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Renewable Energy 202 (2023) 1241–1247

Contents lists available at ScienceDirect

Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Experimental and theoretical feasibility study of methanol application for


Echium oil-based biodiesel production
Mohamad mehdi Naraki a, Payam Parvasi a, *, Seyyed Mohammad Jokar a, Adolfo Iulianelli b
a
Department of Chemical, Petroleum and Gas Engineering, Shiraz University of Technology, Shiraz, Iran
b
Institute on Membrane Technology of the Italian National Research Council (CNR-ITM), Via Pietro Bucci, Cubo 17/C, 87036, Rende, CS, Italy

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, the effect of ultrasound waves on biodiesel production from methanol and Echium oil is evaluated
Biodiesel production experimentally under different operating conditions. A two-step esterification–transesterification process was
Ultrasound applied to improve the biodiesel quality, and, in order to optimize the reaction conditions, the effect of variables
Echium oil
such as methanol to oil molar ratio, KOH catalyst concentration and temperature were experimentally investi­
Response surface method
Reaction rate kinetics
gated. The results showed that the optimum biodiesel yield (97.2%) could be obtained at a catalyst concentration
of 1.875% w.t, feed molar ratio equal to 9.65, and at 50 ◦ C of operating temperature. The acid value, saponi­
fication numbers, iodine value, density, kinematic viscosity, fire point, cloud point and flash point were
measured and compared with ASTM D6751 and EN 14214 standards. The results of the analysis showed that the
produced biodiesel is a good alternative to fossil fuels. The results demonstrate that methanol and Echium Oil can
be used as a proper feedstock for biofuel production. Furthermore, the kinetic study of transesterification is
carried out for Echium oil production and the reaction rate constant and activation energy were determined.
Finally, the sizing calculations and cost estimation of the Echium oil-based biodiesel production were
investigated.

1. Introduction of catalyst [7].


Among the numerous studies dealing with the production of bio­
In the last few years, the world’s energy demand is increasing due to diesel fuel from vegetable oils, Silva et al. [8] illustrated the use of
global economic development and population growth, and most of it soybean oil as a vegetable source for biodiesel production through the
comes from the exploitation of fossil sources, which are non-renewable. methanolysis reaction over Mg–Al hydrotalcites as a heterogeneous
Consequently, scientists are making many efforts to propose suitable catalyst, evaluating the effect of Mg/Al ratio on the basicity and catalytic
renewable alternatives to fossil fuels. Biodiesel represents today a valid activity for biodiesel production. As best results, they found that, at
option and is a favorite possible alternative to fossil fuels due to its lower 230 ◦ C, methanol:soybean oil molar ratio equal to 13:1, 1 h of reaction
emissions than those produced by the fossil fuels, and also because it is time and a catalyst loading of 5 wt%, the soybean oil conversion was
biodegradable, non-toxic, and essentially free of sulphur and aromatics around 90%. Feyzi et al. [9] studied the preparation, characterization,
components [1]. kinetic and thermodynamic behaviors of MgO–La2O3 nanocatalysts for
Biodiesel is defined as mono-alkyl esters of long-chain fatty acids biodiesel production from sunflower oil. They demonstrated that the
coming from vegetable oils [2,3], or animal fats [4,5], or microalgae oil catalyst with Mg/La = 60 wt% was the best nanocatalyst choice. In this
[6]. Methanol is the most frequently applied alcohol to achieve trans­ regard, at 65 ◦ C, methanol/oil = 18/1, a mechanical stirring of 700 rpm
esterification of biodiesel fuel production due to its low cost, physical for 5 h, the nanocatalyst showed high catalytic activity for biodiesel
and chemical advantages. In this reaction, triglycerides, as the main production reaching a biodiesel yield of around 98%.
components of vegetable oils, react with an alcohol to produce fatty acid Recent studies were focused on the ultrasonic-assisted method as it is
mono-alkyl esters and glycerol as a by-product. In this regard, there are one of the simplest and capable way to reduce the reaction time
many parameters affecting the transesterification reaction such as: compared to the conventional stirred procedure during the production
temperature, methanol/oil molar ratio (M/O), catalyst type and amount of biodiesel [10]. However, the effect of ultrasonication on enhancing

