Fuel 280 (2020) 118578

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T
Modeling and optimization of biodiesel production from microalgae in a
batch reactor
Mohammad Reza Talaghata, , Shahin Mokhtarib, Mohammad Saadatc
⁎

a
Chemical Engineering Department, Shiraz University of Technology, Shiraz, Iran
b
Master of Science in Chemical Engineering, Islamic Azad University, Shiraz Branch, Shiraz, Iran
c
Master of Science Student in Chemical Engineering Department, Shiraz University of Technology, Shiraz, Iran

A R T I C LE I N FO A B S T R A C T

Keywords: In this research, biodiesel production from two types microalgae including Enteromorphacompressa, and
Biodiesel Scenedesmus in the presence of acid catalyst and methanol in batch reactors was modeled. In this study, the
Microalgae reaction rate constants have been considered as different functions of both temperatures and catalyst con-
Modeling centrations to evaluate and compare the effect of these reaction rate constants on biodiesel production yield.
Optimization
Then the models were used to find the optimal conditions in order to maximize the biodiesel yield. In this regard,
Enteromorphacompressa
Scenedesmus
the kinetic parameters of models were calculated by using experimental data. Then, the effect of temperature,
catalyst concentration, and methanol to oil ratio on the biodiesel yield were calculated. According to results, the
models can accurately predict the effect of temperature, catalyst concentration, and methanol to oil ratio on the
biodiesel yield. According to the results, there are direct relationship between biodiesel yield and the effective
parameters. Results showed that the efficiency of biodiesel production more than 99% can be achieved at op-
timal condition.

1. Introduction transesterification of oils. In the transesterification reactions, trigly-

cerides react with an alcohol (methanol) in the presence of a catalyst to
Primary sources of energy can be divided into two categories: re- produce biodiesel (fatty acid methyl esters) as the main product and
newable and non-renewable. Non-renewable resources are, in fact, glycerol as the byproduct [10]. The biodiesel production consists of
limited resources and on the other hand, their recovery, processing and three consecutive reactions as shown by Eqs. (1) to (3) [11].
energy use can have a significant impact on the environment [1–2]. k1, k2
Fossil fuels have been around for many years and are a non-renewable TG + MeOH ⟷DG + FAME (1)
resource. In fact, today more than 80% of our energy use comes from k3, k 4
DG + MeOH ⟷ MG + FAME (2)
three fossil fuel sources [3]. Another problem with fossil fuels is their
heterogeneous distribution globally [4]. Increased energy demand and k5, k 6
MG + MeOH ⟷ G + FAME (3)
net oil prices, global greenhouse gas emissions, environmental pollution
and rapid decline in fossil fuel resources are key factors that have led to where, TG is triglyceride, MeOH is methanol, DG is diglyceride as an
research into alternative fuels. Some of these more important alter- intermediate, MG is monoglyceride as an intermediate, FAME is bio-
native energy sources include water, wind, solar and green fuels [5–6]. diesel as the main product and G is glycerol as the byproduct. Gen-
One of the types of renewable fuels that have high potential is biofuels. erally, each mole triglyceride reacts with three moles of methanol to
The term biofuel can refer to liquid or gaseous fuels used in the produce three moles of biodiesel and one mole glycerol, as can be seen
transport sector that are produced from biomass sources. in these equations.
Biodiesel as a fuel is a mixture of long-chain methyl esters such as k7, k8
TG + 3MeOH ⟷G + 3FAME (4)
palmitic acid, oleic acid, and stearic acid. The physical properties of this
fuel are very similar to the diesel fuel, thus biodiesel can be a good However, additional methanol is usually used to increase the biodiesel
alternative to the diesel fuel. Biodiesel is produced from animal re- yield, because the reactions are equilibrium reactions. Usually, the
sources such as fat, or plant sources such as edible or non-edible oils, methanol to oil ratio of 5 to 12 is used in the industrial production of
and microalgae [7–9]. The biodiesel is traditionally produced by the biodiesel. Since 20 to 50 wt% of the microalgae consist of oils,

⁎
Corresponding author.

https://doi.org/10.1016/j.fuel.2020.118578

0016-2361/ © 2020 Elsevier Ltd. All rights reserved.

