Applied Energy 114 (2014) 827836

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Intensication of biodiesel production from waste goat tallow using

infrared radiation: Process evaluation through response surface
methodology and articial neural network
R. Chakraborty , H. Sahu
Chemical Engineering Department, Jadavpur University, Kolkata 700 032, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Enhanced and signicantly

accelerated biodiesel synthesis from
waste goat tallow by infrared
radiation.
 In situ water removal by adsorbent
profoundly promotes achieving high
free fatty acids (FFAs) conversion.
 Process optimization and parametric
interaction-effects assessment by
response surface method.
 Articial Neural Network Modeling
for prediction of triglycerides and FFA
conversion.
 At optimal conditions, product
biodiesel contains 98.5 wt.% FAME.

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

Article history: For the rst time, an efcient simultaneous trans/esterication process for biodiesel synthesis from waste
Received 2 December 2012 goat tallow with considerable free fatty acids (FFAs) content has been explored employing an infrared
Received in revised form 26 March 2013 radiation assisted reactor (IRAR). The impacts of methanol to tallow molar ratio, IRAR temperature and
Accepted 8 April 2013
H2SO4 concentration on goat tallow conversion were evaluated by response surface methodology
Available online 4 May 2013
(RSM). Under optimal conditions, 96.7% FFA conversion was achieved within 2.5 h at 59.93 wt.% H2SO4,
69.97 C IRAR temperature and 31.88:1 methanol to tallow molar ratio. The experimental results were
Keywords:
also modeled using articial neural network (ANN) and marginal improvement in modeling efciency
Infrared radiation
Waste goat tallow
was observed in comparison with RSM. The infrared radiation strategy could signicantly accelerate
Biodiesel the conversion process as demonstrated through a substantial reduction in reaction time compared to
Articial neural network conventionally heated reactor while providing appreciably high biodiesel yield. Moreover, the in situ
RSM optimization water removal using silica-gel adsorbent could also facilitate achieving higher FFA conversion to fatty
In situ water removal acid methyl ester (FAME). Owing to the occurrence of simultaneous transesterication of triglycerides
present in goat tallow, overall 98.5 wt.% FAME content was determined at optimal conditions in the prod-
uct biodiesel which conformed to ASTM and EN biodiesel specications.
2013 Elsevier Ltd. All rights reserved.

Corresponding author. Tel./fax: +91 3324146378.

E-mail address: rajat_chakraborty25@yahoo.com (R. Chakraborty).