* Corresponding author.
E-mail address: parvasi@sutech.ac.ir (P. Parvasi).

https://doi.org/10.1016/j.renene.2022.11.118
Received 28 July 2022; Received in revised form 7 November 2022; Accepted 27 November 2022
Available online 1 December 2022
0960-1481/© 2022 Elsevier Ltd. All rights reserved.
M. Naraki et al. Renewable Energy 202 (2023) 1241–1247

the transesterification reaction lies mainly in intensifying the mixing of of 30 experiments. Four variables such as catalyst weight, reaction
the immiscible methanol and triglyceride phases [11,12]. Furthermore, temperature, processing time and methanol to melon seed oil molar
ultrasonic irradiation causes cavitation of bubbles near the phase ratio in five levels were used to design the best set of operating condi­
boundary between the alcohol and oil phases. As a result, micro-fine tions. An optimal biodiesel yield was found to be ~95% at methanol to
bubbles are formed. The asymmetric collapse of the cavitation bubbles melon oil ratio equal to 6/1, 0.8% (w/w) of catalyst load, and a pro­
disrupts the phase boundary and impinging of the liquids creates micro cessing time of 60 min at 55 ◦ C of reaction temperature.
jets, leading to intensive mixing of the system near the phase boundary. In this study, the catalytic transesterification reaction by using a
The cavitation may also lead to a localized increase in temperature at the KOH catalyst and methanol was studied for biodiesel production. The
phase boundary, enhancing the transesterification reaction. Because of novelty of the work is the use of Echium oil as a new feedstock to pro­
the formation of micro jets and localized temperature increase, neither duce biodiesel. Also, in the biodiesel synthesis process, ultrasonic wave
agitation nor heating are required to produce biodiesel by ultrasound technology has been used instead of a mechanical stirrer.
application [13,14]. The variables were optimized by using a CCD approach-based RSM to
On the other hand, recent research findings confirmed that the use of maximize the biodiesel yield with the aid of Design-Expert software. The
homogeneous catalysts in combination with ultrasonication may be experimental results obtained at two different temperatures have been
effective in saving time, resulting in an economical method for pro­ used to develop a simple kinetic model for the transesterification pro­
ducing biodiesel from different types of feedstocks [15–17]. In short, the cess. Then, the fuel properties of the biodiesel produced from optimized
use of ultrasonic assisted process could lead to high yields in short re­ conditions were determined and compared with the biodiesel standard
action time, low reaction temperature and reduce the amount of hy­ of EN 14214. The results of the research have shown that cloud point,
droxide catalysts needed. Besides hydroxides, another type of catalyst flash point and fire point of biodiesel fuels are better than fossil fuels.
could be used, such as liquid acid, particularly useful for feedstocks with
high free fatty acid (FFA) content [16]. For example, Colucci et al. [17] 2. Materials, methods and analysis
studied the production of biodiesel from soybean oil over basic catalyst
potassium hydroxide in a temperature range between 40 and 60 ◦ C. As 2.1. Materials
the best result, they obtained a yield of around 90% in 15 min under
reaction. They attributed the high reaction rate to the increase of the Methanol (99.5%), sulfuric acid (98%) and KOH pellets were sup­
interfacial area between the reactants resulting from cavitation bubbles plied from Merck Chemical Company. The Echium seed was purchased
generated by ultrasonic irradiation. This phenomenon allowed a more from local oil stores. The refined oil seed was extracted using the cold
efficient contact between the catalyst and the reactants, favoring the pressing method. The molecular weight, acid number and FFA content of
achievement of high yield. the refined Echium seed oil are measured as 881.417 g/mol, 95 mg
Optimization methods are used in many areas of study to find solu­ KOH/g and 9.5%, respectively.
tions that maximize or minimize some study parameters. In biodiesel
synthesis formulation, the optimization of reaction variables and con­
ditions for transesterification reaction is one of the most important steps 2.2. Ultrasonic reactor setup
in the process to attain maximum yield with minimum cost. Conven­
tional optimization (one-factor at a time) methods are well known [18]; Fig. 1 shows a schematic of the experimental setup. The Elma ul­
they possess some disadvantages like the need for a high number of trasonic bath model TI-H5 was used to perform the transesterification
experimental runtime, and an insufficient ability to provide a clear reaction [21]. The ultrasound device could operate with frequency of 45
synergistic effect of the process variables. kHz, a sound power level up to 100 W, and a temperature range up to
On the other hand, the utilization of the response surface method­ 70 ◦ C. All the experiments were carried out in a triple-neck flask with
ology (RSM) to optimize the transesterification reaction is attracting condenser reflux (for returning the condensed alcohol vapor to the
particular attention as it provides a detailed response of the effects due
to the variables interacting with each other during the reaction process
with fewer experiments [19]. RSM has many advantages when
compared to classical methods. It needs fewer experiments to study the
effects of the factors and the optimum combination of all the variables
can be revealed. The interaction (the behavior of one factor may be
dependent on the level of another factor) between factors can be
determined. It also requires less time and effort. These fewer experi­
mental careers are sufficient to provide a statistically significant result,
designing experiments to maximize performance and minimize pro­
duction costs. In this regard, the Design Expert software is based on RSM
data modeling and provides a set of mathematical and statistical
methods used to model and optimize the process variables, where the
response is influenced by several operational or process parameters
[18].
Sarve et al. [19] estimated the prediction ability of the RSM models
for biodiesel production from sesame oil under ultrasonic waves over
barium hydroxide as a basic heterogeneous catalyst. In particular, the
RSM model was based on five levels and four factors in central com­
posite design to obtain the best combination of catalyst concentration,
methanol to oil molar ratio, temperature and reaction time for reaching
the maximum fatty acid methyl esters (FAME) content, which was equal
to around 99%.
For example, Aliozo et al. [20] used melon oil to produce biodiesel
through a statistical analysis of interaction effects of independent vari­
ables using central composite design (CCD) based RSM with a total plan Fig. 1. Schematic of the experimental setup.

