i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 8 4 5 e1 7 8 6 2

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Techno-economic comparison of three biodiesel

production scenarios enhanced by glycerol
supercritical water reforming process

Mohammad Reza Ziyai a, Mehdi Mehrpooya b,c,*, Mortaza Aghbashlo a,**,

Mahmoud Omid a,***, Ali Sulaiman Alsagri d, Meisam Tabatabaei e,f,g
a
Department of Mechanical Engineering of Agricultural Machinery, Faculty of Agricultural Engineering and
Technology, College of Agriculture and Natural Resources, University of Tehran, Karaj, Iran
b
Department of Renewable Energies and Environment, Faculty of New Sciences and Technologies, University of
Tehran, Tehran, Iran
c
Hydrogen and Fuel Cell Laboratory, Faculty of New Sciences and Technologies, University of Tehran, Tehran, Iran
d
Mechanical Engineering Department, Qassim University, Buraydah 51431, Saudi Arabia
e
Faculty of Plantation and Agrotechnology, Universiti Teknologi MARA, 40450, Shah Alam, Selangor, Malaysia
f
Biofuel Research Team (BRTeam), Karaj, Iran
g
Microbial Biotechnology Department, Agricultural Biotechnology Research Institute of Iran (ABRII), Agricultural
Research, Extension and Education Organization (AREEO), Karaj, Iran

article info abstract

Article history: In this study, techno-economic comparison of three different biodiesel production sce-
Received 26 January 2019 narios integrated with glycerol supercritical water reforming (SCWR) process to produce
Received in revised form electricity is conducted. In the first scenario, biodiesel is synthesized from acid-pretreated
21 April 2019 waste cooking oil (WCO) in the presence of alkali catalyst. In the second scenario, biodiesel
Accepted 4 May 2019 is obtained from WCO by acid catalyst. In the third scenario, biodiesel is derived from WCO
Available online 30 May 2019 using acid catalyst, followed by hexane extraction of the produced methyl esters. The
glycerol evolved from all the above-mentioned pathways is then subjected to the SCWR
Keywords: process in order to produce hydrogen. The produced hydrogen is then combusted to pro-
Biodiesel plant vide thermal energy required by biodiesel production and purification processes as well as
Glycerol supercritical water reform- to generate electricity. All the developed scenarios are modeled and simulated in Aspen
ing HYSYS software environment. In order to simplify the simulation process, canola-based
Hydrogen production WCO is considered as triolein with 6 wt% oleic acid (free fatty acid) and, accordingly, the
Techno-economic analysis prepared biodiesel is taken into account as methyl oleate. In order to compare the eco-
Waste cooking oil nomic profitability of the developed approaches, several economic indicators including net
present value (NPV), internal rate of return (IRR), payback period (PBP), discounted payback
period (DPBP), and return on investment (ROI) are used. A sensitivity analysis is also carried
out to show how variations in feedstock, biodiesel, and electricity prices can affect the NPV
of the developed scenarios. According to the results obtained, the highest IRR and ROI
values as decision-making parameters are obtained for the first scenario, manifesting its
suitability from the techno-economic viewpoint. The economic indicators of the second
scenario are also acceptable and very close to the first approach. Overall, upgrading

