Renewable Energy 132 (2019) 898e910

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

Exergoeconomic analysis of conventional and using reactive

distillation biodiesel production scenarios thermally integrated with a
combined power plant
Fatemeh Joda*, Fatemeh Ahmadi
Faculty of Mechanical & Energy Engineering, Shahid Beheshti University, A.C., Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: In this study a conventional and an improved biodiesel production plants, have been simulated in Aspen
Received 29 September 2017 Plus V8.2. Improved process converts waste cooking oil using a reactive distillation catalyzed by a het-
Received in revised form erogeneous catalyst in which catalyst removal and neutralization units are not necessary. Using pinch
30 May 2018
technology and exergoeconoic analysis, exergy destruction of each process are calculated and the best
Accepted 14 August 2018
configuration in order to integrate biodiesel production process with a combined cycle power plant is
Available online 15 August 2018
presented. The results show that the produced electricity in the modified process is less expensive.
Exergy destruction to generated power ratio and the net power generation in the conventional process
Keywords:
Biodiesel production plant
are equal to 1.59 and 17936.6 kW, respectively, and the corresponding values for the modified process are
Process simulation 1.57 and 18346.1 kW, respectively. The costs of electricity are 19.145 $/GJ and 16.91 $/GJ for the con-
Exergy ventional and improved cases, respectively.
Exergoeconomic analysis © 2018 Elsevier Ltd. All rights reserved.
Reactive distillation

1. Introduction triglyceride content. They also studied the effect of operation pa-
rameters such as temperature and methanol to oil ratio on yield.
Biodiesel is a renewable fuel, which can provides part of the After reaction, biodiesel and glycerol are separated by distilla-
energy demand in transport and electricity sectors. Biodiesel can be tion columns, which require high energy. Recently, a number of
prepared from various sources including vegetable oil [1], animal studies have investigated the processes using reactive distillation
fats [2,3], microalgae [4] and waste cooking oil (WCO) [5]. WCO, (RD) for biodiesel production [11e15]. Reaction and separation
which is recycled waste oil, is cheaper because of its lower price and simultaneously take place in this stage, increasing the yield of the
economic benefit [6]. Biodiesel is a methyl ester produced through reaction and reducing the required utilities [16]. Moreover, this
transesterification process in the presence of a catalyst and glycerol process is more economic than the conventional process because of
is the process byproduct [7]. Methanol is often used as the alcohol its lower capital investment and shorter payback period [16]. Since
in transesterification process and optimum methanol to WCO ratio homogeneous catalysts cause reactive distillation corrosion, using
depends on the type of the catalyst and other operating conditions. heterogeneous catalysts, e.g. CaO and MgO, is preferred [17,18].
Homogeneous catalysts such as sodium hydroxide and potas- These catalysts are also less expensive and more environmental
sium hydroxide are used in the transesterification reaction for the friendly than homogenous types [19].
conventional process [8]. Klofutar et al. [9] investigated the effect of Boon-Anuwat et al. [17] compared the energy consumption of
temperature on transesterification reaction rate of rapeseed(RO) two biodiesel production processes catalyzed by homogeneous and
and waste sunflower(SO) oils in presence of potassium hydroxide. heterogeneous catalysts, in which the required energies were 754.8
They calculated the mass-transfer coefficients of tri-acylglycerols and 153.0 kWh/ton biodiesel, respectively.
during initial transestrefication stage, activation energy of SO and Hou and Zheng [20] studied a biodiesel production plant with
RO and optimum methanol recycle ratio. Likozar et al. [10] modeled 8000 t/a capacity, which required 2300 MJ/h of hot utility, 1920 MJ/
transestrerification of lipids to identify the conversions of different h of cold utility and 197 MJ/h of electricity. They suggested that if
the plant use solar utility to supply steam and electricity, 4676 ton
of CO2 released can be eliminated every year.
* Corresponding author. Exergoeconomic analysis are two prominent methods, which
E-mail address: [email protected] (F. Joda).

https://doi.org/10.1016/j.renene.2018.08.052
0960-1481/© 2018 Elsevier Ltd. All rights reserved.
 F. Joda, F. Ahmadi / Renewable Energy 132 (2019) 898e910 899