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M. Naraki et al. Renewable Energy 202 (2023) 1241–1247

reactor). Table 1
CCD experimental design matrix.
2.3. Esterification process Factor Factor 2 Factor 3 Biodiesel Yield
1
Due to the high percentage of FFAs present in the Echium seed oil, a A: B: C: Experimental Predicted Relative
two-step esterification-transesterification mechanism was considered to error
improve biodiesel quality. M/O Catalyst Temperature (%) (%) (%)
Esterification of oils and fats is one of the advanced techniques used ratio (wt %) (◦ C)
to modify the basic structure of glycerides. This process should be per­ 8 1 60 86.97 86.46 0.5864
formed for the oils with high FA content ranging from 0.5 to 5% by mass 8 2 50 88.23 89.17 1.0654
[22]. Hence, the esterification reaction was performed for refined 11 1.5 60 87.89 86.96 1.0581
Echium seed oil with 4.8% FA, and the esterification process was per­ 9 1.5 60 86.54 86.74 0.2311
10 1 50 93.25 94.12 0.9330
formed by 50 gr Echium seed oil, 11.72 gr methanol and 5%w.t H2SO4 as 11 1.5 50 91.76 91.32 0.4795
the acid catalyst, 45 kHz ultrasonic frequency, 1-h of reaction time and 10 2 60 84.60 85.71 1.3120
50 ◦ C of the reaction temperature in the ultrasonic reactor system. After 9 2.5 60 82.82 82.11 0.8573
the completion of the reaction, both methanol and catalyst were sepa­ 7 1.5 60 85.18 85.16 0.0235
10 2 50 88.50 89.31 0.9153
rated from the oil layer. Afterward, the esterified oil was washed with
9 2.5 50 86.75 86.32 0.4957
distilled water three times, until the catalyst was completely removed, 8 2 60 84.75 84.46 0.3422
and finally heated (at 110 ◦ C for 1 h) to remove the residual water 8 1 50 89.97 89.99 0.0222
content. 9 1.5 50 89.99 89.11 0.9779
7 1.5 50 88.21 88.13 0.0907
9 1.5 60 86.54 87.78 1.4329
2.4. Transesterification process 9 1.5 50 89.99 89.17 0.9112
9 0.5 60 – 21.86 –
The ultrasonic reactor system was filled with the esterified oil com­ 9 0.5 50 – 23.67 –
10 1 60 89.82 89.73 0.1002
ing from the esterification process, methanol (methanol to oil molar
ratio in the range 7:1–11:1) and KOH (0.5%–2.5%), at the operating
temperatures of 50 ◦ C and 60 ◦ C. The transesterification reaction time
was set equal to 0.5 h and the ultrasonic frequency at 45 kHz.
The five-levels-three-factor RSM in Design-Expert software was used
to optimize the transesterification reaction parameters. Totally, 20 ex­
periments were performed based on the CCD approach to evaluate the
effect of the variables (M/O ratio, catalyst concentration, and temper­
ature) on the biodiesel yield.
After the transesterification reaction, the produced mixture is
centrifuged for 10 min at 2000 rpm to separate glycerol and biodiesel.
The obtained mixture was settled and the biodiesel was washed with
distilled water three times. Afterward, the washed biodiesel was heated
at 110 ◦ C to eliminate the excess water and methanol [23]. Biodiesel
yield was measured according to the following equation [24]:
Total weight of biodiesel
Biodiesel yield = × 100 (1)
Total weight of Echium oil