* Corresponding author. Department of Renewable Energies and Environment, Faculty of New Sciences and Technologies, University of
Tehran, Tehran, Iran.
** Corresponding author.
*** Corresponding author.
E-mail addresses: mehrpoya@ut.ac.ir (M. Mehrpooya), maghbashlo@ut.ac.ir (M. Aghbashlo), omid@ut.ac.ir (M. Omid).
https://doi.org/10.1016/j.ijhydene.2019.05.017
0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
17846 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 8 4 5 e1 7 8 6 2
glycerol into hydrogen using SCWR process appears to be an attractive strategy for
enhancing the economic viability of biodiesel production plants.
© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Introduction
The world energy consumption is dramatically increasing day
by day due to industrial development and population growth
[1,2]. Accordingly, there is ever increasing demand for fossil
fuel resources like coal, petroleum fuel, and natural gas [3,4].
However, concerns about the devastating impacts of
increasing consumption of fossil fuels on the environment
and more importantly, on human health have spurred efforts
to explore cost-effective and eco-benign substitutes for the
conventional fuels [5e9]. Among the various alternative liquid
fuels introduced to date, biodiesel is one of the most prom-
ising renewable transportation fuels owing to its physico-
chemical similarities with mineral diesel fuel [10,11]. In
addition, this renewable fuel is biodegradable, non-toxic, and
carbon-neutral while its application in the neat or blend form
can profoundly mitigate the emission of toxic pollutants [12].
However, biodiesel suffers from some practical drawbacks
like low calorific value, poor cold properties, high oxidative
degradation, and high NOx emission [13,14].
Biodiesel is usually produced from vegetable oils, animal
fats, and waste-oriented oils using methanol/ethanol in the
presence of an alkali/acid catalyst [15,16]. Nevertheless, bio-
diesel production from food-grade vegetable oils/fats has been
blamed for the food price hikes and shortages [17]. Biodiesel
production from non-edible oil feedstocks has also been crit-
icized as it has triggered an increasing competition over arable
land and water resources [18]. On the other hand, feedstock
itself contributes to more than 80% of the production cost [19],
propelling the biodiesel industry towards the use of low-cost
waste-oriented feedstocks. These waste feedstocks contain
high levels of impurities like free fatty acid (FFA) and water,
leading to the formation of soap during the alkali-catalyzed
transesterification process. Accordingly, additional pretreat-
ment steps would be required to remove FFA and water,
increasing the capital and operating costs of biodiesel plants.
It should be noted that the alkali-assisted transesterification is
the most widely used process in the biodiesel industry
because of its high reaction rate and process yield. In order to
avoid the formation of soap, acid-catalyzed transesterification
process can be implemented in plants producing biodiesel
from feedstocks of high FFA contents. Apart from the
feedstock-related challenges faced, biodiesel production and
refining processes are energy-intensive operations,
consuming huge amounts of thermal and electrical energy.
This can in turn increase the unit cost of product and conse-
quently jeopardize the economic viability of the biodiesel
industry.
Glycerol is the main by-product of the transesterification
process, accounting for approximately 10 wt% of the total
biodiesel produced. The purified glycerol can be used in
cosmetics, pharmaceuticals, and food industries [20]. How-
ever, separation and purification of glycerol obtained from
biodiesel production processes is complicated, involving
expensive operations. On the other hand, the global biodiesel
glycerol production has increased as biodiesel production has
ramped up, swamping the market and lowering its price.
Furthermore, biodiesel-derived glycerol cannot be directly
combusted due to its lower heating value and ineffective
combustion as well as generation of highly-toxic acrolein [21].
These in turn have collectively led to releasing glycerol-
containing biodiesel wastes into the environment, resulting
in serious pollution problems. In order to address these issues,
various methods have been suggested in the published liter-
ature in order to convert biodiesel-derived crude glycerol into
value-added chemicals and fuels [22e30].
Among the various pathways proposed in the literature,
thermochemical conversion of glycerol into hydrogen has
attracted a great deal of attention. For example, Adhikari et al.
[31] performed a thermodynamic equilibrium analysis for the
steam reforming process of glycerol at different pressures,
temperatures, and water-to-glycerol feed ratios. Valliyappan
et al. [32] experimentally investigated hydrogen and syngas
production through pyrolysis of glycerol. May et al. [33]
experimentally studied the catalytic gasification of glycerol
in supercritical water. Ortiz et al. [34] carried out a thermo-
dynamic analysis of the glycerol supercritical water reforming
(SCWR) process using the total Gibbs free energy minimiza-
tion method. Guo et al. [35] used a continuous flow tubular
reactor to produce hydrogen from glycerol by supercritical
water gasification. Ortiz et al. [36] optimized power and
hydrogen production from glycerol using the SCWR process.
Pairojpiriyakul et al. [37] used various cobalt-based catalysts to
produce hydrogen from glycerol through the SCWR process.
Hajjaji et al. [38] energetically and exergetically optimized
hydrogen production from glycerol by autothermal reforming
process. Hajjaji et al. [39] carried out an energetic-exergetic
parametric study on hydrogen production from glycerol
using the steam reforming process. Galera and Ortiz [40]
techno-economically compared hydrogen and power pro-
duction from the SCWR and autothermal SCWR processes of
glycerol. Ortiz et al. [41] experimentally compared the effect of
Ru and Ni catalysts on the SCWR process of glycerol in a
tubular fixed-bed reactor. Cormos and Cormos [42] techno-
economically and environmentally evaluated industrial-
scale hydrogen and power generation from glycerol steam
reforming with and without carbon capture.
According to the above-mentioned studies, converting
glycerol into hydrogen could not only improve the economic
features of biodiesel industry but also could avoid discharging
glycerol-containing waste streams into the environment. The
produced hydrogen can be sold or even used as fuel in burners
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 8 4 5 e1 7 8 6 2
in order to meet the thermal and electrical energy re-
quirements of biodiesel plants. In addition, the huge pressure
energy of the gas leaving the glycerol reforming reactor can be
converted into electrical power through an expander to
further improve the economic viability of biodiesel plants.
Numerous research attempts have been reported in the liter-
ature on the production of biodiesel from various feedstocks
with their focus on techno-economic feasibility of the re-
ported processes [43e45]. In addition, a number of studies
have been conducted to date on the techno-economic analysis
of glycerol conversion into hydrogen and power [36,40,42,46].
However, these research works have mainly concentrated on
the glycerol-reforming unit without considering the main
units of a biodiesel production plant viz. pretreatment,
transesterification, separation, and purification units.
Therefore, unlike previous works published in this domain,
the crude glycerol containing various impurities (evolved
through the transesterification process) is reformed through
the SCWR process in the present study. To the best of our
knowledge, the SCWR process annexed to biodiesel produc-
tion plants has not never been comprehensively investigated
from the techno-economic viewpoint. By reforming the
evolved glycerol and combusting the produced hydrogen, not
only thermal and electrical energy requirements of the bio-
diesel production and purification processes are met but also
an extra power is generated, collectively further economizing
biodiesel production. Accordingly, the goal of this study is to
conduct a comprehensive techno-economic analysis of three
biodiesel production scenarios annexed to the SCWR of the
generated glycerol to meet their energy demands and to
generate electricity. These scenarios are considered to assess
the effects of biodiesel production and refining methods on
the economic viability of the biodiesel industry. It is worth
mentioning that the SCWR process has both high efficiency
and selectivity for hydrogen production due to the unique
attributes of supercritical water, providing higher space-time
yields and decreasing mass transfer constraints [47]. In addi-
tion, the miscibility of organic solvents and gases is favorably
increased under supercritical conditions, accelerating chem-
ical reactions. The scenarios considered herein are as follows:
I) Biodiesel production from acid-pretreated waste cook-
ing oil (WCO) containing 6 wt% FFA, using alkali catalyst
followed by the SCWR of the generated glycerol
II) Biodiesel production from WCO using acid catalyst fol-
lowed by the SCWR of the produced glycerol
III) Biodiesel production from WCO using acid catalyst and
subsequent hexane extraction of the evolved methyl
esters followed by the SCWR of the generated glycerol
All the above-mentioned scenarios are modeled and
simulated in the HYSYS software environment.
Process simulation
Biodiesel production
In order to simulate the above-mentioned scenarios, the
HYSYS software (version 9) is used. To start the simulation
17847
process, chemical compounds involved in the process should
first be defined in the software environment. The chemical
compounds, which are not available in the library of the
software, are introduced using the hypothetical tool. In addi-
tion, for the streams consisting of several chemical com-
pounds, the dominant chemical compounds are considered as
their representatives. For example, canola oil is mainly
composed of triolein (62 wt%) [48], while its biodiesel contains
57.75 wt% methyl oleate [49]. Accordingly, triolein is used as
the representative of canola-based WCO with 6 wt% FFA (oleic
acid). In addition, methyl oleate is taken into account as the
representative of the resultant biodiesel. The thermodynamic
properties of triolein, oleic acid, and methyl oleate are sum-
marized in Table 1. Non-random two liquid (NRTL) thermo-
dynamic activity model is used to predict the activity
coefficients because of the presence of highly polar compo-
nents like methanol and glycerol. Furthermore, the universal
quasi chemical (UNIFAC LLE) model is used to estimate the
interaction parameter coefficients between components
which are not available in the HYSYS library. In order to make
the process more applicable to the real-world conditions, the
percentile conversion of WCO into biodiesel during the
transesterification/esterification process is simulated accord-
ing to the experimental data reported by Zhang et al. [50].
Glycerol SCWR process
Glycerol produced in the developed plants is reformed using
supercritical water in order to produce hydrogen. The glycerol
SCWR process is modeled according to Ortiz et al. [34]. How-
ever, the SCWR process is an energy-intensive process,
requiring high amounts of thermal energy. In order to reduce
the exogenous natural gas consumption, the syngas produced
in the glycerol reforming unit is used as fuel in the burner for
improving energy self-sufficiency of the developed plants. In
order to simulate the reforming unit, the well-known Predic-
tive Soave-Redlich-Kwang (PSRK) model is used as equation of
state (EOS) due to its higher temperature and pressure. The
produced glycerol is first diluted with water in order to reduce
its viscosity for facilitating the pumping process. The mass
flow rate of water fed into the reforming reactor is found by
trial-and-error method through maximizing the hydrogen
production rate while minimizing the methane formation
rate. In addition, water evaporation is an energy consuming
process and higher water contents result in the higher losses
of the thermal energy supplied to the reforming unit propor-
tionally. The pressure of water-glycerol mixture is then
increased to 240 atm [34]. The pressurized mixture is gradually
heated up to 382
C using two heat exchangers. It should be
noted that this temperature is the highest temperature to
keep the water-glycerol mixture in the liquid phase. After-
wards, the water-glycerol mixture at the temperature of 382
C
and the pressure of 240 atm is fed into the reforming unit. The
reforming process is carried out at 800
C.
The input glycerol stream is initially preheated in the first
heat exchanger by thermal energy of the water stream pre-
viously used for preheating natural gas and intake air. This
stream is then heated in the second heat exchanger using the
thermal energy of the furnace outlet stream (G1). Reforming
reactions is a type of equilibrium reaction. Therefore, R-Gibbs
17848 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 8 4 5 e1 7 8 6 2

Table 1 e Thermodynamic properties of the compounds involved in the process.

Component Chemical Molecular Normal Ideal liquid Critical Critical Specific Acentricity
name formula mass boiling density (kg/m3) Temperature pressure (atm) volume
(g/mol) point (ºC) (ºC) (m3/kmol)
Triolein C57H104O6 885.4 606.8 916 680.9 3.555 3.090 1.686
Methyl oleate C19H36O2 296.5 343.9 876.9 490.9 12.63 1.060 1.049
Oleic acid (FFA) C18H34O2 282.5 358.9 893.4 496.9 13.72 1 1.178