0306-2619/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apenergy.2013.04.025
828 R. Chakraborty, H. Sahu / Applied Energy 114 (2014) 827836
Nomenclature
M methanol to processed goat tallow (PGT) molar ratio
T temperature of IRAR(C)
C H2SO4 concentration (wt.%)
m coded value of methanol to processed goat tallow (PGT)
molar ratio
t coded value of IRAR temperature
c coded value of H2SO4 concentration
cFFA conversion of FFA (%)
cFFA; exp experimental conversion of FFA
cFFA;pre predicted conversion of FFA
cANN
FFA;pre predicted conversion of FFA through ANN modeling
cRSM predicted conversion of FFA through RSM modeling
FFA;pre
X input of process input 1
X{M} process input for methanol to oil molar ratio
X{T} process input for reaction temperature
X{C} process input for H2SO4 concentration
1. Introduction
Biodiesel synthesis from biodegradable sources has received
substantial interest all over the globe. Biodiesel derived from ani-
mal fat, vegetable oil, or used cooking oil has desirable fuel charac-
teristics e.g. high ash point, stupendous biodegradability,
admirable lubricity, and higher combustion efciency compared
to the corresponding properties of petro-diesel. Moreover, usage
of biodiesel in combustion applications renders over 90% reduction
in total non-combusted hydrocarbons emission incorporating 75
90% reduction in polycyclic aromatic hydrocarbons [1]. Transeste-
rication of vegetable oils and fats with monohydric alcohol leads
to formation of fatty acid monoalkyl esters, commonly called bio-
diesel [2]. However, for feedstocks with high (>0.5 wt.%) free fatty
acids (FFAs), the conversion of oil to biodiesel when attempted
using KOH or NaOH as catalysts results in formation of undesired
side products, emulsion and soap [3].
Goat tallow is one residual material from slaughter houses hav-
ing main application in the soap industry; it can also be used as
feedstock for biodiesel production [4]. Feedstock with low
(60.5 wt.%) FFAs can be used for synthesis of biodiesel through al-
kali/acid or enzyme-catalyzed transesterication process [5].
Application of MgOKOH heterogeneous base catalyst for methan-
olysis of mutton fat with signicantly low acid number (AN) of
0.514 mg KOH/g fresh fat rendered 98% conversion to biodiesel
[6]. Similarly, transesterication of duck tallow (low AN of
0.56 mg KOH/g) with methanol on alkali catalysts at 65 C resulted
97% FAME (fatty acid methyl ester) content in the product biodie-
sel in 3 h [7]. In another study, NaOH-catalyzed transesterication
of tallow with methanol at 60 C for 3 h yielded biodiesel fuel
which was tested for engine performance evaluation of biodiesel
(tallow methyl ester)petro-diesel blend [8].
Dias et al. [9] reported problem of soap formation in biodiesel
production from high FFA containing pig fat by direct base-
catalyzed-transesterication. To overcome this problem, waste
fryer grease [10] containing 56 wt.% FFAs was processed in
two-steps involving upstream H2SO4 catalyzed esterication for
5 h; followed by base-catalyzed downstream transesterication
using KOH which resulted overall 96 wt.% ester content in nal
biodiesel. Montefrio et al. [11] reported sulfuric acid as more
efcient catalyst than Fe2(SO4)3 in reducing the acid value of
fats, oil and grease to recommended level within 24 h as a
pretreatment step before the conventional alkali-catalyzed
biodiesel production process.
P output of process input 1
P{1} layer 1 input
A{1} layer 1 output, layer 2 input
A{2} layer 2 output
A input of process output 2
Y output of process output 2
YfcFFA g network output
Statistical abbreviations
R2 regression coefcient
EF modeling efciency
J number of runs
N total no. of runs
df degree of freedom
ANOVA analysis of variance
p-value probability value
An alternative to the two step process is the use of single step
acid catalysis [12,13], which can simultaneously transesterify tri-
glycerides and esterify FFAs. Nevertheless, H2SO4 acid-catalyzed