introduce thermodynamic and economical criteria to evaluate the In this study, two scenarios have been presented to produce
performance of energy systems. Exergoeconomic is a method, biodiesel from waste cooking oil. The first one is a conventional
which combines thermodynamic evaluations and economic prin- process while the other one is a modified process, which converts
cipals, in order to specify and design more cost-effective systems. waste cooking oil by introducing a reactive distillation catalyzed
Blanco-Marigorta et al. [21] applied an exergy analysis to a by a heterogeneous catalyst. Since the conventional process uses
biodiesel production plant, which also utilized biodiesel to produce a homogeneous catalyst, it should include the catalyst removal
steam as a utility steam generation. According to their study, the and neutralization units. In the second scenario, appropriate
highest exergy destruction takes place during transesterification biodiesel purity can be achieved because of high yield in the
reaction, which contributes to about 95% of total exergy destruction reactive distillation. In both scenarios, the produced biodiesel is
of plant. The exergetic efficiency of the overall process was 63%. fed into the combined power plant. Electricity cost has been
Karimi [22] performed a new procedure for ultrasound-assisted calculated based on exergoeconomic analysis for both processes.
in-situ transesterification of microalgae slurry to extract lipids and In addition, the required utilities have been evaluated through
convert to biodiesel. He optimized fatty acid methyl ester (FAME) pinch technology.
yield and exergy efficiency in that process. Also he found that
120.4 MJ internal exergy are destructed to produce 1 kg biodiesel. 2. Simulation
Perdomo-Hurtado et al. [23] studied the preheater device
designed based on exergy effectiveness transfer and dimentionless A biodiesel production plant with a 10 million gallon per year
entropy generation approaches. They found out that a 6-3 shell- capacity [28,29], which uses waste cooking oil as the feedstock with
&-tube heat exchanger attains the highest performance in terms of a density of 932.1 kg/cm3, has been simulated. In this study, the
exergy effectiveness transfer and dimensionless entropy operating time has been considered 8000 h per year.
generation. UNIF-DMD (improved UNIFAC) has been selected as an equation
Aghbashlo et al. [24] used exergoeconomic and exergoenvir- of state to calculate the liquid-liquid equilibrium calculation in
onmental approaches to study effects of varies process parameters Aspen Plus V8.2. Waste oil containing triglycerides reacts with
of biodiesel production from waste cooking oil such as methanol to methanol in transesterification reaction, producing biodiesel and
oil ratio, transestrefication temperature and residence time. Under glycerol as the main product and byproduct, respectively. In the
the optimum conditions the cost and environmental impact per reactor, transesterification reaction occurs according to the mech-
unit of exergy for product were calculated respectively 2.23 USD/GJ anism presented in Fig. 1.
and 1.23 mPts/GJ. Both processes and the combined power plant integrated with
The development of biodiesel production technology and the them are individually simulated in Aspen to carry out the ther-
rapid growth of energy demand have made biofuel a power plant modynamic and economic analyses.
feed. Most recently, some researchers have investigated the com- As shown in Figs. 2 and 3, the produced biodiesel has been used
bustion of biodiesel as a power plant fuel [25e27]. as a fuel in the combined cycle to produce power.

Fig. 1. Transesterification reaction [30].

Fig. 2. Conventional biodiesel production unit integrated by combined cycle power generation (case A).
F. Joda, F. Ahmadi / Renewable Energy 132 (2019) 898e910 901

2.1. Case A: simulation of conventional biodiesel production unit

integrated with a combined cycle power plant

First, the conventional process has been simulated. In this unit,

input molar ratio of oil to methanol is equal to 1:6 and NaOH (1% by
weight) is selected as a base catalyst. The feed pressure and tem-
perature are 4 bar and 60
C, respectively.
Unreacted methanol, biodiesel, glycerol, unreacted oil, catalyst
and water are the main components of the product stream after
transesterification reaction. To remove unreacted methanol and
recycle it to the reactor, a distillation tower (DIST1) is used. The
bottom stream of DIST is a two phase liquid, which is fed into an
extraction column to separate the organic and inorganic phases by
injecting water to the column after preheating and increasing its
pressure. Biodiesel, unreacted oil and diglyceride exist in the organic
phase and the inorganic phase is mainly composed of glycerol,
water, catalyst and water. A CSTR(continuous flow stirred-tank)
reactor (NETRAUL) and a separator (SEP) are used to neutralize
the catalyst and separate the neutralized catalyst, respectively. Both
streams (biodiesel and glycerol) then enter the distillation columns
DIST2 and DIST 3 and are purified to about 99% purity.
For power generation, first, air is compressed. The compressed
air and produced biodiesel are then fed into the combustion
chamber, which has been simulated in Aspen by RGIBS. Outlet hot
gas of combustion chamber at 902
C enters a gas turbine and po-
wer is generated. The required steam superheated for steam power
cycle is obtained through transferring the heat of outlet gas of
turbine and cold water using three types of equipment; Economizer
(saturated steam generator), Evaporator (saturated steam gener-
ator) and Superheated (superheated steam generator). The exhaust
steam of the steam turbine enters a condenser and then returns to
the cycle. In this process 17936 kW electricity is generated.
The stream composition and thermodynamic properties of the
convention biodiesel production process streams as shown in Fig. 2
are presented in Tab A-1 and Tab A-2.

2.2. Case B: simulation of an integrated power plant and a biodiesel

production plant by RD

Next, the process is re-simulated using a reactive distillation

(RD) column. As reported in previous work [12,31], RD column is an
equipment in which reaction and separation stages are integrated.
Hence, a considerable reduction in the total capital cost will be
observed. In addition we can reduce the necessary heat energy
demand in this process through employing the proper heat inte-
gration in RD and then decrease the separation stages.
The molar build up ratio and distillation to feed molar ratio of
RD column are selected as 4 and 0.6, respectively. This column has
10 stages and the reaction takes place in the second to ninth trays
with a hold up of 0.045 cubic meters. The column pressure is 5 bar.
A total condenser and a kettle reboiler have been considered for
RD. LLV equilibrium of state has been selected to calculate ther-
modynamic properties of the column.
Since heterogeneous catalysts offer significant benefits
compared with heterogeneous ones in RD, selecting the proper
catalyst type has a considerable effect on RD performance. There-
fore, CaO has been selected as the catalyst. The best oil to methanol
molar ratio has been 1:10. The reaction was assumed to be pseudo-
first-order. The reaction rate for this catalyst based on Arrhenius
equation which shown as the following two equations [29]:

Fig. 3. Integrated improved biodiesel production unit and combined power generation
cycle (case B).
902 F. Joda, F. Ahmadi / Renewable Energy 132 (2019) 898e910

 In this integrated system, 37320 and 4358 kW of power are

dcTG Ea generated in the gas and steam turbines, respectively. Since the
rTG ¼ ¼ 20:697CTG0  exp  ð1  XTG Þ (1)
dt RT pumps and compressors of the unit consume 23331 kW totally, the
net power generated from the integrated unit is equal to 18346 kW.
CTG ¼ CTG0 ð1  XTG Þ (2) Thermodynamic properties of the streams of the conventional
biodiesel production plant by RD unit integrated with a power
Which, R is the gas constant and the value of the activation energy plant as shown in Fig. 3 are presented in Tab A-3 and Tab A-4.
ðEa Þ is30 kj=mol.
Methanol boiling point at column operating pressure is about 3. Energy and exergoeconomic analysis
95
C, which is considerably lower than the boiling points of the
other components. On the other hand, substituting CaO heteroge- In this study, Exergy and exergoeconomic analyses methods are
neous catalyst for NaOH gives a methanol purity of over 99%. employed to compare and specify the value of the products.
Since the contact surface in the RD is high, conversion reaction
increases considerably. The bottom stream of RD contains the a) Exergy analysis
produced biodiesel, glycerol as a byproduct and methanol.
Unreacted oil concentration in this stream is low and biodiesel Total exergy is the sum of chemical potential, physical and ki-
purification has been facilitated because the reaction is nearly netic exergy:
complete. To separate glycerol from biodiesel, the product of RD
enters a liquid-liquid separator decanter column at 1 bar and 25
C. Ex ¼ Exk þ Ex p þ Exph þ Exch (3)
Biodiesel, which is an organic phase, is produced in extreme purity
(96%) because of high conversion reaction. Thus, there is no need in which Exk , Ex p , Exph and Exch are kinetic, potential, physical and
for further purification. Glycerol, as an inorganic phase containing chemical exergy, respectively, and the first two terms are usually
methanol, enters the next distillation (DIST2) column for further assumed negligible since changes in speed and elevation are very
separation. small. The physical and chemical exergy are usually calculated by
Similar to the last case, the produced biodiesel and compressed equations (4) and (5).
the excess air enter the RGIBS reactor. In this case, due to higher
_  ððh  h0 Þ  T0  ðs  s0 ÞÞ
Exph ¼ m (4)
biodiesel production, more air is needed to generate more power in
the turbine. The pressure ratios across the compressor gas and
steam turbine are 10 and 9.6, respectively, and the temperature of X
NC X
NC

the outlet gas of combustion stream is 900
C. The generation net Exch ¼ ni  Exch0 þ N  R  T0  xi Lnðxi Þ (5)
i¼1 i¼1
power is 18345.98 kW.

Fig. 4. The procedure of applying Exergy and Exergoeconomic analyses.

 F. Joda, F. Ahmadi / Renewable Energy 132 (2019) 898e910 903

In this study, the method presented by Arredondo and Mende- b) Exergoeconomic

leyev [32] has been used to calculate the standard chemical exergy of
streams. In this method, the exergy of fuel and biomass components Thermodynamic and economic information is required to carry
are calculated according to their chemical formula (equation (6)). out exergoeconomic analysis. The thermodynamic data is extracted
from simulated models in Aspen and the costs are calculated using
Exch0 ¼ b  LCV (6) the expressed functions of thermodynamic design parameters [6].
For each process equipment (k), a cost balance is written as in
In this equation, b is a non-dimensional factor and LCV is the low
the following equation:
calorific value.
b is a function of the type of the phase and chemical formula X X
stated using equation (7): C_ Q ;k þ C_ i;k þ Z_ k ¼ C_ e;k þ C_ W;k (12)
i e
H o
b ¼ 1:0374 þ 0:0159 þ 0:0567 (7) Z_ k is the monetary value which is the sum of the investment and
C c
maintenance costs of the kth unit of the system (Equation (13)).
in which H, C and O are the weight percentages of hydrogen, carbon
and oxygen of the component, respectively. CI OM
LCV and HCV (high heating value) are calculated by equation (8) Z_ k ¼ Z_ k þ Z_ (13)
k
if Arrenda method is used.
C_ represents the cost rate of each stream and is defined as
LCV ¼ HCV  0:0894  2:4423  H (8) follows:

, ,
HCV ¼ 0:3491  C þ 1:1783  H þ 0:1005  S  0:1034  O C ¼ c*E x (14)
 0:0151  N  0:211  A _ and c are the exergy rate and cost per unit of exergy,
Ex
(9) respectively.
In analyzing a component, we may assume that the costs per
If Mendeleyev method is used, the equation (10) is applied to
exergy unit are known for all entering streams. These costs are
calculate the LCV.
known from the components they exit or, if a stream enters the
LCV ¼ 0:339  C þ 1:03  H  0:109  ðO  SÞ  24  W (10) overall system consisting of all components under consideration,
from the purchase cost of this stream. Consequently, the unknown
in which C, H, S, O, N, A and W are the mass percentages of carbon, variables to be calculated from a cost balance for the kth compo-
hydrogen, sulfur, oxygen, nitrogen, ash and moisture in the oil, nent are the costs per exergy unit of the exiting material streams
respectively. HCV and LCV have units of MJ/kg and the values for C, ðCe;k Þ and, if power or useful heat are generated in that component,
H, S, O, N, A and W must be written in percentage. the cost per unit of exergy associated with the transfer of power
The calculated values of standard chemical exergy for biomass ðCW;k Þ or heat ðCQ ;k Þ.
component are calculated. These values for other components such To estimate the cost of each stream, the cost balance for each
as NaOH, H3PO4, Na3PO4, O2, N2, CO2 and glycerol have been taken component is solved. In some equipments, there are more than one
from other studies [33,34]. inlet and outlet flows. In such cases, the number of unknown costs
Exergy destruction of each equipment is calculated from the is higher than that of cost balances. Therefore, auxiliary equations
exergy balance equation shown below: must be developed to solve the problem.
The Aspen Plus doesn't provide the exergy value so a Visual
Exdes ¼ Exin  Exout þ Win þ Qin (11) Basic code linked with Aspen Plus has been written to calculate the
stream exergy, equipment exergy destruction and exergy cost in
each plant. The procedure of this analysis is shown in Fig. 4.

Table 1
Exergy destruction of equipment in conventional process.

Equipment Exergy Percentage of exergy Equipment Exergy Percentage of exergy

destruction(kW) destruction destruction(kW) destruction

Dist1 37.24 0.13 COMB 16687.87 58.58

Dist2 342.05 1.20 GT 2123.05 7.45
DIST3 306.51 1.08 ST 609.63 2.14
Reactor 634.48 2.23 COND 3390.40 11.90
NEUTRAL 7.07 0.03 ECO 680.11 2.39
EXTRACT 7.94 0.03 EVAP 1569.48 5.51
HX1 0.61 0.00 SUP 307.07 1.08
HX3 4.43 0.02 PUMP4 4.75 0.02
HX4 4.74 0.02 COMP 1731.53 6.08
HX5 1.78 0.01 Total exergy destruction (biodiesel production 1383.76 4.86
HX6 7.80 0.03 unit)
PUMP1 0.04 0.00 Total exergy destruction (powe generation unit) 27103.88 95.14
PUMP2 0.16 0.00
PUMP3 0.21 0.00
MIXER1 8.58 0.03
MIXER2 16.03 0.06 Total 28487.64 100
SEP 4.08 0.01
904 F. Joda, F. Ahmadi / Renewable Energy 132 (2019) 898e910

c) Pinch Technology (heat sink), respectively, such that in any temperature range, the
enthalpy change of the composite stream is the sum of the enthalpy
Pinch analysis is a systematic method for reducing energy changes of the individual streams. The point with the minimum
consumption of processes to calculate minimum energy con- temperature approach between the hot and cold composite curves
sumption. Pinch technology has been successfully used in a wide is defined as the pinch point. Where the cold composite curve ex-
range of industries, including non-chemicals: food industry, paper tends beyond the start of the hot composite curve, heat recovery is
mill, etc to reduce the global energy consumption. The method is not possible, and the cold composite must be supplied with
based on the first and second thermodynamic principles and allows external hot utility. In the same way external cold utility can be
to determine the best heat exchangers network and utility system. determined. Finally maximum heat recovery must be calculated by
Possible heat exchanges between cold streams (requiring heat) and trading of (hot and cold) utility requirement and heat exchangers
hot streams (releasing heat) in order to maximize the heat recovery area.
has been identified through using the pinch analysis. The process
data is represented by plotting thee hot and cold streams on the 3.1. Energy and exergoeconomic analyses of conventional process
temperature-enthalpy axes.
Hot and cold composite curves have been constructed by 3.1.1. Exergy analysis
combining data for all the streams (heat source) and cold streams As expected, the combustion chamber, condenser, HRSG (heat

A: B:

C: D:

Fig. 5. A) CC, B) GCC before integration, C) CC and D) GCC after integration with power plant of conventional process.
 F. Joda, F. Ahmadi / Renewable Energy 132 (2019) 898e910 905

recovery steam generator), gas turbine and compressor with exergy could be recovered and minimum 2393.05 and 2041.55 kW of hot
destructions of 58.8, 11.9, 9.01, 7.48 and 6.10%, respectively, are the and cold energies should be provided from external utilities,
main sources of exergy destruction in the conventional process respectively, in the process. After integrating with a power plant,
integrated with a power plant. It has been observed that exergy according to GCC, this unit needs just 19255.18 kW of cold utility
destruction in biodiesel production section is very low in compar- supplied from the cooling water.
ison with the power generation section.
In this integrated system, 36425 kW of power are generated in
the gas turbine and the steam turbine also generates 4321 of kW 3.1.3. Exergoeconomic analysis
power. Totally, 22810.12 kW of power are consumed in the pumps To apply exergoeconomic analysis, the cost of equipment and
and compressor so that the amount of the net power generated is utilities are calculated according to [35e37]. In this study, extrac-
equal to 17936.58 kW. The ratio of Exergy destruction to electricity tion (EXTRACT) and separator (SEP) columns are considered as
power generated is equal to 1.58. The result of exergy analysis is tower and vessel, respectively, and the required heats are supplied.
shown in Table 1. These costs have been annualized for plan life time (15 years) and
then the cost rate are converted to dollar per hour (8000 h oper-
ating time per year). The calculated equipment cost rates are pre-
3.1.2. Energy analysis and utility calculation sented in Table 2.
The amount of the minimum required utility has been calcu-
lated. 2393.05 kW and 2041.55 kW of hot and cold utility are
Table 4
required in the biodiesel production section, respectively. These
The result of conventional plant exergoeconomic analysis.
values change to 0 kW and 19255.18 kW, respectively, after inte-
grating with this combined power plant. Stream Cost/Exergy($/GJ) Stream Cost/Exergy($/GJ)
As mentioned earlier, superheated steam is produced through 1 WCO 4.662066 20 H3PO4 1064.31
recovering the heat of outlet gas of gas turbine in HRSG. A cold 2 WCO2 4.663334 21 XPO4 0
utility is needed to for the utility outlet stream of steam turbine to 3 WCO3 4.663573 22 WMEOH 0
4 MEOH 22.23197 23 GLCR 4.164792
reach environmental conditions. The amount of this utility is equal
5 NAOH 462.6384 24 GLYCROL 4.202
to 19606.68 kW, which is significantly higher than that of the other 6 MIX1 23.54582 25 AIR 0
streams. 7 MIX2 23.54778 26 CAIR 18.90677
Composite Curve (CC) and Grand Composite Curve (GCC) of 8 MIX3 23.54131 27 HOTG 15.87579
9 REACOUT 6.6686 28 TURBOUT 15.87579
conventional process before and after integrating with a power
10 REMEOH 22.23197 29 FLUEGAS 15.87579
plant for pinch point temperature of 10
C are shown in Fig. 5. 11 EST 5.701194 30 WIN 20.63223
According to CCs and GCCs, before integrating, 919.22 kW energy 12 EST2 5.701435 31 W2 20.56834
13 EST3 5.703085 32 SUPSTM 20.63223
14 WATER 0.758217 33 STMOUT 20.63223
Table 2 15 WBD 0 34 COND 20.63223
The equipment cost rates for case A. 16 BD 8.88169 35 CWIN 0
17 BDIESEL 8.898 36 CWOUT 0.314608
Num. equipment _
Z($/hr) Num. Equipment _
Z($/hr) 18 REOIL 4.634661 37 W_GT 17.12003
1 REACTOR 0.21 13 HX5 0.03 19 REOIL2 4.662066 38 W_ST 25.52689
2 NEUTRAL 0.05 14 HX6 0.08
3 SEP 0.06 15 COND 2.75
4 EXTRACT 0.19 16 COMB 2.03
Table 5
5 MIXER1 0.02 17 HRSG 8.15
Exergy destruction of Equipment for case B.
6 MIXER2 0.02 18 pump1 0.06
7 DIST1 1.34 19 pump2 0.06 Equipment Exergy Percentage of
8 DIST2 6.30 20 pump3 0.06 destruction (kW) exergy
9 DIST3 2.62 21 pump4 0.17 destruction
10 HX1 0.02 22 GT 41.82
11 HX3 0.05 23 ST 30.87 RD 768.26 2.67
12 HX4 0.05 24 COMP 40.51 DIST2 182.62 0.63
total 137.51 DECANTER 11.44 0.04
HX1 0.00 0.00
HX2 3.70 0.01
HX3 20.14 0.07
Table 3 HX4 1.79 0.01
The auxiliary equations to determine cost of conventional plant streams. Mixer1 6.59 0.02
Mixer2 0.00 0.00
Num Equations Pump1 0.36 0.00
1 cMEOH ¼ cREMEOH Pump2 1.36 0.00
2 cREOIL2 ¼ cWCO Total exergy destruction 996.26 3.46
3 cMEOH ¼ 0.5 '$/kg (biodiesel production unit)
4 cWCO ¼ 0.18 ' $/kg
5 cWATER ¼ 0.0004 ' $/kg ECO 715.93 2.48
6 cH3PO4 ¼ 0.85$/kg EVAP 1598.68 5.55
7 cWIN ¼ cCONDW SUP 307.83 1.07
8 cWOIL ¼ cWMEOH ¼ cX3PO4 ¼ cAIR ¼ cCWIN ¼ 0 COND 3427.17 11.89
9 cFLUEGAS ¼ cTURBOUT Pump3 11.14 0.04
10 cNAOH ¼ 0.35$/kg COMP 1758.36 6.10
11 cHOTG ¼ cTRBOUT COMB 17322.03 60.12
12 cSUPSTM ¼ cSTMOUT GT 2073.75 7.20
13 cBD cGLCR ST 603.37 2.09
¼
CSBIODIESEL CSGLYCROL Total exergy destruction 27818.25 96.54
14 cSTMOUT ¼ cCONDW (power generation cycle)
906 F. Joda, F. Ahmadi / Renewable Energy 132 (2019) 898e910