reactor (GBR-100) as a simplified model is used to simulate the
reforming reactor. This reactor is used to calculate the reac-
tion equilibrium by minimizing the Gibbs free energy. In order
to thoroughly convert glycerol into hydrogen, reaction tem-
perature and pressure are considered to be 800
C and 240 atm,
respectively. This reaction temperature is selected due to the
fact that at reaction temperatures above 600
C, the reforming
process produces more hydrogen and less methane. The
temperature considered for the reforming reactor might be
higher than that of stream 4. Accordingly, to compensate for
this shortage, this reactor is further heated by the thermal
energy released from the furnace reactor (F-100) which sur-
rounds the reforming reactor.
Glycerol reforming through the SCWR process is an endo-
thermic chemical reaction, requiring more thermal energy to
drive and sustain the chemical reactions. Thermal energy is
provided to the glycerol reforming reactor by a reformer
furnace modeled as a separate furnace-combustor. This
furnace-combustor provides the required thermal energy
through combusting the syngas resulted from the glycerol
reforming reactor plus an exogenous support fuel. The gas
produced (syngas) in the glycerol reforming reactor containing
H2, CH4, CO2, and CO, is first sent to an expander (K-100) in
order to maximize power generation. The syngas is then sent
to the gaseliquid separator in order to eliminate the
condensed water vapor after cooling in the heat exchanger
using cooling water. The thermal energy absorbed by cooling
water is also used for preheating all the inlet streams, i.e.,
syngas, natural gas, and air feeding into the furnace reactor.
Scenario 1
The process flow diagram (PFD) of biodiesel production from
acid-pretreated WCO containing 6 wt% FFA, using an alkali
catalyst followed by the SCWR of the produced glycerol is
illustrated in Fig. 1. The first section of this scenario named
“Alkali-WCO” is a slight modification of the scenario devel-
oped by Zhang et al. [50]. The biodiesel production section is
divided into two parts, i.e., esterification and trans-
esterification processes. The esterification process is a

Fig. 1 e PFD of biodiesel production from acid-pretreated WCO containing 6% FFA, using alkali catalyst followed by the
SCWR of the produced glycerol.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 8 4 5 e1 7 8 6 2 17849

Table 2 e Simulation results of biodiesel production from acid-pretreated WCO containing 6% FFA, using alkali catalyst
followed by the SCWR of the produced glycerol.
Unit H2SO4 WCO 103 105A 107 108 109 110 methanol-A
Vapor fraction 0 0 0 0 0 0 0 0 0
Temperature ºC 25.00 25.00 28.01 70.00 47.26 47.26 28.20 73.35 25.00
Pressure kPa 100.00 100.00 400.00 400.00 200.00 200.00 20.00 30.00 100.00
Molar flow rate kmol/h 0.10 1.34 6.51 7.84 1.32 7.71 5.78 1.70 3.57
Mass flow rate kg/h 10.00 1050.00 215.20 1265.20 1042.47 332.74 185.20 133.65 114.40
Triolein 0.0000 0.9400 0.0000 0.7802 0.9373 0.0297 0.0000 0.0000 0.0000
Oleic Acid 0.0000 0.0600 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Methanol 0.0000 0.0000 0.9535 0.1565 0.0000 0.5952 1.0000 0.0962 1.0000
H2SO4 1.0000 0.0000 0.0465 0.0079 0.0000 0.0301 0.0000 0.0748 0.0000
NaOH 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Oleate 0.0000 0.0000 0.0000 0.0522 0.0627 0.0024 0.0000 0.0059 0.0000
Glycerol 0.0000 0.0000 0.0000 0.0000 0.0000 0.3306 0.0000 0.8231 0.0000
CaO 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
CaSO4 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
H3PO4 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
NA3PO4 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
107B 116 201 202 301A 305 401 502
Vapor fraction 0 0 0 0 0 0 0 0
Temperature ºC 60.00 60.00 28.20 86.62 60.00 60.00 80.76 151.64
Pressure kPa 400.00 400.00 20.00 30.00 110.00 110.00 10.00 60.00
Molar flow rate kmol/h 1.32 8.61 3.47 5.14 3.66 2.08 3.45 1.08
Mass flow rate kg/h 1042.47 1278.08 111.19 1166.89 1051.55 120.20 1013.52 99.03
Triolein 0.9373 0.0229 0.0000 0.0251 0.0276 0.0021 0.0000 0.0026
Oleic Acid 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Methanol 0.0000 0.0960 1.0000 0.0099 0.0042 0.0590 0.0010 0.0000
H2SO4 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
NaOH 0.0000 0.0078 0.0000 0.0086 0.0000 0.0000 0.0000 0.0000
Oleate 0.0627 0.7961 0.0000 0.8720 0.9671 0.0000 0.9990 0.0000
Glycerol 0.0000 0.0771 0.0000 0.0845 0.0000 0.8200 0.0000 0.9955
CaO 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
CaSO4 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
H3PO4 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
NA3PO4 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
H2O 0.0000 0.0000 0.0000 0.0000 0.0010 0.1188 0.0000 0.0019
01þ 1 Water2 2 3 4 05A 05B 6
Vapor fraction 0 0 0 0 0 0 1 0 1
Temperature ºC 105.00 28.53 25.00 33.35 95.13 382.00 799.96 799.96 237.46
Pressure kPa 60.00 60.00 101.30 24318.00 24318.00 24318.00 24318.00 24318.00 151.99
Molar flow rate kmol/h 2.34 235.48 233.14 235.48 235.48 235.48 249.35 0.00 249.35
Mass flow rate kg/h 215.08 4415.08 4200.00 4415.08 4415.08 4415.08 4415.08 0.00 4415.08
Glycerol 0.9991 0.0487 0.0000 0.0487 0.0487 0.0487 0.0000 0.0000 0.0000
Water 0.0009 0.9513 1.0000 0.9513 0.9513 0.9513 0.9292 0.8258 0.9292
Methanol 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Carbon dioxide 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0548 0.0403 0.0548
Carbon monoxide 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0091 0.1301 0.0091
Methane 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0003 0.0002
Hydrogen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0067 0.0035 0.0067
Oxygen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Nitrogen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
7 8 water3 10 11 12 13 14 15
Vapor fraction 0 0 0 0 0 0 0 0 0
Temperature ºC 60.00 60.00 25.00 25.00 99.81 99.81 99.81 96.74 96.45
Pressure kPa 121.59 121.59 96.26 111.46 111.46 111.46 111.46 111.46 111.46
Molar flow rate kmol/h 249.35 223.43 1942.80 1942.80 1942.80 388.56 1554.24 1554.24 1554.24
Mass flow rate kg/h 4415.08 4025.48 35000.00 35000.00 35000.00 7000.00 28000.00 28000.00 28000.00
Glycerol 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Water 0.9292 0.9998 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000
Methanol 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Carbon dioxide 0.0548 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Carbon monoxide 0.0091 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Methane 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Hydrogen 0.0067 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Oxygen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
(continued on next page)
17850 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 8 4 5 e1 7 8 6 2

Table 2 e (continued )
Unit H2SO4 WCO 103 105A 107 108 109 110 methanol-A
Nitrogen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
16 17 18 N- G Nat-1 Nat-2 AIR AIRC AIRN
Vapor fraction 0 0 0 1 1 1 1 1 1
Temperature ºC 97.13 89.41 89.25 25.00 38.08 94.74 25.00 42.63 97.81
Pressure kPa 111.46 101.32 101.32 101.32 116.52 101.32 100.06 116.52 101.32
Molar flow rate kmol/h 1942.80 1942.80 1942.80 15.71 15.71 15.71 223.18 223.18 223.18
Mass flow rate kg/h 35000.00 35000.00 35000.00 252.00 252.00 252.00 6420.00 6420.00 6420.00
Glycerol 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Water 1.0000 1.0000 1.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Methanol 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Carbon dioxide 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Carbon monoxide 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Methane 0.0000 0.0000 0.0000 1.0000 1.0000 1.0000 0.0000 0.0000 0.0000
Hydrogen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Oxygen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.2100 0.2100 0.2100
Nitrogen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.7900 0.7900 0.7900
SG SGC SG OUT SG IN G1 G2 G3
Vapor fraction 1 1 1 1 1 0 1