3. Results and discussions

In this section, the results of laboratory tests, synthesis process


optimization, transesterification reaction kinetic study, physicochem­
ical properties analysis and economic estimation are presented and
discussed.

3.1. Experimental design results

Table 1 lists the results of the CCD experimental design matrix for the
Fig. 2. Graphical assessment of the Echium oil-based biodiesel yield: predicted
transesterification reaction. The design expert software is used to fit a vs. experimental data.
quadratic (second-order) polynomial model to calculate the yield as a
function of the process variables (A: M/O ratio, B: Catalyst (wt %), and
3.2. Effect of process variables on biodiesel production
C: Temperature (◦ C)). In the last column, the relative error of the pre­
dicted biodiesel yield is presented in terms of experimental biodiesel
As mentioned, Design-expert software fitted a quadratic (second-
yield. The fitting model supported the clearly, a good consistency was
order) polynomial model of biodiesel yield data in terms of reaction
observed between the experimental and the predicted biodiesel yield.
temperature, catalyst concentration and M/O molar ratio. In the
A line of unit slope for biodiesel yield is illustrated in Fig. 2. This line
following, the Design-expert software used to investigate the effect of
displays the zero deviation between the predicted and observed values.
operating parameters on biodiesel yield variation by the fitted model.
As shown, all the points are close to the line of the perfect fit and small
The impact of reaction temperature, catalyst concentration and Meth­
errors are detected between the values predicted by the second-order
anol to oil (M/O) molar ratio on the synthesis of Echium biodiesel with
model and experimental values. The figure shows that the model is
the ultrasonic frequency of 45 kHz is illustrated in Figs. 3–4.
accurate.

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M. Naraki et al. Renewable Energy 202 (2023) 1241–1247

saponification reaction is an unwanted reaction that affects the main


reaction by reducing the biodiesel yield. With a KOH catalyst of 2.5 wt
%, due to the saponification problem, there was a rather low conversion
rate of 80%. Hence, it was observed that a reduction in the KOH con­
centration from 2.0 wt % to 1.875 wt % enhanced the biodiesel yield to
97.2%, since saponification was considerably decreased.
Fig. 5(a and b) shows the 3-D and contour diagrams of the interaction
of M/O molar ratio and catalyst concentration on the biodiesel synthesis
yield. As shown, the red area shows a higher yield, while the blue area
indicates a lower one. The biodiesel yield is relatively affected by the M/
O at low catalyst concentrations.

Fig. 3. Effect of M/O molar ratio on biodiesel synthesis yield (catalyst con­
centration = 1.5%).

Fig. 4. Effect of catalyst concentration on the biodiesel synthesis yield (T =


50 ◦ C and M/O molar ratio = 9).