reactions with CH3OH are slow, requiring typically 48 h for feed
with 10.7% FFA content. In recent past, although researchers
[14] had achieved 93.21 5.07% FAME yield from waste mutton
tallow using 50 wt.% (on mutton tallow weight basis) H2SO4 as
catalyst; however, it could be achieved at the expense of remark-
ably long reaction time of 24 h. Several researchers reported
usage of very high concentration of H2SO4 and methanol in single
step conversion. In one such single step process [15], molar ratio
of methanol to oil and H2SO4 concentration (wt.% on oil basis)
were varied from 100 to 300 and from 16 to 100 respectively.
Maximum 98.2% methyl ester yield was reported at 300:1 molar
ratio using 100 wt.% H2SO4 catalyst in 4 h reaction span. In yet an-
other single step biodiesel production process [16], four levels
(25%, 50%, 60% and 100%) of H2SO4 quantity (based on oil weight)
and six levels (25:1, 30:1, 45:1, 56:1, 70:1 and 84:1) of methanol
to oil molar ratio were investigated. The best-reported process
conditions corresponding to maximum 70-wt.% biodiesel yield
were 56:1 molar ratio of methanol to oil, 100 wt.% H2SO4 and
4 h of reaction time. Boucher et al. [17] also used substantial
(50 wt.%) amount of H2SO4 in association with 93.710.86 meth-
anol to FFA molar ratio for the oil-fatty acid mixture containing
215 wt.% FFAs. Notably, they also demonstrated that greater
than 95% by weight of H2SO4 catalyst could be recovered under
all conditions investigated.
Soldi et al. [18] employed heterogeneous acid catalyst (sulfo-
nated polystyrene compounds) for synthesis of biodiesel from beef
tallow with high AN (53 mg KOH/g tallow) and reported 85% con-
version into methyl ester at the expense of signicantly high meth-
anol to oil molar ratio and reaction time of 100 and 18 h
respectively.
Beyond catalysts, intensication of biodiesel synthesis process
had focused on development of process technologies involving
microwave radiation, static mixers, micro-channel, oscillatory ow
and cavitational methods [19]. These technologies can render high
product yield through enhancement of mass and heat transfer in
the reactor. Biodiesel production by transesterication of rened
sunower oil through ultrasonic irradiation was found energy ef-
cient [20]. Moreover, radio frequency [21] heating could result fast
conversion (96.3 0.5%) of food-grade beef tallow to biodiesel.
However, in all these intensication studies waste tallow/animal
fat(s) was not employed as feedstocks. Besides, to the best of our
 R. Chakraborty, H. Sahu / Applied Energy 114 (2014) 827836
knowledge, no intensication study on biodiesel production from
high FFA containing waste tallow/animal fat has been reported
through the application of infrared radiation.
Supercritical methods involving high pressure and temperature
were investigated for conversion of animal fats to biodiesel. Only
40% conversion of lamb fats to biodiesel could be achieved at
50 C, 200 bar and 30% lipase loading [22] over a lengthy 24 h of
reaction time. Transesterication of rened lard in supercritical
methanol [23] at considerably high temperature (335 C) and pres-
sure (20 MPa) could result 89.91% FAMEs yield. Similarly, chicken
fat [24] was converted to biodiesel at supercritical conditions at
the expense of remarkably high temperature (300400 C) and
pressure (41.1 MPa).
Although, acid catalysis is ideal for biodiesel production from
oils and fats with high AN; nonetheless, development of a fast
and efcient acid catalyzed process to synthesize biodiesel from
waste goat tallow containing high FFA is still a challenging task
for practicing technologists and researchers.
Over past few years, articial neural networks (ANNs) had
been extensively applied to simulate complex and ill-dened
problems. ANN is capable of handling incomplete data and can
execute fast predictions and generalizations even for nonlinear