Received 27 August 2019; Received in revised form 26 May 2020; Accepted 29 June 2020
M. Reza Talaghat, et al. Fuel 280 (2020) 118578

microalgae are potential sources of oils for the production of biodiesel international markets [22].
[12]. Microalgae have attracted the attention of researchers in biodiesel One of the important sources of biodiesel fuels are algae. The dif-
production. Therefore, the modeling of biodiesel production from mi- ferent types are suitable for different fuels. These plants require almost
croalgae is necessary for the design and optimization of this process. no climatic conditions and unique cultivation conditions and grow in
The first scientific research on biodiesel production was studied by both sewage and saline conditions. Low energy consumption is also
Freedman et al. [11]. They were the first researchers to model the ki- effective in their growth. This plant can be a good alternative to oil
netics of transesterification. Noureddini and Zhu are other researchers fuels, plus no harm or contamination. About 50 percent by weight of
investigating transesterification of soybean oil with methanol [13]. microalgae, fat and oil can be used as biodiesel raw material [23]. We
Ehimen et al. studied the production of biodiesel from microalgae know that the price of the raw material has an impact on the final price
chlorella in the presence of hydrochloric acid catalyst [14]. Chen et al. of the product. Therefore, because the price of edible and non-edible
studied the production of biodiesel from Syndrome microalgae in the vegetable oils is higher than micro algae. Therefore, the cost of bio-
presence of potassium hydroxide catalyst and temperature of 65 °C and diesel production using micro algae is reduced. Therefore, this raw
achieved more than 90% production yield [15]. Berchmans et al. in- material can be used as a source for biodiesel production [24].
vestigated the effect of free fatty acids contained in oil on biodiesel Microalgae can also use carbon dioxide gas produced by fossil fuels
production and were able to develop a model that could predict, in from power plants and other sources, resulting in a reduction in
addition to biodiesel, the amount of soap and water produced by free greenhouse gas emissions [25]. Microalgae are easily found in nature,
fatty acids [16]. Clark et al. investigated the biodiesel production but there are generally two main ways to grow them: outdoor ponds
process and found a relationship between ambient pH and the amount and photo-bioreactors.
of biodiesel produced [17]. Reddy et al. were able to produce biodiesel Microalgae are divided into 4 general categories:
using nanochloropsis microalgae and supercritical ethanol without the
use of a catalyst. In that study, biodiesel production at 245 to 270 °C, 2 1. Brown microalgae found practically everywhere including saline
to 30 min retention time, and alcohol to oil ratio of 6 to 15 were se- and freshwater
lected. Under optimal conditions, they were able to achieve 67% pro- 2. Green algae
duction efficiency [18]. Guldhe et al. produced Aspergillus biodiesel 3. Blue green algae
from algae. In that study, at a temperature of 35 °C and an alcohol-to-oil 4. Golden algae
ratio of 5, the biodiesel production yield was 53% [19].
Biodiesel is pure fuel itself (B100). For this reason it is also called It is also estimated that there are more than 100,000 species of
clean fuel. The biodiesel mixtures is a pure biodiesel blend with pet- algae. These plants are commonly used as food, animal feed, aqua-
roleum fuels, referred to as BXX [20]. The properties of biodiesel ex- culture feed and biofertilizers [26].
tracted from some plant sources are listed in Table 1. In general, there are several well-known methods for biodiesel
In the present study, the biodiesel production by the extracted oil of production. There are four main ways to produce biodiesel using ve-
two type’s microalgae including Enteromorphacompressa, and getable oils and animal fats. These are:
Scenedesmus in the presence of acid as the catalyst is modeled to in-
vestigate the effects of temperature, catalyst concentration and me- 1) Direct use of vegetable oils as biofuels
thanol to oil ratio on the biodiesel yield. 2) Micro-emulsion
3) Pyrolysis
4) Transesterification reaction of vegetable oils
1.1. Biodiesel resources

