 | Glycerol washing unit
The addition of 100 kg/hr of glycerin (stream 103) at 25
C and 1 bar
substantially removes about 99% of sulfuric acid from the stream S-7
after the 5th stage of the washing process (stream EXTRACT). The
stream EXTRACT of the glycerin washing is sent to the separator
SEP-3 to separate glycerin and oil. The stream S-8 is sent to the meth-
anol recovery distillation tower. Finally, the stream oil (stream OIL)
with 95.82 kg/hr (free oil of free fatty acid) is sent from the separator
as transesterified processed oil to the reactor R-CONVER.
3.2.3 | Methanol recovery unit
In the distillation tower T-MEOH-1, five theoretical stages and reflux
ratio of 2 are employed. At 83.2
C and 2 atm, 65% of the total dis-
tilled methanol is returned by the PUMP-5 to the esterification reac-
tor R-ESTR.
The bottom stream of the distillation tower is formed at 92.6
C,
2 bar and 283.96 kg/hr of 35% glycerin, 49% methanol, and 15%
FIGURE 3 Homogeneous alkaline catalytic process of waste cooking oil (Process 2) [Colour figure can be viewed at wileyonlinelibrary.com]
5 of 12
sulfuric acid (stream GLYCEROL). This stream is considered as a waste
due to the presence of a significant amount of sulfuric acid that can-
not be sold.
3.2.4 | Transesterification unit
Figure 3 depicts the flow diagram of an alkaline catalyst process using
WCO. The bottom stream of the separator from the SEP-3 (free fatty
acid oil), with stream 104 (free fatty acid oil), is mixed in MIXER-3 and
pumped to HEATER-2 by PUMP-6, where it is heated to 60
C.
The output stream from the HEATER-2 enters the transesterification
reactor R-CONVER. The 154.2 kg/hr of fresh methanol (stream 105) and
104.65 kg/hr of recycled methanol (stream 107) are mixed with
9.25 kg/hr of sodium hydroxide (stream 106) and then pumped to the
transesterification reactor by PUMP-7.
Transesterification reaction with methanol to oil molar ratio of
4:61, sodium hydroxide 1 wt% (oil-based) is carried out at 60
C and
4 atm (Equation (4)).
TRIOL− 01 + 3 MEOH ! GLYCE− 01 + 3 METHY− 01 95%conversion of TRIOL− 01
ðEq4Þ
In the transesterification reactor, 95% of the TRIOL-01 is trans-
formed to METHY-01. Glycerin is also produced as a by-product. The
stream S-16 is sent to the distillation tower T-MEOH-2.
3.2.5 | Water washing unit
The goal of this stage is to separate METHY-01 from other materials.
The tower T-WASH is used with five theoretical stages.
By adding 25 kg/hr of water (with water to oil molar ratio of 1:33) at