processes [25,26]. The response surface methodology (RSM)
determines the optimal working embodiment, through combina-
tion of a number of variables, resulting in fewer experiments.
RSM was applied to predict ve-level-three-factors parametric
interactions and optimal process conditions of biodiesel produc-
tion from rened/bleached lard [27] and in extraction of pheno-
lics [28].
It is clearly manifested from the literature review, that for feed-
stock viz. waste goat tallow (WGT) with high FFA content; remark-
ably high reaction time is required under conventional heating
protocol using both homogeneous and heterogeneous acid cata-
lysts. Hence, the present work endeavors to reduce the reaction
time for such high FFA containing WGT feedstock through the
application of IR radiation assisted reactor (IRAR) while achieving
the desired level of biodiesel yield. In order to reveal the interactive
effects among process independent parameters viz. methanol to
processed goat tallow (PGT) molar ratio (M), IRAR temperature
(T) and wt.% of H2SO4 (C) on FFA conversion of PGT (cFFA ) to FAME,
a three factor-three level face centered central composite design
(FCCD) was employed coupled with RSM to determine the optimal
process conditions corresponding to maximum FAME yield. Be-
sides, an ANN model viz. Articial Double Layer Feed-forward Net-
work (ADFFN) was also formulated involving the same factors and
its predictive ability was compared with that of RSM. Moreover, ef-
fect of in situ water adsorption (using silica-gel) on FFA conversion
has also been investigated.
Fig. 1. Schematic diagram of IR radiation assisted reactor (IRAR) for simultaneous trans/esterication of PGT.
829
2. Materials and methods
2.1. Materials
Waste goat tallow (WGT) was collected from a local slaughter
house and washed with deionized water to remove tiny bone
and esh particles. Subsequently, fats of WGT were melted by
heating at 60 C and the suspended fat insoluble matters were re-
moved by ltration to obtain the processed goat tallow (PGT) and
the PGT was stored in an air tight glass container. All the chemicals
used were of reagent grade. Sulfuric acid (98% pure), methyl alco-
hol, silica gel (adsorbent), phenolphthalein (indicator), HPLC grade
methanol, methyl oleate, methyl stearate, etc. were purchased
from Merck.
2.2. Feed stock characterization
FFAs content in PGT was determined by reported method [29]
and was found to be 8.4 mg KOH/g of PGT. Its saponication value
and molecular weight were determined as 195 and 896.94 respec-
tively [30]. Moisture content in PGT was measured using a digital
moisture analyzer (Mettler Toledo, Model: MJ33) and found to be
0.29 wt.%.
2.3. Experimental setup
The infrared radiation assisted reactor (IRAR) [31] consisted of a
1 L three-necked glass ask provided with an Infrared lamp (50 Hz,
100 W and 220 V) to generate IR radiation (Fig. 1) for the conver-
sion of PGT into fatty acid methyl ester (FAME). The reactor tem-
perature was controlled within the range of 5070 1 C by a
PID temperature controller at the selected set point by regulating
the radiation of the infrared heating lamp. The three-necked ask
was tted with two reux condensers and one mixing impeller
equipped with digital speed indicator and regulator (600 rpm).
2.4. Conversion of PGT to FAME (biodiesel)
The experiments were performed choosing three different lev-
els (Table 1) each for temperature of IRAR (50 < T < 70), methanol
to PGT molar ratio (20:1 < M < 32:1) and sulfuric acid concentra-
tion (40 < C < 60) in order to investigate the parametric effects
[32] on the conversion of FFAs (cFFA ) and triglycerides of PGT under
the inuence of IR radiation. A small packing of silica gel (10 g) was
inserted in the condenser to adsorb the byproduct water in ester-
ication of FFAs to facilitate higher conversion. The reactor tem-
perature in the range from 50 C to 70 C corresponded to
830 R. Chakraborty, H. Sahu / Applied Energy 114 (2014) 827836