Fig. 3 shows the effect of M/O molar ratio on the biodiesel yield at
different temperatures. By increasing the M/O molar ratio, the biodiesel
synthesis yield increases, reaching the best value of ~95% at M/O ratio
of 9.5. However, a further increase in M/O molar ratio to 11 was
responsible for a decrease in the biodiesel yield due to the dilution of the
reaction medium. Furthermore, Fig. 3 also shows that the biodiesel yield
plot at 50 ◦ C results to be higher than that at 60 ◦ C in the whole range of
M/O ratio investigated in this work. This was due to the low boiling
point of methanol (~62 ◦ C); indeed, at 60 ◦ C of operating temperature,
methanol was transformed mostly into methanol vapor, affecting the
synthesis reaction and causing a depletion of the biodiesel yield with
respect to the values obtained at a lower temperature (50 ◦ C).
Fig. 4 illustrates how, by increasing the catalyst concentration up to
1.7–1.8 wt%, the reaction efficiency increases up to reaching a
maximum. At higher values of catalyst concentration, a relative reduc­
tion in biodiesel yield was observed. This phenomenon was due to the
increase in the concentration of the KOH catalyst and, consequently, to
Fig. 5. a) 3-D plot; b) contour plot; The effect of operating parameters on the
the possibility of further development of the saponification reaction. The biodiesel synthesis yield (T = 50 ◦ C).

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M. Naraki et al. Renewable Energy 202 (2023) 1241–1247

3.3. Optimization of process variables

The optimal values of operating parameters were evaluated by


Design Expert software (Fig. 6). The simulations demonstrated that a
maximum yield of 97.2% could be obtained with the KOH catalyst
concentration of 1.875 wt% and M/O of 9.65:1 (Figs. 3–5).

3.4. Fuel properties of Echium oil-based biodiesel

A number of gas chromatography–mass spectrometry (GC-MS)


experimental tests were carried out for Echium biodiesel and, as an
example, one of the chromatograms describing the biodiesel results
obtained at steady state conditions is reported in Fig. 7. Table 2 reports
the compounds present in the biodiesel depending on the typical
retention time. The data reported in the latter table demonstrated that
biodiesel contains a variety of FAMEs from C14 to C20, including pal­
mitic acid (C16: 0), stearic acid (C18: 0) and linolenic acid (C18: 2).
The characteristics of studied biodiesel were obtained based on
ASTM standard procedures. Table 3 presents the Echium oil biodiesel
characteristics in comparison with the standards. As shown, the gained
values are within the standard range for diesel fuel. The analysis ap­ Fig. 7. The GC/MS chromatogram analysis of Echium biodiesel.
proves a reliable performance of biodiesel fuel produced from Echium
oil.
Table 2
3.5. Kinetics modeling for methanol + Echium oil mixture for biodiesel The comparison of the FA composition (wt.%) of the Echium biodiesel.
generation FA Chemical FAME composition Type of fatty
structure (wt)% acid
The proposed mechanism reported in Eq. (2) is based on the
Lauric acid C12:0 3.081 saturated
assumption of a homogeneous catalytic reaction. The former follows
Myristic C14:0 1.846 saturated
first-order kinetics as a function of the concentration of oil (Triglyceride
Palmitic acid C16:0 14.908 saturated
(TG)) and the reaction temperature [25]. Due to the high methanol Stearic acid C18:0 9.272 saturated
concentration (200% excess), methanol was not considered a limiting Oleic acid C18:1 5.409 unsaturated
reactant. This also shifted the equilibrium to the reaction products Linoleic acid C18:2 46.279 unsaturated
(forward reaction); therefore, the overall reaction was assumed to be a Nonadecylic C19:0 0.722 saturated
acid
single-step shunt reaction (neglecting the intermediate reaction).
Arachidic acid C20:0 0.914 saturated
TG + 3M → P + G (2)
The actual reaction rate is the mole of fame product over time. The
where M is methanol, P is biodiesel and G is glycerol. As per the
reaction rate constant (k) was obtained by taking the TG amount at the
assumption stated above, the rate equation is given by Ref. [25]:
reaction time for the individual test. The parameters of equation (4) are
rP =
dCP
= kCTG (3) estimated by the fitting k at two different temperatures for 20 experi­
dt ments. The estimated values for k0 and E are presented in Table 4.
The reaction rate constant with respect to temperature was calcu­
lated as an Arrhenius-like equation [25]:

(4)
E
k = k0 e− RT

Fig. 6. Desirability ramp of yield.