25 C (stream 108), FAME in the stream S-19 is separated from glycerin,
methanol, and catalyst. The upper stream of the tower (stream S-21) con-
tains glycerin, water, and methanol. The bottom stream of the tower
(stream S-20), which contains a significant amount of METHY-01, is sent
6 of 12
to the separator SEP-4 to be separated from glycerin, methanol, and so
forth.
3.2.6 | FAME purification unit
The bottom stream of SEP-4 (S-22) enters the distillation tower T-
FAME. The distillation tower (T-FAME) with five theoretical stages
and the reflux ratio of 2, is used to keep the temperature down to pre-
vent thermal decomposition.
The product of FAME (848 kg/hr) is obtained as a distilled liquid
at 168.27
C and 5 kPa pressure. Unconverted oil remains in the bot-
tom stream of the tower (stream S-32), leaving only a small portion of
it (46.9 kg/hr) as the waste.
Methanol recovery units, removal of alkaline catalyst, and purifica-
tion of glycerin in terms of operating conditions are exactly same as
the Process 1. Therefore, for further explanations, it is recommended
to refer to the results of the glycerin purification unit. 74 kg/hr glyc-
erin is obtained at this stage.
3.3 | Acid catalytic process of WCO (Process 3)
Temperature, pressure, mass percent of catalyst, and transesterification
reaction time are obtained from Zhang et al research. For the reaction of
esterification and neutralization as well as removal of the catalyst, the
conversion reactor is used; therefore, the kinetic formula is not required.
The esterification and neutralization reactors are simulated only by enter-
ing the chemical reaction equation (stoichiometric coefficients), tempera-
ture and pressure, and the percentage of conversion of the reaction.17
The sulfuric acid and calcium oxide mass flow rates as well as the metha-
nol to the oil molar ratio are obtained from this simulation.
The acid catalytic process is not sensitive to the free fatty acid con-
tent of oil. Consequently, the acid catalytic process seems to be an appro-
priate option for the production of biodiesel from WCO (Figure 4).
3.3.1 | Transesterification unit
First, 107.5 kg/hr of fresh methanol (with methanol to oil molar ratio of
3:22) is mixed with 100 kg/hr of recycled methanol (stream 103) and
FIGURE 4 Acid catalytic process of waste cooking oil (Process 3) [Colour figure can be viewed at wileyonlinelibrary.com]
SALEHI ET AL.
138.2 kg/hr of H2SO4 with H2SO4 to oil molar ratio of 1.35:1 (stream
101). Then, the stream of mix-1 to the transesterification reactor is sent
by PUMP-1. The WCO flow (stream 102 at 921.7 kg/hr) was sent to the
heat exchanger HEATER-1 and heated to 60
C before entering the trans-
esterification reactor by an oil pump.
In the reactor R-CSTR1, a mixed feed with triolein is reacted
(transesterification at 80
C and pressure of 4 atm) assuming that 97%
of the oil is converted into FAME (the main product) and glycerol (by-
product) after 4 hr. The kinetic formula and data are exactly like the
Process 1 (Equation (1) and Table 1).
Two reactors R-CSTR1 and R-CSTR2 are used as series, as shown
in Figure 4. The liquid product of the reactor consists of glycerin
(C3H8O3), methyl oleate (C19H36O2) and insignificant amounts of
unreacted methanol, acid, and oil, which enter the distillation tower of
methanol.
3.3.2 | Methanol recovery unit
In order to recover the extra methanol in the stream S-5 and thereby
reduce the load on the downstream unit of the distillation tower T-
MEOH-1, the six-theoretical stages, the reflux ratio of 2 is used. The
upper stream of the distillation column is recycled into the MIXER-1
by PUMP-3. The bottom stream of the tower (stream S-7) containing
glycerol, methyl oleate with unreacted oil, and H2SO4 is cooled down
to 25
C by the COOLER and transferred to the converting reactor R-
CONVER.
3.3.3 | Esterification unit
A general conversion reactor is used for complete conversion of
OLEIC-01. In the conversion reactor R-CONVER, all OLEIC-01 is
converted into METHY-01 based on Equation (3).
3.3.4 | Acid removal unit
The design principles for the removal of the acid catalyst are similar to
the removal of alkaline catalyst in Process 1. The output stream from
the reactor R-CONVER enters the neutralizing reactor R-NUTR.
SALEHI ET AL. 7 of 12