Table 1 centrifugal force) to generate an aqueous bottom layer containing

Experimental ranges and levels of the independent variables for RSM study. H2SO4 and upper organic layer. The washing process was repeated
Factors Name Units 1 0 +1 twice for the upper organic layer and this layer was nally distilled
Level Level Level under vacuum to recover remaining methanol and water to obtain
M Methanol to PGT molar 20:1 26:1 32:1 the product FAME layer i.e. biodiesel.
ratio In order to assess the effectiveness of IR radiation in intensify-
T Reactor temperature C 50 60 70 ing FFA conversion elaborately, several experiments were con-
C Catalyst concentration Wt.% 40 50 60
ducted using conventional heater both in presence and in
m M26 T60 C50
6 ; t 10 ; c 10 . absence of silica gel adsorbent under otherwise identical process
conditions. Moreover, with the purpose of evaluating the efcacy
92.5 mm Hg to 233.7 mm Hg water vapor pressure; which implied of the novel IRAR at lower H2SO4 concentrations, additional exper-
presence of sufcient water vapor that eventually passed through iments were conducted at 10, 20, 30, 40 and 50 wt.% of H2SO4 at
and got adsorbed by the silica gel packing kept at the condenser. the derived optimal values of M and T and other combinations of
As such, present study intended to use sulfuric acid as catalyst, C and M at optimal T. The experiments were allowed to continue
placing silica gel in the round bottom ask could lead to the forma- beyond 2.5 h and the time required to achieve the same optimal
tion of a different catalyst (silica-sulfuric acid) besides making the conversion level in each case was recorded.
recovery and reuse of silica gel (adsorbent/desiccator) difcult. In
all experiments, 40 g of PGT and proportionate amount of 2.5. Analyses of produced biodiesel at optimal condition
methanol (according to 20:1 < M < 32:1) were poured into the ask
and stirred for 5 min to make a mixture while being heated to a de- For the determination of wt.% FAME in product biodiesel, HPLC
sired reaction temperature by the IR radiator (IRR). Subsequently, (Perkin Elmer; model 1022) tted with a pump (Perkin Elmer ser-
sulfuric acid was added to the mixture and the stirring was contin- ies 200 LC pump) and RI detector (Perkin Elmer series 200 RI) was
ued up to 2.5 h under total reux. Finally, the mixing was extended used by maintaining a methanol (mobile phase) ow rate of
for an incremental time of 10 min after turning off the IRR to allow 1 mL min1, injection volume of 20 lL, and at a controlled temper-
the reactor contents to properly utilize the energy absorbed during ature of 45 C [33]. The important fuel properties of B100 (pure
the 2.5 h span [21]. In order to remove H2SO4 from the product, the FAME) and B20 (mix of 80% petro-diesel with 20% FAME) have
reactor content was mixed with hot deionized water (70 C) and been tested using Density meter (DMA 4500 M; 0.00005 g/cm3;
stirred at 800 rpm. This mixture was centrifuged (627G relative 0.03 C), Redwood viscometer 1 (0 C to 45 C), Montel Pour Point
tester (1 C), PenskyMartens Flash point tester (ambient to
400 C) and Herzog Cetane ID 510 Analyzer(ASTM D7668).
Table 2
FCCD layout for conversion of FFA present in PGT. 2.6. Modeling of experimental observations through RSM
Run c m t cFFA
Design Expert 8.1 software was used for the statistical assess-
1 1 0 0 91.91 ment. The FCCD layout for three factors viz. M, T, C (Table 2) was
2 0 0 1 93.3
3 0 0 0 90.72
prepared [34]. According to the 15 different combinations of coded
4 1 1 1 92.11 variables, experiments were conducted. Coded process factors viz.
5 0 0 1 87.91 m, t, c were formulated in terms of actual factorial values as pre-
6 1 0 0 90.54 sented in footnote of Table 1.
7 0 1 0 88.49
8 1 1 1 91.32
9 1 1 1 90.04 2.7. Modeling of experimental observations through ANN
10 1 1 1 94.84
11 0 1 0 93.44 MATLAB 7.10.0 (R2010a) was exercised to model the PGT con-
12 1 1 1 84.59 version process employing Articial Neural Network Modeling
13 1 1 1 90.74
14 1 1 1 83.98
(ANNM). An ADFFN was framed which consisted of one input layer
15 1 1 1 96.4 with three input variables, two hidden layers, one output layer
with one output variable (Fig. 2) [35]. The ADFFN was trained with

Fig. 2. Conguration of a 3-2-1 neural network for the prediction of FFA conversion of PGT.
 R. Chakraborty, H. Sahu / Applied Energy 114 (2014) 827836 831

LevenbergMarquardt back-propagation algorithm. In order to Table 3

train the ADFFN, a learning set consisting of an adequate number ANOVA results for cFFA corresponding to RSM modeling (Eq. (5)).

of input and target output variable couples were specied. In the Source Sum of df Mean F value p-Value
current work, ADFFN was used for the prediction of cFFA . In ADFFN squares square prob > F
the X{M}, X{T}, X{C} were input state variables and YfcFFA g was the Model 161.83824 6 26.97304 142.381 <0.0001
output variable. M 2.530089 1 2.53 13.355 0.0065
To determine the ADFFN model, 47 numbers of input and target T 62.35009 1 62.35 329.125 <0.0001
C 94.31041 1 94.31 497.833 <0.0001
output variable pairs were generated by conducting experiments MT 0.09245 1 0.0924 0.488 0.5046
over the ranges of the process independent (input) variables MC 0.1352 1 0.1352 0.7136 0.4228
X{M} (20:132:1), X{T} (5070), X{C} (4060). Three steps were fol- TC 2.4199 1 2.419 12.774 0.0072
lowed in the ANN modeling viz. training, validating and testing Residual 1.5155 8 0.1894
[36]. Accordingly, 50% of the dataset was allotted to training, 30% Cor. 163.3537 14
to validating and 20% to testing .Hyperbolic tangent sigmoid trans- total
fer function (tan sig) and linear transfer function (purelin) were
used in the rst and second layers of ADFFN respectively. Algo-
rithms of tan sig and purelin are as follows: Table 4
Comparison between RSM and ANN models based on statistical parameters.
2
tan sig X 1 1 Statistical parameter RSM ANN
1 e2X
R2 0.99072 0.9966
EF 0.9907223875 0.996694
A purelin X X 2