Transesterification is the reaction of a fat or oil with an alcohol to

The main sources of biodiesel fuel production are various types of
form esters and glycerol. A catalyst is usually used to improve the re-
fatty organic compounds which are divided into four groups in a logical
action rate and yield. Excess alcohol is used to shift the equilibrium
classification [21]:
toward the product because of reversible nature of reaction [10].
The main purpose of this reaction is to reduce the viscosity of the
a) Raw vegetable oil raw material such as soybean oil and rapeseed oil
oil, increase the volatility and also burn the fatty acid alkyl in the diesel
which are more common and other vegetable oils such as mustard
engine without any modification to the engine [27]. The reaction that
oil, dates, sunflower oil, hemp
typically occurs with the ester exchange reaction is the esterification
b) Residual vegetable oils.
reaction. This reaction occurs when free fatty acid is next to acid or
c) Animal fat including tallow, pig fat and yellow fatty oil
base. Alkyl esters are also produced in this reaction, except that the
d) Algae oils
reaction is a single step and in addition to alkyl esters, water is also
produced. In order to improve the performance of the dissolution of oil
The choice of oil or fat for fuel production depends, process
and alcohol in the transesterification reaction, the solvent is a good
chemistry, process economics and, most importantly, on the content of
solution. Solvent assistance by increasing the solubility of these two
feed oil. Table 2 presents the oil content of some of the most commonly
substances together creates a single phase environment for the reaction
used biodiesel sources. The content of feed oil is a very important factor
[28].
and in the future it is likely to become a competitive factor in

Table 1
Properties of biodiesel produced from some plant sources (Barnwal and Sharma, 2005).
Feed Temperature (°C) MIU (wt%) density (Kg/m3) viscosity 40°C mm2/s CetaneNo. Thermal value (MJ/kg) Flash point (°C)

Corn 14–21 1.67 909.5 30.75 37.6 39.5 277

Soya 22–27 0.77 913.8 28.87 37.9 39.6 254
Sunflower 16–20 0.65 916.1 35.84 37.1 39.6 274
Date 42–45 0.03 918 44.79 42 – 267
Coconut 20–24 2.74 918 27.26 – – –
Jatropha 31 0.16 940 33.9 – 38.65 225
peanut 26–32 – 902.6 39.6 41.8 39.8 271

2
M. Reza Talaghat, et al. Fuel 280 (2020) 118578

Table 2
Percentage of oil available from various plant sources for biodiesel production (Grepen et al., 2004; Lewis, 2005)
Feed type Soya oil Sunfloweroil Date oil Date oil seed Peanut oil olive oil

Oil % 15–20% 25–35% 30–60% 44–65% 45–55% 45–75%

Feed type Coconut oil Jatropha oil Jojoba oil Mahua oil Moringa oil Linseed oil
Oil% 63–65% 30–40% 45–50% 35–42% 35–40% 40–44%

Although the use of solvent increases the efficiency and rate of the temperatures (65 °C) and can be ignored [32].
reaction, it has problems such as elimination and disposal after the 3. The reaction mixture is considered a homogeneous phase.
reaction which can cause environmental damage. 4. Mixed density is assumed during the steady process.
5. The reaction rates are assumed to be a function of temperature and
1.2. Economic viability of biodiesel catalyst concentration.