Temperature C 60.00 87.41 87.41 87.41 1000.05 1000.05 148.62
Pressure kPa 121.59 111.46 111.46 111.46 101.32 101.32 94.84
Molar flow rate kmol/h 25.92 25.92 0.03 25.90 256.76 0.00 256.76
Mass flow rate kg/h 389.60 389.60 0.39 389.21 7061.21 0.00 7061.21
Glycerol 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Water 0.1989 0.1989 0.1989 0.1989 0.1287 0.0871 0.1287
Methanol 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Carbon dioxide 0.6195 0.6195 0.6195 0.6195 0.1414 0.1511 0.1414
Carbon monoxide 0.1032 0.1032 0.1032 0.1032 0.0000 0.0000 0.0000
Methane 0.0027 0.0027 0.0027 0.0027 0.0000 0.0000 0.0000
Hydrogen 0.0757 0.0757 0.0757 0.0757 0.0000 0.0000 0.0000
Oxygen 0.0000 0.0000 0.0000 0.0000 0.0116 0.1554 0.0116
Nitrogen 0.0000 0.0000 0.0000 0.0000 0.7183 0.6064 0.7183

Fig. 2 e PFD of biodiesel production from WCO using acid catalyst followed by the SCWR of the produced glycerol.
Table 3 e Simulation results of biodiesel production from WCO using acid catalyst followed by the SCWR of the generated glycerol.
Unit Methanol H2SO4 101C Crude oil 103 201 202 203 203B 301 302 401 402 501 502
Vapor fraction 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Temperature ºC 25.00 25.00 73.44 25.00 80.00 81.36 101.11 60.00 60.00 58.87 60.58 47.93 340.10 38.01 67.20
Pressure kPa 100.00 100.00 400.00 100.00 400.00 190.00 200.00 200.00 130.00 110.00 120.00 40.00 50.00 40.00 50.00
Molar flow rate kmol/h 6.75 1.53 58.03 1.16 59.19 49.75 9.44 9.33 1.34 4.31 4.79 4.20 0.07 2.98 1.80
Mass flow rate kg/h 216.28 150.00 1960.27 1030.00 2990.31 1594.08 1396.23 1466.23 218.54 1059.90 207.79 1014.21 41.10 107.95 106.78
Triolein 0.0000 0.0000 0.0000 1.0000 0.0103 0.0000 0.0221 0.0211 0.0000 0.0271 0.0106 0.0010 0.6980 0.0000 0.0000
Methanol 1.0000 0.0000 0.9235 0.0000 0.5691 1.0000 0.0772 0.0735 0.0000 0.0257 0.3874 0.0044 0.0000 0.7572 0.0000

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 8 4 5 e1 7 8 6 2
H2SO4 0.0000 1.0000 0.0765 0.0000 0.0502 0.0000 0.1074 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
M-Oleate 0.0000 0.0000 0.0000 0.0000 0.3356 0.0000 0.7189 0.6845 0.0000 0.9458 0.0059 0.9937 0.3020 0.0020 0.0000
Glycerol 0.0000 0.0000 0.0000 0.0000 0.0348 0.0000 0.0744 0.0709 0.0000 0.0007 0.4965 0.0004 0.0000 0.0000 0.9748
CaO 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0006 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
CaSO4 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.1490 0.9994 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
H2O 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0010 0.0000 0.0007 0.0995 0.0006 0.0000 0.2408 0.0252
water1 1 2 3 4 05A 05B 6 7 8 9 10 11 12 13
Vapor fraction 0 0 0 0 0 1 0 1 0 0 0 0 0 0 0
Temperature ºC 25.00 27.13 31.93 95.83 382.00 799.97 799.97 237.48 60.00 60.00 20.00 20.00 100.86 100.86 100.86
Pressure kPa 100.00 50.00 24318.00 24318.00 24318.00 24318.00 24318.00 151.99 121.59 121.59 100.01 111.46 111.46 111.46 111.46
Molar flow rate kmol/h 111.02 112.81 112.81 112.81 112.81 119.47 0.00 119.47 119.47 107.03 860.38 860.38 860.38 86.04 774.34
Mass flow rate kg/h 2000.00 2115.36 2115.36 2115.36 2115.36 2115.36 0.00 2115.36 2115.36 1928.30 15500.00 15500.00 15500.00 1550.00 13950.00
Glycerol 0.0000 0.0488 0.0488 0.0488 0.0488 0.0488 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Water 1.0000 0.9512 0.9512 0.9512 0.9512 0.9512 0.9290 0.9290 0.9290 0.9998 1.0000 1.0000 1.0000 1.0000 1.0000
Carbon dioxide 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0549 0.0549 0.0549 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
Carbon monoxide 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0091 0.0091 0.0091 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Methane 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0002 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Hydrogen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0067 0.0067 0.0067 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Nitrogen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Oxygen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
14 15 16 17 18 AIR AIRN AIRC N-G Nat-g Nat-g in SG SGC SGIN SGOUT
Vapor fraction 0 0 0 0 0 1 1 1 1 1 1 1 1 1 1
Temperature ºC 97.77 97.49 97.83 89.19 89.02 25.00 98.86 42.30 25.00 39.00 95.77 60.00 87.19 87.1886458 87.19
Pressure kPa 111.46 111.46 111.46 101.32 101.32 101.32 101.32 116.52 101.32 116.52 101.32 121.59 111.46 111.457496 111.46
Molar flow rate kmol/h 774.34 774.34 860.38 860.38 860.38 109.23 109.23 109.23 7.60 7.60 7.60 12.45 12.45 12.4460573 0.00
Mass flow rate kg/h 13950.00 13950.00 15500.00 15500.00 15500.00 3142.00 3142.00 3142.00 122.00 122.00 122.00 187.06 187.06 187.058919 0.00
Glycerol 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Water 1.0000 1.0000 1.0000 1.0000 1.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.1989 0.1989 0.1989 0.1989
Carbon dioxide 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.6193 0.6193 0.6193 0.6193
Carbon monoxide 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.1034 0.1034 0.1034 0.1034
Methane 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 1.0000 1.0000 1.0000 0.0027 0.0027 0.0027 0.0027
Hydrogen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0757 0.0757 0.0757 0.0757
Nitrogen 0.0000 0.0000 0.0000 0.0000 0.0000 0.7900 0.7900 0.7900 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Oxygen 0.0000 0.0000 0.0000 0.0000 0.0000 0.2100 0.2100 0.2100 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
G1 G2 G3
Vapor fraction 1 0 1
Temperature ºC 1000.15 1000.15 167.53

17851
Pressure kPa 101.32 101.32 91.19
(continued on next page)
17852 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 8 4 5 e1 7 8 6 2

pretreatment step carried out using acid catalyst to remove

FFA. The FFA of WCO accounting for 6 wt% of stream 104 is
502

converted into methyl ester using methanol in the presence of

sulfuric acid within the esterification reactor (R-100). The re-
action temperature and pressure of the esterification reactor
are respectively considered to be 70
C and 400 kPa, while
501

methanol to oil molar ratio is considered at 6:1. The exoge-

nous glycerol stream is used to remove methanol and acid
catalyst from oil and biodiesel leaving the esterification
402

reactor. The upstream of the washing tower (stream 107)

containing oil and biodiesel is sent into the alkaline catalyst
process in order to convert the remained oil into biodiesel. In
401

addition, the downstream of the washing tower (108) is fed

into the reforming process (112A) after recovering methanol
(stream 109) and removing acid catalyst. Further to the glyc-
erol generated in the process (99.03 kg/h), i.e., the stream
302

leaving the distillate tower (stream 502) in the glycerol puri-

fication unit (T-500), an additional exogenous glycerol (stream
112A) with a mass flow rate of 110 kg/h is supplied to the
301

SCWR process. After trial-and-error, the amount of water

needed for the reformer reactor (Water-2) is found to be
203B

4,415 kg/h, while the amount of water for the heat transfer
from the turbine output stream (stream 6) to the inputs of the
reformer reactor (3) and furnace (N-1, AIRN) is determined to
be 35,000 kg/h. Furthermore, 252 kg/h natural gas and
203