In the neutralizing reactor R-NUTR, the sulfuric acid is completely
removed by neutralizing and adding 140 kg/hr calcium oxide (stream
104) by forming CaSO4 and H2O. Equation (5) is performed at 25
C
and 1 atm.
H2 SO4 + CaO ! H2 O + CaSO4 100%conversion of H2 SO4 ðEq5Þ
The output stream of the neutralizing reactor (stream S-10) is sent
to remove the gravity separator SEP-1. The upper stream of the sepa-
rator (stream S-11) is composed of 79.64% FAME, 7.4% glycerin, and
12.34% water. This stream is sent to the separator SEP-2 for separat-
ing FAME and glycerin. Separation is done by weight difference
between glycerin and methyl ester.
The upper stream of the second separator containing the main
product of methyl ester and unreacted triolein enters the second dis-
tillation column, where most biodiesel are distilled as distillated. The
bottom stream of the second separator contains 95% glycerol solu-
tion, which is collected as a heavy ingredient.
3.3.5 | Glycerin purification unit
The bottom stream of the separator SEP-2 enters the glycerin distilla-
tion tower. In distillation tower, T-GLYCEROL (under vacuum condi-
tions) with five theoretical stages and a reflux ratio of 2 is used to
purify glycerin. At the bottom stream of the distillation tower,
78 kg/hr glycerin is obtained as a by-product.
3.4 | Two-step supercritical methanol process of
edible oil residue (Process 4)
In this process, the two-step supercritical methanol method (non-
catalytic) is used to produce biodiesel (Figure 5). The above process
involves hydrolysis and esterification. The advantages of this method
are the absence of a catalyst, removal of separation and neutralization
units, and short reaction times. The supercritical methanol process
reduces the reaction time significantly, but there are disadvantages
like toxicity and high-energy consumption. These benefits reduce pro-
duction costs. The temperature and pressure of hydrolysis and esteri-
fication reactions, methanol to oil and water to oil molar ratios, and
percentages of conversion of the hydrolyser reactors and the esterifi-
cation obtained from this simulation are some examples in this regard.
3.4.1 | Hydrolysis unit
According to Figure 5, initially 921.7 kg/hr triolein and 374.7 kg/hr water
(with water to oil molar ratio of 20:1) are mixed in the Mix-100 and then
transferred to the HEATER-1 after increasing the pressure to 17 atm by
the PUMP-100. The temperature of this mixture increases to 270
C in
HEATER-1. Next, the output stream of the HEATER-1 is sent to the
hydrolysis reactor (R-HYDROL) to convert triolein to OLEIC-01.
According to Equation (6), the hydrolysis reaction is carried out at
17 atm and 270
C that 98.5% of triolein is converted to OLEIC-01.
TIROL− 01 + 3 H2 O ! GLYCE− 01 + 3 OLEIC−01 98:5%conversion of TIROL− 01
ðEq6Þ

3.3.6 | FAME purification unit

3.4.2 | Unit of esterification
The upper stream of separator SEP-2 enters the purification tower T-
Methanol with a flow rate of 666.2 kg/hr (with methanol to oil molar
ESTR. In order to purify FAME from the distillation tower with five theo-
ratio of 20:1) is transferred to the HEATER-2 and heated to 270
C.
retical stages, the reflux ratio of 2 is used. The methyl ester purification
Methanol is compressed by a PUMP-200 to 27 atm. The output
tower operates under vacuum conditions, the 10 kPa pressure of con-
stream from the PUMP-200 and the main stream from the R-
denser and 15 kPa pressure of the reboiler to keep the temperature of
HYDROL reactor are sent to the R-ESTER esterification reactor.
the distilled product and the bottom stream, since the biodiesel is
According to Equation (7), the esterification reaction is carried out
decomposed at above 250
C. Finally, 909 kg/hr FAME is produced as
at 27 atm, 270
C that 98% of OLEIC-01 is converted to FAME.
the main product of the process.