Biodiesel has become more attractive recently because of its en- Biodiesel production reaction involves six components, including
vironmental benefits and the fact that it is made from renewable re- two reactants: TG and MeOH, two intermediate: DG and MG, the main
sources. The remaining challenges are its cost and limited availability of product: FAME, and the byproduct: G. As mentioned before, there are
fat and oil resources. There are two aspects of the cost of Biodiesel, the three equilibrium reactions (Eqs. 1 to 3) in this process. The rates of
costs of raw material (fats and oils) and the cost of processing. The cost these reactions were proposed by Freedman et al. as follows [11]:
of raw materials accounts for 60–75% of the total cost of Biodiesel fuel
r1 = −k1 [TG][MeOH ] + k2 [DG][FAME ] (4)
[29].
The use of used cooking oil can lower the cost significantly. r1 = −k3 [DG][MeOH ] + k 4 [MG][FAME ] (5)
However, the quality of used cooking oils can be bad [30]. Studies are
needed to find a cheaper way to utilize used cooking oils to make r1 = −k5 [MG][MeOH ] + k6 [G][FAME ] (6)
Biodiesel fuel. There are several choices, first removing free fatty acids
from used cooking oil before transesterification, using acid catalyzed where r1, r2 and r3 are the reaction rates of Eqs. (1) to (3), respectively.
transesterification, or using high pressure and temperature [31]. In In the present study, reaction rate constants have been considered as
terms of production cost, there also are two aspects, the transester- different functions of both temperature and catalyst concentration to
ification process and by-product (glycerol) recovery. A continuous evaluate and compare the effect of these reaction rate constants on
transesterification process is one choice to lower the production cost. biodiesel production yield (as shown by Eqs. (7a) to (7d). In these
The foundations of this process are a shorter reaction time and greater equations, the temperature dependence is expressed by Arrhenius
production capacity. The recovery of high quality glycerol is another equation.
way to lower production cost. Because little water is present in the E
system, the Biodiesel glycerol is more concentrated. Unlike the tradi- ki = Ai exp ⎛− i ⎞ i = 1, 2, 3, 4, 5, 6
⎝ RT ⎠ (7a)
tional soap glycerol recovery process, the energy required to recover
Biodiesel glycerol is low due to the elimination of the evaporation E
ki = Ai exp ⎛− i ⎞ + Bi (cat .) i = 1, 2, 3, 4, 5, 6
process. In addition, the process is also simpler than soap glycerol re- ⎝ RT ⎠ (7b)
covery since there is a negligible amount of soap in Biodiesel glycerol.
This implies that the cost of recovering high quality glycerol from E
ki = Ai exp ⎛− i ⎞ + Ci (cat .)2 i = 1, 2, 3, 4, 5, 6
Biodiesel glycerol is lower than that of soap glycerol and that the cost of ⎝ RT ⎠ (7c)
Biodiesel fuel can be lowered if a Biodiesel plant has its own glycerol
E
ki = Ai exp ⎛− i ⎞ + Bi (cat .) i + Ci (cat .)2 i = 1, 2, 3, 4, 5, 6
recovery facility. With the increase in global human population, more
land may be needed to produce food for human consumption (indirectly ⎝ RT ⎠ (7d)
via animal feed). So insufficient land may also increase the production
where, Ai, Ei and Bi are the Arrhenius constant, activation energy and
cost of Biodiesel plants. The problem already exists in Asia where ve-
the catalyst effect coefficient, respectively. Based on the mass balance
getable oil prices are relatively high. The same trend will eventually
in a batch reactor, the governing equation of concentration distribution
happen in the rest of the world. This is the potential challenge to Bio-
is obtained as Eq. (8):
diesel production. Biodiesel can be used most effectively as a supple-
ment to other energy forms. Biodiesel is particularly useful in mining 1 dNi dCi
ri = =
and marine situations where lower pollution levels are important. V dt dt (8)
Biodiesel also can lower US dependence on imported petroleum based
where ri and Ci are the reaction rate and the concentration of compo-
fuel [31].
nent i, respectively. By substituting Eqs. (4) to (7) in Eq. (8), the re-
action rates of all six components are obtained as follows
2. Mathematical modeling
d [TG]
= −k1 [TG][MeOH ] + k2 [DG][FAME ]
The purpose of the modeling in the present study is to calculate the dt (9)
concentration distribution of the materials present in the biodiesel
d [DG]
production process over time and finally to calculate the biodiesel = k1 [TG][MeOH ] − k2 [DG][FAME ] − k3 [DG][MeOH ] + k 4 [MG]
production efficiency under different conditions to obtain the optimal dt
conditions of biodiesel production. The following assumptions are used [FAME ] (10)
to perform the modeling
d [MG]
1. The general kinetics of the quadratic reaction is considered. dt
2. The saponification reaction is considered to be negligible, Vicente = k3 [DG][MeOH ] − k 4 [MG][FAME ] − k5 [MG][MeOH ] + k6
et al. showed that soap-making reactions are negligible even at high
[G][FAME ] (11)