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M. Naraki et al. Renewable Energy 202 (2023) 1241–1247

Table 3
The total feed entering per batch
Physiochemical properties of Echium oil biodiesel. VR = = 16890 lit = 16.89 m3 (8)
Average feed density
characteristic Unit ASTM- EN- Diesel Echium oil
D6751 14214 fuel Biodiesel Batch reactors should not be filled to more than three-fourths of their
ASTM (this study) available free space (headspace), and the charge must be decreased for
D975
safe operation [27,28]. For reactors less than 1.9 m3 15% space is
Density (@ 15 ◦ C) g/cm3 – 860–900 840–860 894 allowed and for reactors greater than 1.9 m3 10% space is allowed [29].
Kinematic mm2/s 3.5–5 1.9–6 1.9–3.8 4.23
With 10% headspace allowance [29], the vessel volume is estimated at
Viscosity (@ (40 ◦ C) (40 ◦ C)
21 ◦ C)
approximately 18.58 m3 for 20,000 tons/year of biodiesel production.
Acid Value mg 0.8 max 0.5 max – 0.47 The optimum length to the diameter of this batch reactor is considered
KOH/ about 3 but a range of 2.5–5.0 is most common [30].
g
Saponification mg/kg 500 312.5 204.76
π
– H/D = 3and Vb = HD2 (9)
value max max 4
Iodine value gI2/ 120 38.07
Therefore, the reactor diameter and length are 2 m and 6 m,
– –
100g max
Flash Point ◦
C 130 120 min 70 176 respectively. For a 304 stainless steel batch reactor with atmospheric
min operating pressure, a reactor wall thickness of 3.9 mm and a reactor
Fire Point ◦
C – – 74 194 head thickness of 4 mm are recommended [31].
Cloud Point C (-3)-12 (-15)-5 − 2
The cost of a batch reactor made of 304 stainless steel with a length

of 6 m, a diameter of 2 m and a wall thickness of 3.9 mm is equal to


$90,000 [27].
Table 4
The reaction rate constant parameters. 5. Conclusions
Parameter Value

k0 (min− 1 ) 0.1445 By application of KOH catalyst and an ultrasound-assisted system,


( j ) 2288.2 the two-step esterification–transesterification process for biodiesel pro­
duction from Echium oil was investigated in a Batch reactor. A response
E
mol K
surface design methodology was assisted to evaluate the effects of M/O
molar ratio, KOH catalyst concentration and temperature on biodiesel
4. Sizing and cost estimation of an industrial batch reactor for
yield at the frequency of 45 kHz and reaction time of 0.5 h. The
methanol þ Echium oil mixture for biodiesel generation
experimental design showed that the maximum yield of 97.2% could be
achieved at optimal values (KOH catalyst concentration of 1.875 wt%
In this section, sizing and cost estimations were calculated theoret­
and M/O of 9.65:1(.
ically to develop an industrial batch reactor for 20,000 tons/year (60
In the following, the reaction rate was obtained based on the
tons/day) of biodiesel production via a two-step process consisting of
experimental results and was used for reactor sizing. Results showed
Echium oil esterification and transesterification. The esterification re­
that 20,000 tons/year (60 tons/day) of biodiesel could be produced in a
action was carried out using 1:7 oil to methanol molar ratio, 5 wt%
batch reactor having a length of 6 m and an outside diameter of 2 m, and
sulfuric acid in oil at 50 ◦ C. The transesterification reaction was carried
a wall thickness of 3.9 mm and a head thickness of 4 mm. This reactor
out at 50 ◦ C, using 1.63 wt% KOH catalyst and a molar ratio of M/O of
will cost $90,000.
9.3:1. The ultrasonic frequency of the reactor in both steps was set at 45
kHz.
After determining the reaction rate, the batch reactor design Declaration of competing interest
included: the reactor volume reactor, the length, diameter and wall
thickness of the reactor. The authors declare that they have no known competing financial
At the higher concentration of Methanol (200% excess), the rate of interests or personal relationships that could have appeared to influence
reaction depends only on the concentration of Triglycerides and the the work reported in this paper.
order of reaction becomes the first order [25].
Acknowledgment
Oil + Methanol → FAME + Water (5)
For the first-order reaction with the specified reaction rate constant The authors would like to thank the Iran National Science Founda­
and the conversion rate of 97%, the reaction time is: tion (INSF) for supporting this work.

tr = −
ln(1 − 0.97)
≅ 45 min (6) References
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