FIGURE 5 Two-step supercritical methanol process of edible oil residue (Process 4) [Colour figure can be viewed at wileyonlinelibrary.com]
8 of 12
OLEIC−01 + MEOH ! METHY−01 + H2 O 98%conversion of OLEIC−01
ðEq7Þ
3.4.3 | FAME purification unit
In order to achieve high purity biodiesel, the flow of the outlet from
the esterification reactor, after cooling in the COOLER-1, is intro-
duced to the T-100 with six theoretical stages and the reflux ratio of
2. In the upper part of the tower, 861.6 kg/hr biodiesel is obtained.
3.4.4 | Glycerin purification unit
In order to produce high purity glycerin, the lower stream of the T-100
tower is sent to the T-200. The number of theoretical stages and reflux
ratio of the glycerin distillation tower is similar to the T-100 tower. At the
lower part of the tower, 94.43 kg/hr of glycerin is obtained.
3.4.5 | Methanol recovery unit
To recover methanol and water, the upper stream of the T-200 is sent
to the SEP-100. Water is recycled from the upper part of the separa-
tor. The flow of the outlet from the middle section separator is con-
sidered as the return methanol. Finally, the bottom flow of the
separator is regarded as a waste.
3.5 | Acid catalyst process using hexane extraction
(Process 5)
A liquid–liquid extraction tower is used to extract FAME from hexane.
The results reveal the incorrect recovery of FAME from hexane due
to the shortage of sufficient information in the software to interact
with parameters such as complex multicomponents, as well as hexane
solubility in anhydrous methanol. Operating conditions from the
transesterification unit to the neutralization reactor are exactly same
as Process 3. As a result, the description of the process begins at hex-
ane extraction unit.
FIGURE 6 Acid catalyst process using hexane extraction (Process 5) [Colour figure can be viewed at wileyonlinelibrary.com]
SALEHI ET AL.
Furthermore, water to methanol volume ratio is derived from
Zhang et al research.17 The volumes flow rates of water and hexane
are the result of this simulation.
3.5.1 | Hexane extraction unit
According to Figure 6, the output stream S-11 from the separator
SEP-1 (SS-11 stream at 1167.45 kg/hr) in Process 3 is fed by a
PUMP-200 to a liquid–liquid extraction tower (hexane extraction from
FAME). Then, 0.15 m3/hr hexane (stream 202 at 100 kg/hr) and
0.01 m3/hr water (stream 201 at 10 kg/hr) with water to methanol
volume ratio of 1:10 are added to the hexane extraction tower
EXTER-1 at 25
C and 200 kPa to reduce the hexane solubility.
After hexane extraction, the stream S-103 is sent to the tower EXTER-2
at 25
C and 200 kPa. The stream S-103 is composed of 9% hexane, 71.6%
FAME, 12% water, and 6.6% glycerol. The main downstream flow material
contains 7.3% glycerin, 12.3% water, and 79.6% FAME (stream S-104).
3.5.2 | Washing unit
The second methanol–water washing unit (EXTER-2 tower) is used to
remove water and glycerin from the hexane and FAME of stream S-
103 at ambient temperature. Therefore, 0.05 m3/hr of methanol–
water is added to the tower EXTER-2 with a 1.15:1 volume ratio
(streams 203, 204 at 20 kg/hr).
After washing, the upper stream of the tower EXTER-2 (stream S-
108) and the upper stream of the hexane extraction tower (EXTER-1)
are mixed and then sent to the separator SEP200. In this unit, all of
the glycerin and water and methanol from the hexane - FAME is sepa-
rated and sent to the distillation tower T-100 (stream S-110). Finally,
the stream of S-111 is carried out to remove hexane from the FAME
in distillation tower T-200.
3.5.3 | Glycerin purification unit
The stream S-110 is fed to the distillation tower T-100 with five theo-
retical stages and the reflux ratio of 2 that operates in vacuum condi-
tions. Methanol and water are extracted from the upper part of the
tower and 86 kg/hr glycerin is obtained from the bottom stream.
SALEHI ET AL. 9 of 12