3
M. Reza Talaghat, et al. Fuel 280 (2020) 118578

= k1 [TG][MeOH ] − k2 [DG][FAME ] + k3 [DG][MeOH ]

d [FAME ] Table 4
dt
Kinetic parameters (using Eq. 7b) of biodiesel production from the Scenedesmus
− k 4 [MG][FAME ]+ microalgae.
k5 [MG][MeOH ] − k6 [G][FAME ] (12) Rate constant reaction A(mol. L-1.min−1) B(mol. L-1.min−1)

d [G]
= k5 [MG][MeOH ] − k6 [G][FAME ] k1 0.0039 0.0579
dt (13) k2 0.7883 0.1424
k3 0.2200 0.9231
d [MeOH ] d [FAME ]
=−
k4 1.1617 0.0688
dt dt (14) k5 0.8904 0.7763
k6 0.5912 0.0385
According to these equations, there are six reaction rate constants
(k1 to k6) in the model equations. In addition, each reaction rate con-
stant involves two, three, three and four constants according to Eq. 50
(7a)-(7d), respectively. Thus, there are 12, 18, 18 and 24 coefficients in
the model equations that will be estimated by experimental data related 40

Biodiesel Yield%
to the transesterification of the oil extracted from
Enteromorphacompressa. The experimental data were gathered from 30
the literature [33]. The experiments include temperature, catalyst
concentration, methanol to oil ratio, and the biodiesel yield. Experi- 20
ments are related to three temperatures of 45, 55 and 64 °C, catalyst
concentrations of 0.7, 1.1 and 1.5 wt%, and methanol to oil ratios of 6, 10
9, 12 and 14. The model equations (Eqs. 9–14) are solved by the Runge-
Kutta method, while the 18 coefficients of the model are calculate by 0
the combination of Genetic Algorithm and the Runge-Kutta method. 0 20 40 60 80
The objective function for the calculation of model coefficients is the time (min)
average absolute error between experimental yields and the yields Fig. 1. Biodiesel production efficiency of the Enteromorphacompressa micro-
calculated by the model, as defined by Eq. (15): algae oil vs. time. Temperature = 55° C, catalyst concentration = 0.6%, and
N methanol to oil ratio = 6.
∑ |ηexp − ηcal|
1
OF =
N j=1 (15) 100
where N is the number experimental data, ηexp and ηcal are experimental
and calculated yields, respectively. The model is validated by com- 80
paring the results with experimental data. Then, the model is used to
60
Yield%

investigate the effect temperature, catalyst concentration and methanol

to oil ratio on the biodiesel yield, and finally, the optimal condition is
calculated to maximize the biodiesel yield. 40

3. Results and discussion 20

3.1. Kinetic parameters 0

0 20 40 60 80
time (min)
As mentioned before, in the production of biodiesel from
Enteromorphacompressa, and Scenedesmus microalgae according to Fig. 2. Biodiesel production efficiency of the Scenedesmus microalgae oil vs.
Eqs. (7a) to (7d), there are 12, 18, 18 and 24 coefficients, respectively, time. Temperature = 65 °C, catalyst concentration = 2%, and methanol to oil
(two, three or four coefficients per reaction rate constant) related to six ratio = 9.
reaction constants (k1 to k6) should be calculated by experimental data.
The coefficients of Eqs. (7b and 7a) are calculated and listed in Tables 3 study, the calculated biodiesel yield at various conditions is compared
and 4, for the production of biodiesel from Enteromorpha compassa and with experimental data. In these studies, Eq. (7b) is used to calculate
Scenedesmus microalgae, respectively. the reaction rate constants. Figs. 1–2 show the results of the model and
experimental data for the production of biodiesel from En-
3.2. Model evaluation: Comparison between results of model and teromorphacompressa and Scenedesmus microalgae, respectively. As
experiments can be seen in these figures, the model is able to predict the biodiesel
yield well. Thus, it can be concluded that the proposed model is a re-
In order to evaluate the accuracy of the proposed model in this liable model to investigate the effect of temperature, catalyst con-
centration and methanol to oil ratio on the biodiesel yield. Also, it can
Table 3 be used to calculate the optimal condition of the process in order to
Kinetic parameters (using Eq. 7b) of biodiesel production from the maximize the biodiesel yield.
Enteromorphacompressa microalgae
Rate constant reaction A(mol. L-1.min−1) E(kJ. mol−1) B(mol. L-1.min−1)
3.3. Effect of different parameters on biodiesel yield
k1 5.112E + 11 87.236 0.0032
k2 2.069E + 05 33.688 0.0426 After examining the accuracy of the model in predicting biodiesel
k3 4.996E + 16 112.697 0.0180 production from Enteromorphacompressa and Scenedesmus micro-
k4 2.002E + 10 69.738 1.1744
algae, and ensuring the accuracy of the model, this section uses model
k5 1.196E + 00 92.951 0.8723
k6 6.810E-01 104.923 0.0034 results to investigate the effect of temperature, catalyst concentration
and methanol-to-oil ratio. In order to calculate the optimum conditions