2.8. Statistical analysis 3.1.2. Optimal process conditions and signicance of IR radiation
Statistical optimization of the experimental results obtained
In order to compare the predictive ability between RSM and according to the FCCD was computed through RSM for maxi-
ANN models, the following statistical formulas were used: mization of cFFA : The parametric values corresponding to max-
imum cFFA i.e. 96.7 were 59.93 wt.% H2SO4 concentration,
N 
X 2 69.97 C IRAR temperature and 31.88:1 methanol/PGT molar
cFFA exp;j  cFFA pre;j ratio. The results (Table 5) indicate that IR radiation could lead
j1
R2 1  N 
3 to higher FFA conversion of PGT as compared to the conven-
X 2
tional heating system [14,18] in remarkably reduced reaction
cFFA exp;j  cFFA av g;j
j1
time of 2.5 h. The signicantly accelerated and enhanced
conversion of PGT due to IR radiation may be briey explained
N 
as follows:
X 2 N 
X 2
cFFAexp;j  cFFAexp;av g  cFFApre;j  cFFAexp;j Infrared radiation represents energy spectra over 0.0011.7 eV
j1 j1 which correspond to the range of energies separating the quan-
EF N 
4 tum states of molecular vibrations. It can penetrate reaction
X 2
cFFAexp;j  cFFAexp;av g mass deeper than visible light and is more intensely absorbed
j1 than microwaves. It interacts with molecules to set them into
vibration causing severe molecular collisions and facilitating fas-
ter transfer of thermal energy into the reactant molecules which
3. Results and discussion results in signicantly enhanced activation of reactive species
compared to conventional heating system. Hence, the PGT con-
3.1. Analyses of experimental results through RSM modeling version to FAME (biodiesel) using IR radiation can be considered
as an efcient, time saving and economical method for biodiesel
3.1.1. Formulation of model equation synthesis.
A RSM model based on FCCD with the coded factors (m, t and c)
of the corresponding input variables viz. M, T, C was constructed to 3.1.3. Effects of individual process parameters on FFA conversion
appraise the effects of process input variables on the process out- In order to evaluate the effects of a single process variable on
put variables i.e. cFFA . The ANNOVA (Table 3) manifested that a the response i.e. cFFA the experiments were conducted at the
2FI model (Eq. (5)) was signicant with p-value less than 0.05 for optimal conditions of the other two variables. Fig. 3ac elucidate
the prediction of cFFA . For other possible models, most of the model that all the process factors have accelerating effects on the cFFA
terms were greater than 0.1000 which are trivial. M, T, C and TC over the ranges of parametric values considered in the present
were found to be signicant model terms (with 95% condence study.
intervals) as their p-values were less than 0.05 while MT, MC were
insignicant terms as their p-values were greater than 0.1000. The 3.1.4. Effects of parametric interactions on FFA conversion
2FI model equation in terms of coded factors that represents the Fig. 4a corresponds to optimal value of M and elucidates that at
relationship between cFFA (response) and process parameters (fac- lowest T i.e. at 50 C an increase in C would render higher cFFA ;
tors) is given by the following equation: which is analogous to the observation at all other reaction temper-
atures up to the maximum reaction temperature i.e. 70 C. It is also
cFFA 90:68867 0:503 m 2:497 t 3:071 c  0:55 tc 5
evident from the same contour plot that over the entire range of C
It is evident from Eq. (5) that, all the process factors had positive used in this study an increase in T over the studied range would
effects on cFFA . More specically, H2SO4 concentration had the most lead to a higher cFFA : In a similar manner it can be observed from
signicant effect followed by IRAR temperature and methanol to Fig. 4b, that at optimal reaction temperature, there would be an
PGT molar ratio on cFFA . increase in FFA conversion with gradual increase in M keeping
832 R. Chakraborty, H. Sahu / Applied Energy 114 (2014) 827836

Table 5
Effects of heat sources and adsorbent (silica gel) on FFA conversion of PGT (%).