The unknown cost rates are specified for each unit according to market price with the mass flow rate. In fact, an equal proportion of
equation (12) and auxiliary equations stated in Table 3. the cost per unit of exergy to market price are considered for the
As shown in Table 3, 8th row, the cost of feed streams (AIR and different products in multiple product separation units.
CWIN) and waste outlet streams (WOIL, WMEOH and X3PO4) are The final cost is shown in Table 4.
assigned zero because these streams have no prices. The relation These results represent that the cost of biodiesel and glycerol
presented in row 13 of this Table, presents an auxiliary equation for per unit exergy are 8.9 and 4.2 $/Gj, respectively, which are equal to
separators (EXTRACT, DIST2, NEUTRAL, SEP and DIST3). CSBIODIESEL 0.34 and 0.08 $/kg, respectively, and the cost of electricity is 19.15
  $/GJ.
and CSGLYCROL 4:86 $=kg are given by multiplication of their

A:
B:

C: D:

Fig. 6. A) CC, B) GCC before integration, C) CC and D) GCC after integration with power plant of modified biodiesel production process.
 F. Joda, F. Ahmadi / Renewable Energy 132 (2019) 898e910 907

Table 6
Hot and cold streams by Pinch analysis for B case.

Stream Equipment Supply Temp(C) Outlet Temp(C) Required energy(kW)

Hot stream condRD Condenser 111.2 1227.92

condDIST Condenser 115.8 46.8 396.4
HX3 EST_to_EST2 122.3 25.0 397.2
HX4 GLCR_to_GLYCROL 260 80 59.9
TRBOUT to FLUEG HRSG (ECO, EVAP and SUP) 455.7 145.7 24052.7
COND 103.6 35 19731.3
Total 45865.42
Cold stream rebRD Reboiler 111.2 122.3 1634.89
rebDIST Reboiler 259.8 260.9 483.8
HX2 WCO3_to_WCO4 25 60 87.0
W1 to SUPSTM HRSG (ECO, EVAP and SUP) 35.4 401.5 24052.76
Total 26258.45

3.2. Energy and exergoeconomic analyses of improved biodiesel 3.2.2. Energy analysis and utility calculation
production integrated to power generation unit As Composite Curves and Grand Composite Curves illustrated in
Fig. 6; The improved process requires 2145.21 kW and 2030.74 kW
3.2.1. Exergy analysis of hot and cold utilities, respectively, to produce biodiesel, which is
In the improved process, the exergy lost in the biodiesel pro- 10.36% and 0.053% less than the previous case. After integrating the
duction section decreased 28% in comparison with the conven- improved biodiesel with an 18346 kW power plant, the total hot
tional process. Since power generated is raised to 18346.1 KW, and cold utilities are 0 and 19616.77 kW, respectively.
exergy lost is increased by 2.6%. Similar to case A, exergy destruc- As depicted in these diagrams, 26248.65 kW of energy could be
tion of the power plant is considerably more than that of biodiesel recovered in the improved biodiesel production plant integrated
production section. The exergy destruction to electricity power with a power plant. Therefore, 0 and 19616.77 kW of hot and cold
generated ratio is equal to 1.57. The significant part of exergy utilities, respectively, are required. The stream data of case B is
destruction is caused by the combustion chamber (60.12%). In represented in Table 6.
addition, 11.89 and 9.1% of exergy destruction occurred in the In the improved process, the reaction and separation sections
condenser and HRSG units, respectively. The results of exergy are merged into a unit such that the transesterification reaction and
analysis are presented in Table 5. separation operations take place simultaneously in a reaction
Since the majority of the exergy destruction has taken place by distillation tower. On the other hand, both proposed processes are
the reaction section, an RD column has been employed to integrate integrated to a power plant such that the produced biodiesel is fed
this section to reduce the destructed exergy. In the improved pro- into the power plant as a fuel. The required hot and cold utilities are
cess, 768.26 kW of exergy have been destructed in the RD column, calculated by pinch technology for both proposed processes. This
while the total corresponding values in the DIST1, REACTOR and means one can identify and act upon the opportunities for
DIST2 for base case, which are doing same as RD, is 1013.77 kW, improvement of heat integration in the improved process more in
which is reduced by 24.2%. the conventional process.

Table 7 3.2.3. Exergoeconomic analysis

The equipment cost rates for case B. In this case (B), the reactive distillation is used instead of
Num. equipment _
Z($/hr) Num. Equipment _
Z($/hr) transesterification reactor and methanol recovery distillation col-
umn. The capital cost of the reactive distillation column is calcu-
1 COMB 2.08 9 DECANTER 0.19
2 HRSG 7.69 10 MIXER1 0.02 lated almost like a distillation column. Catalyst cost is also included
3 PUMP1 0.06 11 RD 3.29 in the distillation column cost. Since a heterogeneous catalyst is
4 PUMP2 0.07 12 DIST2 2.05 used in case B, the purification of biodiesel, neutralization of ho-
5 PUMP3 0.20 13 HX2 0.03 mogenous catalyst and separation of neutralized catalyst units are
6 GT 42.78 14 HX3 0.12
7 ST 31.00 15 HX4 0.03
8 COMP 41.00 16 COND 2.79
Table 9
total 133.40
The case B streams costs of exergy.