6,420 kg/h air are considered for providing 2,373 kW as addi-

tional thermal energy required by the reformer reactor. The
flow characteristics of this scenario are presented in Table 2.
202

Scenario 2
201

The PFD of biodiesel production from WCO using acid catalyst

followed by the SCWR of the produced glycerol is displayed in
Fig. 2. Notably, this process does not suffer from the soap-
103

formation problems frequently occurring in the presence of

alkali catalysts since acid catalyst acids are not sensitive to the
presence of FFAs in feedstocks. Although biodiesel production
Crude oil

rates are very low in the presence of acid catalysts, their

conversion efficiencies are higher than those of alkali cata-
lysts. Accordingly, this process has attracted more attention
in recent years. In this process, methanol to oil and sulfuric
3451.06
101C
125.42

0.0000
0.1272
0.1397
0.0000
0.0000
0.0000
0.7193
0.0138

acid to oil molar ratios are considered to be 50:1 and 1.3:1,

respectively. Fresh methanol and sulfuric acid with mass flow
rates of 216 and 150 kg/h, respectively, are fed into the ester-
H2SO4

ification reactor. The temperature and pressure of WCO

0.0000
0.0796
0.1396
0.0000
0.0000
0.0000
0.5783
0.2025

(stream WCO) are respectively adjusted to 60
C and 400 kPa

0.00
0.00

before being fed into the reactor (R-100). The downstream of

Methanol

the esterification reactor (stream 103) containing a large

3451.06
125.42

0.0000
0.1272
0.1397
0.0000
0.0000
0.0000
0.7193
0.0138

amount of methanol, is sent to the distillation tower (T-100).

The recycled methanol (1594 kg/h) is used to adjust the molar
ratio of methanol to oil (stream 201). After neutralizing acid
kmol/h

and washing biodiesel, biodiesel and glycerol must be suffi-

Unit

kg/h
Table 3 e (continued )

ciently purified. To this end, the upstream (301) of the

extractor (T-200) is sent to the biodiesel purification tower (T-
Carbon monoxide

300) and its downstream flow (302) is also transferred to the

Molar flow rate

Carbon dioxide
Mass flow rate

glycerol purification tower (T-400). In this unit, glycerol im-

purities such as methanol are completely separated. The
Hydrogen
Methane

Nitrogen
Glycerol

Oxygen

refined glycerol stream (stream 502) is fed into the glycerol

Water

reforming process. In addition, 2000 kg/h water is considered

for diluting the purified glycerol. Moreover, 15500 kg/h water is
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 8 4 5 e1 7 8 6 2
Fig. 3 e PFD of biodiesel production from WCO using acid catalyst and subsequent hexane extraction of the evolved methyl
esters followed by the SCWR of the generated glycerol.
taken into account for the heat transfer from the turbine
output stream. 122 kg/h natural gas and 3142 kg/h air are
considered for providing the thermal energy required by the
reforming reactor. The flow characteristics of this scenario are
tabulated in Table 3.
Scenario 3
The PFD of biodiesel production from WCO using acid catalyst
and subsequent hexane extraction of the evolved methyl es-
ters followed by the SCWR of the generated glycerol is
exhibited in Fig. 3. Unlike the second scenario where water is
used for biodiesel purification, hexane is considered for bio-
diesel refining in this process. This scenario up to stream 203
is similar to the second one, but the rest of this process is
fundamentally different from the acid catalyst process. The
slurry leaving the T-100 reactor (stream 203) with a mass flow
rate of 1,395.04 kg/h includes 71 wt% biodiesel, 10 wt% sulfuric
acid, 7 wt% methanol, 7 wt% glycerol, and 2 wt% unconverted
oil. Since the complete separation of biodiesel from impurities
is not possible using hexane solvent, two component splitters,
i.e., T-101A (hexane extraction of biodiesel) and T-101B
(methanol/water washing) are used instead of an extraction
tower. The solubility of hexane in anhydrous methanol is the
main reason for the incomplete separation of biodiesel from
impurities. Accordingly, water should be added to methanol
17853
with a volumetric ratio of 1:10 to prevent the solution of
hexane in methanol. The volumetric flow rate of n-hexane as
solvent is considered to be 0.13 m3/h on the basis of the
methanol present in the stream 203. In addition, 0.14 m3/h
methanolewater (80 v/v% methanol and 20 v/v% water) is
taken into account for the T-101B unit to ensure complete
separation of biodiesel and hexane from the other compounds
like glycerol and sulfuric acid.
The top stream (301A) of the T-101B unit with a mass flow
rate of 1,158 kg/h containing 86 wt% biodiesel, 10 wt% hex-
ane, and 2 wt% unconverted oil is sent to the biodiesel pu-
rification step. In addition to the biodiesel purification of up
to 99.65% in the T-200 distillation tower, about 98.49 wt% of
the n-hexane present in its input stream is recycled back to
the T-101A (stream 1401). The stream 205B is mixed with
stream 301B. The mixture is then neutralized with CaO and
transferred to the glycerol purification tower (T-300). In
addition, a portion of the methanol available in the stream
501 (112 kg/h) is sent to the T-101B unit. The stream 502 with
a mass flow rate of 104.3 kg/h is directed towards the
reforming process as well. In this scenario, the glycerol
stream being fed into the reforming process is diluted with
2,100 kg/h water. The mass flow rate of the water required to
heat the turbine output flow is found to be 16200 kg/h. The
mass flow rates of the auxiliary natural gas and air feeding
into the furnace are respectively considered to be 125 and
 17854
Table 4 e Simulation results of biodiesel production from WCO using acid catalyst and subsequent hexane extraction of the evolved methyl esters followed by the SCWR of
the generated glycerol.
Unit 101 102 103 104B 105 201 203 205A 301C 303A 303B 401A 401 402 501 502
Vapor fraction 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 ‘


Temperature C 25.00 25.00 73.76 80.00 80.00 81.36 60.00 25.00 60.00 40 40 139.02 139.02 444.40 38.02 100.78
Pressure kPa 100.00 100.00 400.00 400.00 400.00 190.00 200.00 180.00 150.00 160.00 160.00 10.00 10.00 20.00 40.00 50.00
Molar flow rate kmol/h 6.71 1.53 59.76 1.16 60.92 51.52 9.40 5.02 4.84 9.28 1.34 1.38 3.43 0.04 8.12 1.16
Mass flow rate kg/h 215.00 150.00 2015.80 1030.00 3045.84 1650.80 1395.04 1166.40 1158.28 341.82 218.41 120.07 1007.02 31.19 237.25 104.53
Triolein 0.0000 0.0000 0.0000 1.0000 0.0101 0.0000 0.0221 0.0265 0.0266 0.0001 0.0000 0.0000 0.0000 0.9894 0.0000 0.0000