Run Parameter cFFA

C M T IRAR (with silica gel) IRAR (without silica gel) Conventional (with silica gel) Conventional (without silica gel)
1 40 20:1 50 83.98 78.28 74.62 69.32
2 50 26:1 60 90.72 85.2 81.7 76.34
3 60 26.1 60 91.91 86.31 83.52 78.16
4 (optimal) 59.93 31.88 69.97 96.7 91.087 88.28 82.96

Fig. 3. Individual parametric effect on conversion of FFA in PGT at constant optimal parametric values of the other two parameters: (a) methanol to PGT molar ratio, (b)
catalyst concentration (wt.%), (c) IRAR temperature (C).

catalyst concentration constant. In a much similar manner, FFA
conversion was found to increase with the increase in catalyst con-
centration at any M over the studied range.
3.2. Analyses of experimental results through ANN modeling
Model sensitivity was evaluated for six different networks with
1, 2, 5, 9, 10, and 12 nodes in the hidden layer. The network with a
two-node hidden layer was found to have the best performance.
During the training period, the developed ANN model had a 3-2-
1 conguration and 696 training cycles t well with a MSE of
1:99561  102 for the test period. The training stopped after 696
iterations because the validation error increased. The abscissa in
Fig. 5 represents the network that is trained for up to 696 epochs
to an error goal of 1  102 . Here, the test curve had not increased
signicantly before the validation curve increased; hence, it does
not appear that any signicant over tting has occurred. Evidently,
the trends of validation and test curves are very similar.
The training, validation and test errors are plotted to test the
progress of training as depicted Fig. 6ac respectively. Close
examination reveals that the test set error and the validation set
error have similar characteristics, and it does not seem that any
 R. Chakraborty, H. Sahu / Applied Energy 114 (2014) 827836 833

Fig. 4. (a) Contour plot of the conversion of FFA in PGT, catalyst concentration vs. IRAR temperature; (b) catalyst concentration vs. methanol to PGT molar ratio.

3.3. Comparison between RSM and ANN modeling

Comparison (Table 4) between RSM and ANN models reveal

that ANN model has marginally higher R2 and EF compared to RSM.
cANN
FFA;pre 0:99813  cFFA; exp 0:18074 6

cRSM
FFA;pre 0:99067  cFFA; exp 0:84839 7

The comparison between the experimental values of FFA con-

version (run no. 2 of Table 2) and those predicted by the ANN mod-
el (Eq. (6)) i.e. 93.3062 and RSM model (Eq. (7)) i.e. 93.2779
indicate comparable predictive ability of these models. This can
be attributed to almost equal values of R2 and EF of ANN and
RSM models which can be ascribed to the low-non-linearity of
the present conversion process.

Fig. 5. Mean square error of training, test, and validation during training progress of
ADFFN. 3.4. Effect of in situ use of Silica gel adsorbent on FFA conversion