Num Stream Cost/Exergy($/Gj) Num Stream Cost/Exergy($/Gj)

Table 8 1 WCO 4.662066 16 GLYCEROL 3.549187

The auxiliary equations to determine unknown streams cost of 2 WCO2 4.662066 17 AIR 0
improved plant. 3 WCO3 4.662441 18 CAIR 16.87173
4 WCO4 4.662165 19 HOTG 14.0961
Equation Equations 5 MEOH 22.23197 20 TURBOUT 14.0961
1 cMEOH ¼ cREMEOH 6 MIX1 22.23898 21 FLUEGAS 14.0961
2 cMEOH ¼ 0.5 '$/kg 7 MIX2 22.23949 22 WIN 17.98484
3 cWCO ¼ 0.18 ' $/kg 8 MIX3 22.23949 23 W2 17.93147
4 cWIN ¼ cCONDW 9 REMEOH 22.23197 24 SUPSTM 17.98484
5e7 cWMEOH ¼ cAIR ¼ cCWIN ¼ 0 10 EST 7.296936 25 STMOUT 17.98484
8 cTRBOUT ¼ cFLUEGAS 11 EST2 7.305279 26 CONDW 17.98484
9 cHOTG ¼ cTRBOUT 12 BDIESEL 7.81097 27 CWIN 0
10 cSUPSTM ¼ cSTMOUT 13 S2 3.321352 28 CWOUT 0.261079
11 cBDIESEL cGLCR 14 WMEOH 3.321352 29 W_GT 15.23804
¼
CSBIODIESEL CSGLYCROL 15 GLCR 3.517268 30 W_ST 22.50258
908 F. Joda, F. Ahmadi / Renewable Energy 132 (2019) 898e910

eliminated. The employed decanter to purify biodiesel has been Nomenclature

considered as a horizontal vessel. The calculated equipment cost
rates are presented in Table 7. OOO Triolein (C57H104O6)
With the aid of the cost balances and the auxiliary equations LLL Trilinolein(C57H98O6)
presented in Table 8, the cost rates and the costs per unit of exergy PPP Tripalmitin(C51H98O6)
are calculated for each stream in the overall plant. OO Diolein(C39H72O5)
The costs of feed streams (AIR and CWIN) and out stream LL Dilinoleate (C39H68O5)
(WMEOH) are assumed to have no value (equations (5)e(7) of PP Dipalmitate (C35H68O5)
Table 8) and equation (11) is considered for separation section 1O Oleic acid (C18H34O2)
(DECANTER and DIST2). The results of exergoeconomic analysis are 1LI Linoleic acid (C18H32O2)
represented in Table 9. The cost of biodiesel and glycerol per exergy 1P Palmitic acid (C16H32O2)
unit are 7.81 and 3.44 $/GJ, respectively, which are equal to 0.295 METHYL-O Methyl oleate (C19H36O2)
and 0.0655 $/kg, respectively, and the cost of electricity is 16.91 METHYL-LI Methyl linoleate(C19H34O2)
$/GJ. METHYL-P Methyl palmitate(C17H34O2)
Ex Exergy [kW]
H Enthalpy [kj]
T Temperature [C]
4. Conclusion S Entropy [kj/K]
N Number of mole [kmol]
In this study, energy, exergy and exergoeconomic analysis have M Mass flow rate [kg/s]
been applied in the conventional and improved processes using RD R Gas universal constant [kj/K.kmol]
column biodiesel production plant. In order to evaluate the cost of X mole ratio
electricity from biodiesel power generation, these two biodiesel W Electricity power [kW]
plants are also integrated with a combined power plant, Such that Q Heat energy [kW]
biodiesel has been fed to the power plant as fuel and a utility C_ The cost rate [$/hr]
integration between biodiesel production unit and power plant has
Z_ The rate of equipment cost[$/hr]
been accomplished.
In the improved case, because of the high value of reaction
conversion, the produced biodiesel has been increased such that Subscripts
leads to increase in produced power by 2.28% and decrease in K Kinematic
exergy destruction per produced power by 1.1%. Required hot and P Potential
cold utility for biodiesel production unit increased by 10.36 and Ph Physical
0.53%, respectively. In the other hand, overall cold utility for inte- Ch Chemical
grated units has been raised due to increasing power plant capacity. 0 At the standard condition
Cost per unit exergy of glycerol and biodiesel streams and the net
produced power in the improved case are respectively equal to A. Appendix
3.55, 7.81 and 16.96 $= which they have declined 15.54%, 12.22%
Gj
and 11.42% from the conventional case, respectively.

Table A-1
The thermodynamic properties of streams and operating condition of integrated conventional biodiesel production unit and power generation cycle.