3.5.4 | FAME purification unit 4.2 | Pretreatment unit

The tower T-200 is utilized to distillate FAME with five theoretical
stages and the reflux ratio of 2 under vacuum conditions. The upper
stream can be returned to the hexane extraction to reduce the fresh
solvent (stream HEX at 100.1 kg/hr). Furthermore, 934.34 kg/hr
FAME is obtained from the bottom stream which is the main product.
4 | RESULTS AND DISCUSSION
4.1 | Number of main units
In Table 1, the processes are compared in terms of the number of
operating units and materials. Obviously, the number of operating
units and equipment made from stainless steel is higher, which leads
to an increase in the investment costs.
The pretreatment unit is used only in the Process 2. The VVO only
applies to the Process 1. In other words, other processes do not show
any sensitivity to the amount of oleic acid existing in WCO. The pre-
treatment unit consists of the esterification reactor R-ESTER,
glycerin-washing tower T-EXTRA1, and methanol distillation tower.
The size of the esterification reactor is smaller than the trans-
esterification reactor in all processes. Glycerin is used as a washing
solvent, which has the potential to be sold as a by-product. However,
application of H2SO4 as the catalyst increases the need for using
stainless materials in the reactor R-ESTER, T-EXTRA1 and T-MEOH
towers, and other axial equipment. Glycerin is obtained from the pre-
treatment unit, however, other processes contain a large amount of
sulfuric acid, which is not commercially available and is considered as
waste. In sum, these factors increase the complexity of the process
and the cost of equipment as well as operations.

99.90% 99.99% 4.3 | Transesterification unit

99.60%
99.40% The amount of additional methanol used in acid catalyzed Processes
3 and 5 leads to an increase in the volume of the reaction. As a result, two
98.50%
transesterification reactors are used in series. Consequently, the cost of
transesterification reactors increased compared to other processes.

Process 1 Process 2 Process 3 Process 4 Process 5

4.4 | Catalyst neutralization unit
FIGURE 7 Glycerin purity percentage of modeling processes
In Process 4 (supercritical methanol), the catalyst is not used, so the
catalyst neutralization unit is removed from the process. In Processes
99.70% 99.65%
99.50% 1 and 2, the alkaline catalyst in the neutralizing reactor is neutralized

98.88% by H3PO4 agent and in Processes 3 and 5 of the acid catalyst is neu-
98.47% tralized by CaO.

4.5 | Washing unit

Process 1 Process 2 Process 3 Process 4 Process 5
Processes 3 and 4 do not need a washing unit, but in other processes,
FIGURE 8 Biodiesel purity percentage of modeling processes washing is carried out by a liquid–liquid extraction tower. Two towers

TABLE 3 Energy consumption of main process equipment

Main process equipment Process 1 Process 2 Process 3 Process 4 Process 5

Pumps 2.81 4.64 1.71 0.897 1.92
Exchangers 101.06 163 271.4 210.1 273.14
Separators 1.926 4.65 1.124 42.71 5.394
Esterification reactor 0 15.73 11.24 28.02 11.24
Transesterification reactor 277.54 216 167.6 0 167.58
R-NTUR 6.88 12.24 0.332 0 0.332
R-HIROL 0 0 0 53.95 0
T-MEOH 1,074.6 2,470 793.33 0 793.33
T-GLYCRO 1,303.6 6,307.2 1827.6 10,045.36 2,702.66
T-ESTER 3,212.85 4,179.6 1,130 4,886.6 458.56
Sum (MJ/hr) 5,981.266 13,373 4,204.336 15,267.64 4,414.156
10 of 12 SALEHI ET AL.

TABLE 4 Summary of unit operating conditions for each process

T P t
Process Methanol:oila (
C) (mPa) (hr) Conversion (%) Reactor FAME (%) Ref
Process 1 6:1 60 0.4 – 95 Conv 99.7 17
6:1 60 0.4 1 95 CSTR 99.6 20
4:61 60 0.4 1 95 CSTR 99.7 This study
Process 2 6:1 b
70 /60 c
0.4 – b
100 /95 c
Conv 99.7 17
6:1 70b/60c 0.4 1b/4c 100b/95c CSTR 99.97 22
b c b c
6:1 70 /60 0.4 1 100 /95 CSTR 99.7 20
4:61 70b/60c 0.4 – 100b/95c Conv 99.65 This study
Process 3 50:1 80 0.4 4 97 Conv 99.7 17
50:1 80 0.4 4 97 CSTR 99.65 22
3:22 80 0.4 4 97 CSTR 98.88 This study
Process 4 42:1 350 20 0.33 98 CSTR 99.65 22
24:1 350 19 0.25 96 PFR 99.8 20
20:1 270 27 – 98.5d/98e Conv 98.47 This study
Process 5 50:1 80 0.4 4 97 Conv 99.6 17
3:22 80 0.4 4 97 CSTR 99.5 This study
a
Esterification reaction.
b
Transesterification reaction.
c
Hydrolysis reaction.
d
Esterification reaction.
e
Molar ratio.