4
M. Reza Talaghat, et al. Fuel 280 (2020) 118578

60 45
40
50
35

Biodiesel Yield%
Biodiesel Yiel %

40 30
25
30
20

20 15
10 M/O =3
catalyst 0.5% M/O=6
10 catalyst 0.75% 5 M/O=9
catalyst 1.0%
0 0
0 20 40 60 80 0 20 40 60 80
time (min) time (min)

Fig. 3. Effect of Catalyst Concentration on the Production of biodiesel from Fig. 6. The effect of methanol-to-oil ratio on the production of biodiesel from
Enteromorphacompressa microalgae as: Temperature = 55 °C; Methanol to Oil Enteromorphacompassa microalgae: Catalyst concentration = 0.5 wt%;
ratio = 6. Temperature = 45 °C.

80
80

Biodiesel Yield%
Biodiesel Yield%

60 60

40 40

catalyst 0.6%
20 catalyst 1.2% 20 M/O=6
catalyst 2.0% M/O=9
M/O=12
0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
time (min) time (min)
Fig. 4. Effect of Catalyst Concentration on the Production of biodiesel from the Fig. 7. The effect of methanol-to-oil ratio on the production of biodiesel from
Scenedesmus microalgae as: Temperature = 65 °C, Methanol to Oil ratio = 6. the Scenedesmus microalgae: Catalyst concentration = 0.6 wt%;
Temperature = 65 °C.
70
production process of Scenedesmus microalgae is investigated. As can
60
be seen in this figure, as the catalyst concentration increases, the effi-
50 ciency of biodiesel production increases substantially. According to the
Biodiesel Yield%

results of this figure, at 65 °C and methanol to oil ratio of 6, increasing

40 the catalyst concentration from 0.6% to 1.2%, increased the yield from
60.30% to 80.0%. Therefore, catalytic concentration is important as
30
one of the important parameters in biodiesel production from Scene-
20 45 oC desmus microalgae.
55 oC
10 65 oC 3.3.2. Effect of temperature on the biodiesel production
0 In Fig. 5, the effect of temperature on the biodiesel production
0 20 40 60 80 process of Enteromorphacompressa microalgae is investigated. As
time (min)
shown in this figure, as the temperature increases, the process rate in-
Fig. 5. Effect of Temperature on the Process of Production of Biodiesel from creases and the efficiency of biodiesel production increases. It can be
Enteromorphacompressa Microalgae: Catalyst Concentration = 0.5%, seen in Fig. 5 that temperature has a significant effect on biodiesel
Methanol to Oil ratio = 6. production and that by increasing the temperature, the production ef-
ficiency can be increased several times. According to this figure, by
for biodiesel production. increasing the temperature from 45 °C to 65 °C, production efficiency
increased from 30.31% to 67.05%, more than double. Therefore, tem-
3.3.1. Effect of catalyst concentration on biodiesel production perature is important as one of the most important parameters in the
In Fig. 3, the effect of catalyst concentration on biodiesel production production of biodiesel from Enteromorphacompressa microalgae.
from Enteromorphacompressa microalgae is investigated. In this figure, Since the production of biodiesel from Scenedesmus microalgae was
for three catalyst concentrations of 0.5, 0.75 and 0.1 wt%, the dis- investigated only at a constant temperature of 65 °C, therefore, the
tribution of biodiesel production efficiency is plotted over time. Ac- effect of catalyst concentration and methanol-to-oil ratio on biodiesel
cording to this figure, as the catalyst concentration increases, the rate production from this microalgae was studied.
and efficiency of biodiesel production increase. 70 min into the process,
production efficiency increases from 46.39 percent to 50.19 percent. 3.3.3. Effect of methanol to oil ratio on the biodiesel production
Only 3.8% of production efficiency increases. In the Fig. 6, the effect of the methanol-to-oil ratio on the biodiesel
In Fig. 4, the effect of catalyst concentration on the biodiesel production process of Enteromorphacompressa microalgae is