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 8 4 5 e1 7 8 6 2
Methanol 1.0000 0.0000 0.9256 0.0000 0.5770 1.0000 0.0764 0.0040 0.0000 0.6092 0.0000 0.0000 0.0000 0.0000 0.8771 0.0028
H2SO4 0.0000 1.0000 0.0744 0.0000 0.0492 0.0000 0.1075 0.0020 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
M-Oleate 0.0000 0.0000 0.0000 0.0000 0.3295 0.0000 0.7195 0.8620 0.8681 0.0000 0.0000 0.0155 0.9963 0.0106 0.0000 0.0000
Glycerol 0.0000 0.0000 0.0000 0.0000 0.0341 0.0000 0.0745 0.0010 0.0000 0.3039 0.0000 0.0000 0.0000 0.0000 0.0000 0.9941
CaO 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
CaSO4 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 1.0000 0.0000 0.0000 0.0000 0.0000 0.0000
H2O 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0868 0.0000 0.0000 0.0000 0.0000 0.1229 0.0031
n-Hexane 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.1045 0.1053 0.0000 0.0000 0.9845 0.0037 0.0000 0.0000 0.0000
water1 1 2 3 4 05A 05B 6 7 8 12 13 9 10 11 14
Vapor fraction 0 0 0 0 0 1 0 1 0 0 0 0 0 0 0 0
Temperature ºC 25.00 28.27 33.08 100.52 382.00 800.00 800.00 237.97 60.00 60.00 102.64 102.64 25.00 25.00 102.64 102.09
Pressure kPa 101.32 50.00 24318.00 24318.00 24318.00 24318.00 24318.00 151.99 121.59 121.59 111.46 111.46 96.26 111.46 111.46 111.46
Molar flow rate kmol/h 116.57 117.72 117.72 117.72 117.72 124.48 0.00 124.48 124.48 111.24 179.85 719.39 899.24 899.24 899.24 719.39
Mass flow rate kg/h 2100.00 2204.53 2204.53 2204.53 2204.53 2204.53 0.00 2204.53 2204.53 2004.18 3240.00 12960.00 16200.00 16200.00 16200.00 12960.00
Glycerol 0.0000 0.0471 0.0471 0.0471 0.0471 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Water 1.0000 0.9529 0.9529 0.9529 0.9529 0.9271 0.8803 0.9271 0.9271 0.9998 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000
Carbon dioxide 0.0000 0.0000 0.0000 0.0000 0.0000 0.0633 0.0476 0.0633 0.0633 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Carbon monoxide 0.0000 0.0000 0.0000 0.0000 0.0000 0.0025 0.0682 0.0025 0.0025 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Methane 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0002 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Hydrogen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0070 0.0037 0.0070 0.0070 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Nitrogen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Oxygen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Methanol 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
15 16 17 18 N-G Nat- g Nat-g in AIR AIRC AIRN SG SGC SG IN SG OUT G1 G3
Vapor fraction 0 0 0 0 1 1 1 1 1 1 1 1 1 1 1 1
Temperature ºC 101.76 102.52 93.44 93.24 25.00 38.08 100.09 25.00 41.15 100.64 60.00 91.44 91.44 91.44 1000.03 139.37
Pressure kPa 111.46 111.46 101.32 101.32 101.32 116.52 101.32 101.32 116.52 101.32 121.59 111.46 111.46 111.46 101.32 91.19
Molar flow rate kmol/h 719.39 899.24 899.24 899.24 7.79 7.79 7.79 108.29 108.29 108.29 13.24 13.24 13.24 0.00 125.39 125.39
Mass flow rate kg/h 12960.00 16200.00 16200.00 16200.00 125.00 125.00 125.00 3115.00 3115.00 3115.00 200.35 200.35 200.35 0.00 3440.35 3440.35
Glycerol 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Water 1.0000 1.0000 1.0000 1.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.1974 0.1974 0.1974 0.1974 0.1332 0.1332
Carbon dioxide 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.6965 0.6965 0.6965 0.6965 0.1429 0.1429
Carbon monoxide 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0276 0.0276 0.0276 0.0276 0.0000 0.0000
Methane 0.0000 0.0000 0.0000 0.0000 1.0000 1.0000 1.0000 0.0000 0.0000 0.0000 0.0015 0.0015 0.0015 0.0015 0.0000 0.0000
Hydrogen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0770 0.0770 0.0770 0.0770 0.0000 0.0000
Nitrogen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.7900 0.7900 0.7900 0.0000 0.0000 0.0000 0.0000 0.7154 0.7154
Oxygen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.2100 0.2100 0.2100 0.0000 0.0000 0.0000 0.0000 0.0085 0.0085
Methanol 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 8 4 5 e1 7 8 6 2 17855

Economic analysis
Table 5 e Prices of raw materials, products, and utilities.
Component name Pricea (USD/kg) Reference In order to assess the feasibility of the developed scenarios, an
WCO 0.224 [55] economic analysis is carried out. To this end, total capital
Methanol (99.85%) 0.268 [56] investment (TCI) and annual production cost (APC) are
Sodium hydroxide 0.200 [57] computed for the developed plants. Several profitability in-
Sulfuric acid (98%) 0.060 [57]
dicators are also determined for comparing the developed
Phosphoric acid 0.340 [57]
Calcium oxide 0.400 [52]
scenarios.
Natural gas (methane) 0.120 [58]
n-Hexane 0.410 [52] TCI
Products Price (USD/kg) TCI is computed as the summation of fixed capital investment
Biodiesel 0.990 [59] (CFCI), working capital cost (CWC), and land cost (CL) as follows:
Electricity 0.2 (USD/kWh) [40]
Utility Price (USD/ton) TCI ¼ CFCI þCWC þCL (1)
High-pressure steam 16.64 [51]
(superheated) The terms of the above mentioned equation have been
Medium-pressure steam 13.71 [51] comprehensively explained by Zhang et al. [52]. In order to
(superheated) estimate the direct cost, bare module costs (BMC) available in
Low-pressure steam 12.68 [51] Aspen Capital Cost Estimator software is used. In this soft-
(superheated)
ware, the required facilities are first designed using the ther-
Cooling water 0.013 [60]
modynamic conditions applied in the simulation and their
Electricity 0.2 (USD/kWh) [40]
associated costs are estimated accordingly. The costs associ-
a
These prices are considered according to the North America
ated with setting, piping, instrumentation, electrical devices,
conditions.
insulation, buildings, and yard are also considered. The costs
of facilities requiring high-quality materials like reformer,
expander, and furnace are computed according to the eco-
3,115 kg/h, for providing the thermal energy required by the
nomic information provided by HYSYS software. The costs
reforming process. The flow characteristics of this scenario
associated with the Contract, G and A Overheads, and con-
are summarized in Table 4.
tingencies related to the indirect fixed capital investment cost,
All the above-mentioned scenarios are simulated using the
are calculated as follows:
HYSYS software and are then compared using several eco-
nomic indicators viz. net present value (NPV), internal rate of
 Contract Fee ¼ 3% of the total plan direct cost [53].
return (IRR), payback period (PBP), discounted payback period
 G and A Overheads ¼ 2% of the total plan direct cost [53].
(DPBP), and return on Investment (ROI). The methodologies of
 Contingencies ¼ 7% of the total plan direct cost [53].
these indices have been comprehensively detailed by Turton
et al. [51]. The main products of all the above-mentioned
In addition, the working capital cost is taken into account
scenarios are purified biodiesel and electrical power. A
as 15% of the fixed capital cost [54].
sensitivity analysis is also performed to investigate the effects
of feedstock, biodiesel, and electricity prices on the NPVs of
APC
techno-economically feasible scenarios.
APC is obtained as the summation of raw materials costs,
utilities costs, and a series of extra costs required for the
proper functioning of the process. Accordingly, the following
Table 6 e Electrical energy balance of the developed formula is used to compute the APC:
scenarios.
APC ¼ CRM þCU þCE þCWD (2)
Electrical equipment Scenario 1 Scenario 2 Scenario 3
(kWh) Where CRM is the cost of raw materials, CU shows the utility
costs, CE is the extra costs, and CWD stands for the waste
P-100 0.00 1.65 0.04
P-200 0.08 0.07 0.07 disposal costs. The cost associated with waste disposal is
P-300 0.05 0.17 0.18 considered to be zero since the waste produced by the devel-
P-300a 0.00 e e oped plants does not contain toxic substances and does not
P-400 0.03 26.74 0.01 have any negative environmental impacts. The extra costs
P-500 0.02 0.09 0.02 included operating labor, supervision, maintenance, oper-
P-600 0.18 e 27.90
ating supplies, laboratory charges, overhead, insurance, local
P-700 0.02 e 0.12
P-800 55.85 e
taxes, royalties, and administrative costs. The depreciation is
P-900 0.26 e e assumed to be a straight line and the salvage value is 10% after
C-100 2.05 1.06 1.01 25 years (life span of the project).
C-200 31.91 15.32 14.18 The prices of raw materials, products, and utilities are
Total electricity 90.46 45.12 43.53 presented in Table 5. The required utilities including steam,
consumption
electricity, and cooling water are estimated by setting the
Total electricity produced 1368.61 664.30 662.60
mass and energy balance between the input and output
Net electricity 1278.15 619.18 619.07
17856 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 8 4 5 e1 7 8 6 2

Table 7 e Mass balance of the developed scenarios.