signicant overtting has occurred. The network regression plots The effect of application of solid desiccant viz. silica gel on the
demonstrate the correlation between the outputs (predicted) of FFA conversion under the inuence of different heat sources at dif-
the network and the targets (experimental) with R2 of 0.9966 com- ferent temperatures are also presented in Table 5. It is evident that
puted from Eq. (3). under otherwise optimal parametric conditions, a signicant
834 R. Chakraborty, H. Sahu / Applied Energy 114 (2014) 827836
Fig. 6. Predicted and experimental conversion of FFA in PGT (a) training, (b) validating, and (c) testing processes of the ADFFN.
Fig. 7. HPLC chromatograph of the product biodiesel obtained at optimal conditions
depicting the characteristic peaks corresponding to different methyl esters.
enhancement in cFFA could be feasible in presence of the mentioned
adsorbent.
3.5. Computation of methyl esters yield
The main FAMEs in the produced biodiesel obtained through
simultaneously occurring esterication and transesterication
reactions between PGT and methanol under the inuence of IR
heat source, were determined through HPLC chromatogram of
the produced biodiesel as shown in Fig. 7. As can be seen from
Fig. 7, the produced biodiesel from PGT mainly consisted of four
FAMEs. The retention times of 2.96, 3.34, 4.23, 4.68 min
respectively corresponding to methyl linoleate (MeLnO), methyl
palmitate (MeP), methyl oleate (MeO), and methyl stearate (MeS)
were detected for the product biodiesel (i.e. FAME layer) synthe-
sized at optimal conditions. Based on the calibration curves, the
concentrations of the four FAMEs in the produced biodiesel were
calculated. The results indicated that the concentration of methyl
oleate (42.69%) was much higher than other esters viz. methyl pal-
mitate 29.23%, methyl stearate 19.58% and methyl linoleate 7%.
The overall FAME content in the product biodiesel is 98.5%, which
is above the minimum 96.5 FAME content as per ASTM D6751
standard.
3.6. Efcacy of the IRAR at lower amounts of methanol and sulfuric
acid
The main aim of the present research was to assess the efcacy
of novel IR assisted reactor (IRAR) in intensifying conversion of
processed goat tallow (PGT) to biodiesel in a single step reaction.
The experimental results (Table 5) have evidently demonstrated
the superior performance (higher conversion at otherwise identical
conditions) of the IR radiation in comparison with conventional
heating system at various levels of methanol and sulfuric acid con-
centrations. Since, transesterication of the triglycerides is much
slower than esterication of the FFAs present in PGT; therefore,
usage of higher amounts of H2SO4 and methanol could facilitate
the simultaneous reactions rendering enhanced PGT conversion;
the observation corroborates well with the ndings of Boucher
et al. [17].
The reaction time required to achieve the same highest level
(96.7%) of FFA conversion at lower values of sulfuric acid concen-
tration and methanol/PGT molar ratio (at the optimal temperature
of 69.97 1 C) has been exhibited in Fig. 8a. The results indicated
 R. Chakraborty, H. Sahu / Applied Energy 114 (2014) 827836 835

nal level of FFA conversion could be achieved even with a modest

10 wt.% H2SO4 concentration in nearly 4 h reaction time. It may be
noted that much higher H2SO4 concentration and methanol/oil mo-
lar ratio were required [15,16] for conventionally heated reactor to
obtain biodiesel in 4 h reaction time. Clearly, the novel IRAR could
be successfully operated even at low amount of H2SO4 to render
the desired yield of biodiesel making the process economically
and technically more viable compared to conventionally heated
reactor system.

3.7. Fuel properties of synthesized biodiesel and blended biodiesel

The important fuel properties of B100 (pure FAME obtained at

optimal conditions) and B20 (mix of 80% petro-diesel with 20%
FAME) have been tested as per ASTM standard methods and the re-
sults are shown in (Table 6). The results conrmed a satisfactory
fuel quality of the blended and pure product.

4. Conclusions

This exploratory work presents an efcient process for en-

hanced and accelerated synthesis of fuel grade biodiesel from
waste goat tallow using an infrared radiation assisted reactor
(IRAR). A substantial reduction in reaction time and superior FFA
conversion and FAME yield could be achieved in comparison with
conventionally heated batch reactor. Present study also explores
the usefulness of suitable adsorbent incorporated in the IRAR in
rendering enhanced yield of FAME through improved FFA conver-
sion. The RSM optimization method could effectively determine
the optimal parametric values corresponding to maximum FFA
conversion while attaining a commendable high FAME yield con-
forming to ASTM biodiesel specications. Both RSM and ANN mod-
els demonstrated high predictive ability. Thus, an intensication
method for procient waste goat tallow conversion into green fuel
could be discovered through optimal application of infrared radia-
tion in presence of water adsorbent.

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