5
M. Reza Talaghat, et al. Fuel 280 (2020) 118578

1
triglyceride 5 methanol

concentration (mol/L)

concentration (mol/L)
0.8
4.5
0.6
4

0.4
3.5

0.2
0 20 40 60 80 0 20 40 60 80
t (min) t (min)
0.06

0.05 diglyceride 1.5

concentration (mol/L)

concentration (mol/L)
monoglyceride
0.04
1 biodiesel
0.03 glycerol

0.02
0.5
0.01

0 0
0 20 40 60 80 0 20 40 60 80
t (min) t (min)
Fig. 8. Concentration distribution of the of biodiesel production components from Enteromorphacompassa microalgae vs. time.

triglyceride methanol
0.6 9.5
concentration (mol/L)
concentration (mol/L)

0.5
0.4 9

0.3
8.5
0.2
0.1
8
0
0 20 40 60 0 20 40 60
t (min) t (min)
2

0.15 diglyceride
concentration (mol/L)

concentration (mol/L)

monoglyceride 1.5 biodiesel

glycerol
0.1
1

0.05 0.5

0 0
0 20 40 60 0 20 40 60
t (min) t (min)
Fig. 9. Concentration distribution of the of biodiesel production components from the Scenedesmus microalgae vs. time.

compared. According to this figure, as the amount of methanol in- production increased from 60.30% to 83.23%. Finally, based on the
creases, the process speed and efficiency increase substantially. As the results, it can be concluded that the effect of methanol to oil ratio and
ratio of methanol to oil increased from 3 to 9, biodiesel production catalyst concentration on biodiesel production from these two types of
efficiency increased from 17.42% to 40.75%. Fig. 7, shows the effect of microalgae is remarkable.
the methanol-to-oil ratio on the biodiesel production from Scenedesmus
microalgae. This figure shows that as the amount of methanol increases,
the process rate and efficiency increase substantially. As the ratio of
methanol to oil increased from 6 to 12, the efficiency of biodiesel

6
M. Reza Talaghat, et al. Fuel 280 (2020) 118578

rate constant using Eq. 7d 3.4. Distribution of component concentrations in biodiesel production
100.00 rate constant using Eq. 7c processes
90.00 rate constant using Eq. 7b
80.00 rate constant using Eq. 7a
Fig. 8, shows the concentration distribution of the components in
Biodiesel Yield (%)

70.00 the biodiesel production from Enteromorphacompressa microalgae.

60.00 According to this figure, in the first 20 min, the reaction rate is high, so
50.00 the gradient of material concentration changes is high, but then the
40.00 reaction rate gradually decreases and after 50–60 min the reaction rate
30.00 approaches zero. Concentration changes are reduced. The concentra-
20.00 tion of intermediates (monoglycerides and diglycerides) is low com-
10.00 pared to other substances. The concentration of the two substances
0.00 reaches their peak within about 5 min and then decreases and remains
0.50 2.30 5.00 10.00 20.00 40.00 60.00
Reaction Time (min) constant, which means that the rate of production and consumption of
intermediate materials is equal. It is high and decreases with time. The
Fig. 10. The effect of various rate constant functions on biodiesel production same applies to the production of products. Fig. 9, shows the con-
efficiency from Scenedesmus microalgae. centration distribution of the biodiesel production components of the
Scenedesmus microalgae. In this process the production rate is high and
100.00 the production process is completed after approximately 7 min.
90.00
3.5. Effect of various reaction rate constant equations on biodiesel efficiency
80.00
70.00 In this research, the effect of various reaction rate constant equa-
Biodiesel Yield (%)