Scenario 1 Scenario 2 Scenario 3
Inlet stream Mass flow rate (kg/h) Inlet stream Mass flow rate (kg/h) Inlet stream Mass flow rate (kg/h)
Methanol 20 Methanol 216.28 101 215
H2SO4 10 H2SO4 150 102 150
104 1050 Crude oil 1030 104 1030
Glycerol 110 CaO 70 111 9.98
Methanol-A 114.4 Water 28 Water 4.39
NaOH-A 10 Water1 2000 Methanol 3.50
CaO 4.7 Water2 15500 CaO 69.87
201B 111.2 Natural gas 122 Water1 2000
Water 11 Air 3145 9 16200
H3PO4 8.2 Natural gas 122
Water2 4200 Air 3145
Water3 35000
Natural gas 254
Air 6420

Outlet stream Mass flow rate (kg/h) Outlet stream Mass flow rate (kg/h) Outlet stream Mass flow rate (kg/h)

108B 13.89 203B 218.54 303B 218.41

112B 28.35 401A 1.15 401 1007.02
400 4.43 401 1014.21 402 31.19
401 1013.52 402 41.11 501C 125.30
402 33.21 501 107.95 502 104.53
306 14.34 502 106.78 8 2004.18
501 21.19 8 1928.30 18 16200
502 99.03 18 15500 G3 3440.35
SG out 0.39 G3 3451.06
8 4025.48
G3 7061.21
18 35000

streams in Aspen HYSYS. In addition, the operating labor cost
(COL) is calculated as follows:
COL ¼ operators per shift
 cost operator=h  operating hours per year
Results and discussion
Table 6 tabulates the electrical energy balance of the devel-
oped scenarios. The net electrical power is obtained by sub-
tracting the power consumed by compressors, fans, and
pumps from that produced by expander. In spite of the fact
that the first scenario has the highest electrical consumption
due to pump P-800, this approach leads to the highest net
electricity generation (1278.15 kWh). The net electrical power
(3) generation of the second and third scenarios is close to each
other. According to the results of mass balance presented for
the developed scenarios in Table 7, the second scenario has
the highest biodiesel production rate (1014.21 kg/h) followed
very closely by the first scenario (1013.52 kg/h). Overall, the
first scenario seems to be a better option in terms of mass and
energy balances compared with the other scenarios.

Table 8 e Total capital investment costs of the developed scenarios (MUSD).

Scenario 1 Scenario 2 Scenario 3
Purchased Equipment (1) (1) ¼ BMC 3.6615 3.3140 3.5044
Equipment Setting (2) (2) ¼ 0.2 * (1) 0.7323 0.6628 0.7009
Piping (3) (3) ¼ 0.3 * (1) 1.0985 0.9942 1.0513
Instrumentation (4) (4) ¼ 0.2 * (1) 0.7323 0.6628 0.7009
Electrical (5) (5) ¼ 0.1 * (1) 0.3662 0.3314 0.3504
Insulation (6) (6) ¼ 0.03 * (1) 0.1098 0.0994 0.1051
Buildings (7) (7) ¼ 0.3 * (1) 1.0985 0.9942 1.0513
Yard (8) (8) ¼ 0.1 * (1) 0.3662 0.3314 0.3504
Total plan direct cost (TPDC) (9) (9) ¼ (1) þ (2) þ (3) þ … þ (8) 8.1652 7.3902 7.8148
G and A Overheads (10) (10) ¼ 0.02*(9) 0.1796 0.1626 0.1719
Contract Fee (11) (11) ¼ 0.03*(9) 0.2450 0.2217 0.2344
Contingencies (12) (12) ¼ 0.07*(9) 0.5716 0.5173 0.5470
Fixed capital cost (13) (13) ¼ (9) þ (10) þ (11) þ (12) 9.1614 8.2918 8.7682
Working Capital (14) (14) ¼ 0.05*(13) 0.4581 0.4146 0.4384
Total capital investment cost (TCI) (15) (15) ¼ (13) þ (14) 9.62 8.71 9.21
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 8 4 5 e1 7 8 6 2 17857

Fig. 4 e Detailed purchasing costs of the reforming section of the first scenario.

Table 9 e APC of the developed scenarios.

Process Formula Production cost (USD/year)
Scenario 1 Scenario 2 Scenario 3
Methanol 288,920.12 464,931.25 469,706.08
NaOH 16,000.00 e e
H3PO4 22,306.03 e e
Natural gas 243,841.54 117,120.38 117,120.00
H 2O 3,729.12 1,853.97 1,938.03
CaO 26.86 22,399.49 399.25
WCO 1,881,600.00 1,845,760.00 1,845,760.00
H2SO4 4,800.38 72,000.58 72,000.58
n-Hexane e e 12,138.56
Raw Materials 2,461,224.05 2,524,065.67 2,519,062.50
Electricity 94,079.62 118,834.98 45,271.74
Low-pressure steam 99,128.70 310,655.68 351,389.57
Medium-pressure steam 0.00 243.47 0.00
High-pressure steam 821,957.54 526,753.58 699,232.12
Cooling water 63,407.93 60,860.01 75,919.90
Operating labor (1) (1) ¼ A*B*C 1,120,000.00 1,051,920.00 1,051,920.00
Supervision (2) (2) ¼ 0.25*(1) 280,000.00 262,980.00 262,980.00
Maintenance (3) (3) ¼ 0.03*(CFCI) 568,700.79 475,286.33 502,011.76
Operating supplies (4) (4) ¼ 0.1*(3) 56,870.07 47,528.63 50,201.17
Laboratory charges (5) (5) ¼ 0.163*(1) 179,200.00 171,462.96 171,462.96
Plan overhead (6) (6) ¼ 0.5*((1)þ(3)) 844,350.39 763,603.16 776,965.88
Insurance, local taxes, and royalties (7) (7) ¼ 0.04*(CFCI) 758,267.722 633,715.10 669,349.02
General and Administrative costs (9) (8) ¼ 0.15*(7) 571,108.34 510,974.43 522,733.62
Total production cost (10) (9) ¼ (7)þ(8) 7,918,295.16 USD 7,458,884.51 USD 7,698,500.26 USD
Total production cost (MUSD) 7.92 7.46 7.70

Table 8 summarizes the total capital investment costs of
the developed scenarios. All the scenarios are designed to
produce 8,000 tons biodiesel annually. The reasons for
selecting this capacity have been comprehensively described
by Zhang et al [50]. In addition, this capacity is selected in
order to compare the outcomes of the present survey with
those reported in the published literature. Obviously, the total
capital investment cost of the first scenario is higher than
those of the other scenarios due to the large number of facil-
ities involved. In addition, the higher mass flow rate of glyc-
erol reformed in this scenario compared with the other
scenarios can be mentioned as another reason justifying this
finding.
Fig. 4 shows the purchasing costs of the reforming section
of the first scenario in detail. The purchasing costs of pumping
units of this scenario are very high because of the higher
operating pressure of the pump P-800 and the higher mass
flow rate of the pump P-900, Similarly, compressors C-100 and
C-200 compressing large volumes of air and natural gas,
respectively, need high purchasing costs.
Table 9 summarizes the APC values of the developed sce-
narios. Clearly, the APC of the first scenario is slightly higher
than those of the other scenarios. In addition, raw materials
accounts for 31.08%, 33.84%, and 32.72%, while utilities
contribute to 13.62%, 13.64%, and 15.22% of the APC of the first,
second, and third scenarios, respectively. Extra costs amount
17858 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 8 4 5 e1 7 8 6 2

Table 10 e Revenues and annual profits of the developed scenarios.