are required in Processes 5 and 2. Since sulfuric acid is present in the
process of alkaline catalyst (Process 2), stainless steel is selected as a
construction materials for the tower T-EXTRA1, while carbon steel
content in Processes 1 and 5 is sufficient.
4.6 | Glycerin purification unit
In Figure 7, the percent glycerol purity of all processes is presented. The
under vacuum operation has a great influence on the glycerin purity.
4.7 | FAME purification unit
Figure 8 shows the biodiesel purity percentage of all processes. Unit opera-
tion under vacuum conditions has a great impact on the biodiesel purity
percentage. The highest degree of purity is associated with the Process 1.
4.8 | Energy consumption
According to Table 3, the main equipment of all processes is com-
pared in terms of energy. The highest and lowest energy consump-
tions belong to Processes 4 and 2, respectively.
simulated processes of this research and other similar studies is pres-
ented in Table 4.
Based on the obtained results, it is reported that acidic catalyst
has a better effect on oil with free fatty acid content than the one
with 1% by weight, but it has problems like corrosion of equipment,
low reaction speed, high temperature conditions, and methanol to
high oil molar ratio.
In general, the homogeneous alkaline catalyst reaction is faster
than the homogeneous acidic catalyst reaction, but the conversion
efficiency of the oil to the ester is less due to the formation of soap in
the reaction. In addition, the biodiesel separation from glycerin
becomes more difficult.
In Processes 1, 2, and 5, lower methanol to oil molar ratio is used.
Furthermore, the simulation results indicate that the biodiesel purity
is similar to that of other processes. In Process 3, despite the use of a
lower methanol to oil molar ratio, the biodiesel purity is lower than
the ASTM standard. In Process 4, the temperature and pressure as
well as lower methanol to oil molar ratio are used, but the resulting
biodiesel is slightly different from the similar processes.
5 | C O N CL U S I O N

4.9 | Comparison with simulated processes by other

researchers
To sum up, the results of this study are compared with those of the
previous studies. A summary of the important parameters of the
There is a need for cheap and renewable resources like WCO in order
to overcome the limitations of fossil fuels as well as the environmental
contamination. Assuming that the number of cultural and industrial
restaurants and self-service centers in Tehran province is 20 thousand
SALEHI ET AL. 11 of 12

units, and each unit produces 1 kg of frying oil daily, 7,300 ton of res- DG diglyceride
taurant waste is collected annually. Biodiesel is currently produced by MG monoglyceride
WCO in Europe, South-East Asia, and North and South America. PFR plug reactor
Therefore, using the Aspen Plus v 8.6 simulation software, a factory
with a capacity of 7,200 tons per year is designed using raw materials
like VVO and restaurant waste oil in a five different process. The
OR CID
results of simulating the technical assessment are as follows: The
homogeneous alkaline catalytic process of WCO has the highest num- Abdolreza Karbassi https://orcid.org/0000-0002-9408-908X
ber of units, and the smallest number of process units belongs to the
two-step supercritical methanol process (Process 4). In all processes,
vacuum distillation is required to produce high-purity glycerol. The RE FE RE NCE S
lowest purity of glycerin belongs to the Process 5 (98.5%) and the
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How to cite this article: Salehi A, Karbassi A, Ghobadian B,
Ghasemi A, Doustgani A. Simulation process of biodiesel
production plant. Environ Prog Sustainable Energy. 2019;
e13264. https://doi.org/10.1002/ep.13264