60.00 tions on biodiesel production yield using Scenedesmus and

Enteromorphacompressa, microalgae’s according to Eqs. (7a) to (7d),
50.00
were investigated. The results are shown in Figs. 10 and 11, respec-
40.00 tively.
30.00 When the reaction rate constant is only a function of temperature
(using Eq. 7a), the results show that biodiesel yield of these algae is
20.00
very low. By observing the figures, it is shown that the reaction rate
10.00 constant is dependent on the concentration of the catalyst. And the rate
0.00 constant is affected by the concentration of the catalyst. Also, when the
10.00 20.00 30.00 40.00 50.00 60.00 70.00
reaction rate constant is a function of the temperature and the second
Reaction Time (min)
rate constant using Eq. 7d power of the catalyst concentration (using Eq. 7C), the results show that
rate constant using Eq. 7c the biodiesel yield is low but its yield is higher than the previous state.
rate constant using Eq. 7b
rate constant using Eq. 7a But when the reaction rate constant is a function of temperature and the
quadratic equation of the catalyst concentration (using Eq. 7d), then the
Fig. 11. The effect of various rate constant functions on biodiesel production
biodiesel yield is greater than all other states. However, when the re-
efficiency from Enteromorphacompressa microalgae.
action rate constant is a function of temperature and has a linear re-
lationship with the catalyst concentration (using Eq. 7b), then the ef-
100 ficiency of biodiesel production at the initial reaction times is less than
when the reaction rate constant is calculated from Eq. 7d. But as the
80 reaction progresses and time elapses, the biodiesel yield increases and
Biodiesel Yield%

the biodiesel efficiency in both cases is approximately equal. But as the

60 reaction progresses and time elapses, the biodiesel yield increases until
the biodiesel yield is equalized using both equations 7b and 7d.
40 The results show that the effect of different reaction rate constant
equations on biodiesel yield is similar for both microalgae investigated
20 in the present study. But the results show that for all the equations
considered for reaction rate constants, the biodiesel yield using
Scenedesmus microalgae is less than Enteromorphacompressa micro-
0
0 20 40 60 80 algae.
time (min)
3.6. Process optimization
Fig. 12. Production of biodiesel from Enteromorphacompassa microalgae at
optimum conditions.
The results showed that three factors: temperature, catalyst con-
centration and methanol-to-oil ratio were effective on biodiesel pro-
Table 5 duction efficiency, although their effect was not the same. Choosing the
Optimum conditions for biodiesel production from Enteromorphacompassa optimum amount of these parameters is important for maximizing
microalgae.
biodiesel production. In this section, the optimum conditions for bio-
Temperature (°C) Catalyst Methanol to Biodiesel production diesel production from these algae are studied. Genetic Algorithm
concentration (wt%) oil ratio efficiency percentage method is used to maximize the efficiency of biodiesel production.
65 0.65 15 96.62
3.6.1. Optimization of biodiesel production from Enteromorphacompressa
microalgae
Using the genetic algorithm optimization method, optimal condi-
tions were calculated to maximize the biodiesel production efficiency of

7
M. Reza Talaghat, et al. Fuel 280 (2020) 118578

Table 6
Optimum conditions for biodiesel production from Scenedesmus microalgae
• By increasing the methanol-to-oil ratio and catalyst concentration,
increase substantially the biodiesel production yield and reaction
Catalyst concentrationwt% Methanol to oil Biodiesel production rate using Scenedesmus microalgae.
ratio efficiency percentage • The maximum biodiesel production yield was used as the objective
function for calculation of optimum conditions using microalgae
1.5 15 93.96
• At the optimum conditions, biodiesel production yield is more than
99%
100 • The type of constant reaction rate function affects biodiesel pro-
duction yield

80 CRediT authorship contribution statement

Biodiesel Yield%

60 Mohammad Reza Talaghat: Supervision, Writing - review &

editing. Shahin Mokhtari: Conceptualization, Methodology, Software,
40 Data curation, Writing - original draft, Validation. Mohammad Saadat:
Software, Validation.
20
Declaration of Competing Interest

0
0 20 40 60 The authors declare that they have no known competing financial
time (min) interests or personal relationships that could have appeared to influ-
Fig. 13. Production of biodiesel from the Scenedesmus microalgae at optimum ence the work reported in this paper.
conditions.
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