Scenario Product Revenues per year (USD/year) Total revenues per Annual profit (USD/year)
year (USD/year)
1 Biodiesel (kg/h) 1013.89 8,031,776.74 10,221,552.74 2,303,249.63
Electricity (kWh) 1368.61 2,189,776.00
2 Biodiesel (kg/h) 1014.21 8,030,880.00 9,093,760.00 1,634,875.49
Electricity (kWh) 664.30 1,062,880.00
3 Biodiesel (kg/h) 1007.20 8,032,543.20 9,092,703.20 1,394,202.94
Electricity (kWh) 662.60 1,060,160.00

to 55.30%, 52.52%, and 52.06% of the APC of the first, second, investment cost. This can be ascribed to the relatively high
and third scenarios, respectively. Overall, the contributions of annual profit of this scenario compared with the second and
raw materials, utilities, and extra costs to the APC of the third scenarios. The third scenario shows the longest PBP and
developed scenarios are very close to each other. DPBP values (7.61 and 10.19, respectively) among the scenarios
Table 10 tabulates the revenues and annual profits of the considered herein.
developed scenarios. In order to calculate the annual profit, A sensitivity analysis is performed to show how variations
the production costs of each year is subtracted from the in feedstock, biodiesel, and electricity prices affect the NPVs of
annual revenues of the same year. The first scenario with an the developed scenarios. This analysis is carried out by
annual profit of 2.30 MUSD is the most economically favorable
approach, followed by the second and third scenarios. This is
obtained while the first scenario has the higher APC compared
with the second and third scenarios.
The NPVs of the developed scenarios is shown in Fig. 5. The
NPVs of the developed scenarios is computed by considering
the interest rate of 7%. The NPV of the first scenario is 15.70
MUSD during its life time and is more beneficial than the other
scenarios. This conclusion is inferred from the results while
the first scenario has the highest purchasing and production
costs. Furthermore, the NPVs of the second and third sce-
narios are found to be 12.20 and 7.70 MUSD, respectively.
Fig. 6 illustrates the IRR, ROI, PBP, and DPBP values of the Fig. 5 e NPVs of the developed scenarios.
developed scenarios. The highest IRR and ROI values are
respectively found to be 23.20% and 23.94% for the first sce-
nario. However, the third scenario shows the lowest IRR and
ROI values (14.92% and 15.14%, respectively). Despite the fact
that the first scenario has a higher APC and production costs
compared with the second and third scenarios, its IRR and ROI
values are higher than those of the other scenarios. This can
be attributed to the higher net electrical energy production of
this approach over the other scenarios, as previously dis-
cussed. Accordingly, the first scenario has a higher capability
to repay investment costs annually compared with the other
scenarios. Vlysidis et al. [53] techno-economically analyzed
four biodiesel production scenarios from rapeseed oil. In the
first scenario, the produced glycerol was sent to landfill. In the
second and third scenarios, the produced glycerol was puri-
fied to 80% and 95% purity, respectively. In the fourth scenario,
the produced glycerol was used to produce succinic acid. The
highest IRR was found to be 22.74% for the third scenario,
while the highest ROI was determined to be 23.12% for the
second scenario [53]. Obviously, the IRR and ROI values of the
second scenario developed herein are higher than those re-
ported by Vlysidis et al. [53]. This means that the SCWR pro-
cess of the generated glycerol and its subsequent conversion
into electricity can be an efficient strategy to improve the
economic viability of biodiesel production plants. The shortest
PBP and DPBP values are found to be 5.29 and 6.29 years for the Fig. 6 e IRR, ROI, PBP, and DPBP values of the developed
first scenario, showing its capability for compensating for the scenarios.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 8 4 5 e1 7 8 6 2 17859

Fig. 7 e NPVs variations of the developed scenarios by changing the feedstock, biodiesel, and electricity prices.
17860 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 8 4 5 e1 7 8 6 2
Fig. 8 e NPVs variations of all the developed scenarios by
changing the discount rate.
assuming a variation of the feedstock, biodiesel, and elec-
tricity prices by ±10%, ±20%, ±30%, and ±40% (Fig. 7). It is clear
from Fig. 7 that the NPVs of all the developed scenarios are
linearly increased by decreasing the feedstock price and vice
versa. Interestingly, the NPV of the second scenario comes
close to the first scenario's by increasing the biodiesel price.
This can be attributed to the higher biodiesel production rate
of the second scenario. In addition, increasing the biodiesel
price linearly increased the NPVs of all the developed sce-
narios, while decreasing the biodiesel price acts oppositely.
Like the biodiesel price, the electricity price directly affects the
NPVs of all the developed scenarios. However, changing the
electricity price does not affect the NPVs of the developed
scenarios as much as altering the biodiesel price does. This
can be explained by the lower price of electricity compared
with biodiesel. It is interesting to note that the NPV of the
second scenario approaches the first scenario's by decreasing
the electricity price. This can be attributed to the higher
electrical power production of the first scenario compared
with the second and third scenarios.
Fig. 8 exhibits the NPVs variations of all the developed
scenarios by changing the discount rate. The basal discount
rate throughout this study is 10%. Clearly, the NPVs of all the
developed scenarios are sharply decreased by increasing the
discount rate. Furthermore, NPVs of all the developed sce-
narios are changed by a steep slope at discount rates lower
than 20%. However, NPVs of all the developed scenarios
approach zero or even become negative at discount rates
higher than 20%, showing their economic infeasibility at
higher discount rates.
Conclusions
Techno-economic analysis of three different biodiesel pro-
duction scenarios enhanced by the SCWR of the generated by-
product, i.e., glycerol is carried out. Biodiesel production from
acid-pretreated canola-based WCO with 6 wt% FFA content
using alkali catalyst is taken into account as the first scenario.
Biodiesel synthesis from WCO using acid catalyst is consid-
ered as the second scenario. Biodiesel production from WCO
using acid catalyst and subsequent hexane extraction of the
produced methyl esters is considered as the third scenario.
Glycerol supercritical reforming unit is annexed to all the
developed biodiesel plants in order to upgrade glycerol and
produce hydrogen. This process is carried out to achieve the
energy self-sufficiency in the developed plants. An expander
is also used to produce electricity by reducing the pressure of
the gas leaving the reformer. The developed approaches are
simulated and then compared using several economic in-
dicators including NPV, IRR, ROI, PBP, and DPBP. The main
conclusions drawn from the current study can be summarized
as follows:
➢ The first scenario has the highest net electrical power
generation while the biodiesel production rate of all the
developed scenarios is close to each other.
➢ The APCs of the developed scenarios are very close to each
other.
➢ The NPV of the first scenario (15.70 MUSD) is found to be
highest among the scenarios simulated.
➢ The highest IRR and ROI values are respectively found to be
23.20% and 23.94% for the first scenario.
➢ The shortest PBP and DPBP values are found to 5.29 and
6.29 years for the first scenario.
Overall, glycerol valorization into hydrogen and then con-
verting the produced hydrogen into electricity can increase
the economic viability of biodiesel plants. This can be attrib-
uted to the fact that glycerol valorization not only can provide
the electrical and thermal energy requirements of biodiesel
production and refining processes but also can generate extra
electrical power. According to the results obtained, the first
scenario is the most favorable approach from techno-
economic viewpoint among the pathways considered. The
economic indices of the second scenario are also close to the
first approach. Overall, techno-economic analysis carried out
herein can offer promising insights into feasibility and pro-
ductivity of biodiesel production plants enhanced by various
glycerol-upgrading processes. Future research works should
focus on exergy, exergoeconomic, and exergoenvironmental
analyses of biodiesel plants enhanced by glycerol upgrading
technologies for a better understanding of such biorefineries
from thermodynamic, economic, and environmental
standpoints.
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