WCO MEOH NAOH REACOUT EST WATER BDIESEL H3PO4 GLYCROL

Mole Fraction
METHANOL 0 1.00 0.00 0.09 0.00 0.00 0.00 0.00 0.00
OOO 0.36 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00
METHYLO 0 0.00 0.00 0.26 0.28 0.00 0.36 0.00 0.00
GLYCEROL 0 0.00 0.00 0.06 0.07 0.00 0.00 0.00 1.00
NAOH 0 0.00 0.20 0.00 0.00 0.00 0.00 0.00 0.00
WATER 0 0.00 0.80 0.02 0.01 1.00 0.00 0.42 0.00
H3PO4 0 0.00 0.00 0.00 0.00 0.00 0.00 0.58 0.00
NA3PO4 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
PPP 0.13 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
METHYLP 0 0.00 0.00 0.08 0.09 0.00 0.13 0.00 0.00
METHY-LI 0 0.00 0.00 0.38 0.42 0.00 0.51 0.00 0.00
1P 0 0.00 0.00 0.04 0.04 0.00 0.00 0.00 0.00
1O 0 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00
1LI 0 0.00 0.00 0.01 0.02 0.00 0.00 0.00 0.00
PP 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
OO 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
LLL 0.51 0.00 0.00 0.02 0.02 0.00 0.00 0.00 0.00
LL 0 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00

Total mass flow kg/h 4410.4 499.36 100.00 7205.14 6499.81 90.08 4422.55 238.08 461.13
Enthalpy kj/kg 2353 7452.3 14121.0 3376.5 2810.93 15864.9 2161.29 8403.37 7126.50
Entropy kj/kgK 7.068 7.51 0.52 5.23 4.85 9.05 4.38 3.30 6.27
Temperature C 25 25.00 25.00 60.00 86.87 25.00 100.00 25.00 80.00
Pressure bar 1 1.00 1.00 4.00 0.50 1.00 1.00 1.00 1.00
 F. Joda, F. Ahmadi / Renewable Energy 132 (2019) 898e910 909

Table A-2
The thermodynamic properties of streams and operating condition of integrated conventional biodiesel production unit and power generation cycle.

AIR CAIR HOTG TRBOUT WIN SUPSTM STMOUT

Mole Fraction
WATER 0.00 0.00 0.02 0.02 1.00 1.00 1.00
CO2 0.00 0.00 0.05 0.05 0.00 0.00 0.00
O2 0.23 0.23 0.18 0.18 0.00 0.00 0.00
N2 0.77 0.77 0.75 0.75 0.00 0.00 0.00

Total mass flow kg/h 249555.94 249555.94 253978.48 253978.48 27743.53 27743.53 27743.53
Enthalpy kj/kg 0.22 328.52 285.17 231.14 15823.58 12718.67 13279.42
Entropy kj/kgK 0.15 0.23 1.01 1.11 8.91 2.28 2.02
Temperature C 25.00 343.08 899.04 456.66 35.00 401.71 103.82
Pressure bar 1.00 10.00 9.60 1.00 1.00 20.00 1.00

Table A-3
Thermodynamic properties of stream for improved process by reactive distillation which is integrated with a power plant.

WCO MEOH EST BDIESEL GLYCROL

Mole Fraction
METHANOL 0 1.00 0.14 0.04 0.00
OOO 0.36 0.00 0.00 0.00 0.00
METHYLO 0 0.00 0.28 0.35 0.00
GLYCEROL 0 0.00 0.08 0.00 1.00
PPP 0.13 0.00 0.00 0.00 0.00
METHYLP 0 0.00 0.10 0.12 0.00
METHY-LI 0 0.00 0.40 0.49 0.00
LLL 0.51 0.00 0.00 0.00 0.00

Total mass flow kg/h 4410.39 1281.69 5692.08 4620.01 463.48

Enthalpy kj/kg 2352.98 7452.34 3187.15 2527.29 7124.76
Entropy kj/kgK 7.06836 7.51 4.63 4.96 6.27
Pressure bar 1 1.00 4.70 1.00 1.00
Temperature C 25 25.00 122.26 25.00 80.00

Table A-4
Thermodynamic properties of stream for improved process by reactive distillation which is integrated with a power plant.

AIR CAIR HOTG TRBOUT WIN SUPSTM STMOUT

Mole Fraction
WATER 0.00 0.00 0.02 0.02 1.00 1.00 1.00
CO2 0.00 0.00 0.05 0.05 0.00 0.00 0.00
O2 0.23 0.23 0.18 0.18 0.00 0.00 0.00
N2 0.77 0.77 0.75 0.75 0.00 0.00 0.00

Total mass flow kg/h 255181.76 255181.76 259801.77 259801.77 27923.68 27923.68 27923.68
Enthalpy kj/kg 0.22 328.52 277.74 238.03 15823.58 12719.22 13279.76
Entropy kj/kgK 0.15 0.23 1.01 1.11 8.91 2.29 2.02
Pressure bar 1.00 10.00 9.60 1.00 1.00 20.00 1.00
Temperature C 25.00 343.08 897.52 455.68 35.00 401.46 103.64

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