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Process Safety and Environmental Protection 1 0 7 ( 2 0 1 7 ) 373387

Contents lists available at ScienceDirect

Process Safety and Environmental Protection

journal homepage: www.elsevier.com/locate/psep

Simultaneous extraction and transesterification of


castor seeds for biodiesel production: Assessment
of biodegradability

Swaroopa Rani Dasari, Vaibhav V. Goud


Department of Chemical Engineering, Indian Institute of Technology, Guwahati, Assam 781039, India

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

Article history: The objective of this study was to investigate single step trans-esterification with integra-
Received 7 October 2016 tion of Soxhlet order to find the effect of various reaction variables on the conversion of
Received in revised form 24 castor oil methyl ester (COME) via conventional optimization method. Based on the results
February 2017 obtained from the conventional method, a three-level-three factorial central composite
Accepted 1 March 2017 design (CCD) was employed to study the effect of three significant variables on COME con-
Available online 9 March 2017 version. The optimum conditions to maximise the methyl ester conversion inferred from
the RSM (Response Surface Methodology) were: reaction time6.3 h, oil/methanol molar
Keywords: ratio1:400, catalyst concentration1.5 wt%, seed weight20 g, stirring speed1000 rpm,
Free fatty acid and temperature65 C. At this condition methyl ester conversion could reach as high as
Reactive extraction 95%. The co-solvent (hexane) showed insignificant effect on methyl esters conversion. The
Castor oil methyl ester fuel properties of produced COME conform to the ASTM standards. Biodegradability of pre-
KOH pared COME tested using bio-kinetic model was found to be 51% in 28 days. The lower
Response surface methodology biodegradability attributed to the higher COME viscosity.
Biodegradability 2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction bearing materials than refined oil eliminates separate extraction and oil
refining steps (Zakaria and Harvey, 2012). Reactive extraction can be car-
The uncertainties for security of supply, increased greenhouse gas ried in two ways i.e. direct contact between the reaction reagents and oil
emissions, irresponsible onshore/offshore drilling practices, political bearing material and the other way without direct contact between the
instabilities within the oil producing regimes, rising concerns over reaction reagents by integrating the Soxhlet apparatus in the process
the continual availability of fossil fuels, fluctuating oil markets and called integrated system. The direct contact method requires filtration
the politics of oil trading have resulted in increased interest in veg- to separate the solid material from the reagents, whereas the reactive
etable oil-based diesel fuels (Samuel and Dairo, 2012). Among the extraction by integration of Soxhlet does not require filtration. Various
vegetable oil-based diesel fuels, biodiesel is a renewable fuel produced sources such as inedible oil seeds (jatropha, karanja), waste cooking oil,
by trans-esterification of vegetable oils using alcohol and a catalyst. The algae, animal fat and sewage sludge can be used as direct feed stock to
transesterification reaction can be carried out by using acid or alkali or produce methyl ester (Zakaria and Harvey, 2012). Very few seeds such as
enzyme as the catalyst (El-Enin et al., 2013).The conventional process jatropha seed with KF/ Al2 O3 catalyst (Lian et al., 2012), rapeseed, lin-
of producing biodiesel involves oil extraction, purification (degumming, seed and calendula seed with lipase catalyst (Klaas and Warwel, 2001)
deacidification, dewaxing, dephosphorization, dehydration) and trans- were investigated by an integrated approach. Among non-edible oil
esterification. The cost of oil contributed over 70% of the total cost of crops, castor is cultivated in most of the tropical and sub-tropical zones.
FAME product when refined oil was used (Zeng et al., 2008). Therefore, India being the largest producer of the castor contributes to around 65%
reactive extraction or simultaneous extraction and transesterification of the worlds total production. Castor seeds contain about 4655 wt%
is an alternate way to produce methyl ester directly from oil bearing of oil. The oil consists of approximately 8090% ricinoleic acid, 36%
materials in a single step where alcohol acting as an extracting solvent linoleic acid, 24% oleic acid and 15% saturated fatty acids (Pradhan
and transesterification reagent (Lian et al., 2012). Thus, the use of oil et al., 2012).
Even though biodiesel has several advantages, biodegradability is
the strongest point in the case, for its industrial use. Biodiesel is easily


Corresponding author.
E-mail address: vvgoud@iitg.ac.in (V.V. Goud).
http://dx.doi.org/10.1016/j.psep.2017.03.002
0957-5820/ 2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
374 Process Safety and Environmental Protection 1 0 7 ( 2 0 1 7 ) 373387

biodegradable because it contains esters and compounds that exist nat-


urally in the environment (Silva et al., 2012). Biodegradability means the
breakdown of a complex and probably poisonous substance in to simple
and regular forms in which the elements carbon, hydrogen and oxy-
gen exist. Management regulators and industries are always concern
about the providence of chemicals and waste products when discarded
into the environment, because toxic substances in the environment
eventually affect the ecosystem and humans adversely (Aluyor et al.,
2009). Extent of biodegradability of a substance can be determined by
measuring CO2 release as per EPA (Environmental Protection Agency)
protocol (Silva et al., 2012). Biodegradability of fuels can be evaluated
by methods using microorganisms (Junior et al., 2009) or without using
micro-organisms i.e. bio-kinetic model (Luna et al., 2011). However, very
limited literature is available on the biodegradability of biodiesel by
using bio-kinetic model.
Similarly, there are few reports in the literature on optimization of
reactive extraction of castor seeds by non-integrated approach (direct
contact between the seed material and reagents) using KOH as cata-
lyst (Madankar et al., 2013; Pradhan et al., 2012). But, to the best of our
knowledge no such comprehensive report is available in literature on
reactive extraction of castor seeds by an integrated approach. There-
fore, the present study is aimed to optimize the integrated reactive
extraction of castor seeds using RSM. Further, biodegradability of COME
was also tested by using bio-kinetic model.

2. Materials and methods


Fig. 1 Integrated Soxhlet apparatus used for reactive
2.1. Materials and reagents
extraction.

Castor seeds used in this study were purchased from local


Table 1 Independent variables and levels for response
market in Anantapur district, Andhra Pradesh, India. Manu-
surface design.
ally cleaned castor seeds were pre-treated (heated at 50 C for
Independent Variables Coded Levels
24 h in the oven) and used in all the experiments. Reagents
like analytical grade methanol, NaOH, KOH and other reagents Symbol Unit 1 0 +1
used in this study were procured from Merck and were used
Reaction time A h 6 9 12
without purification.
Oil to methanol molar ratio B 400 450 500
Catalyst concentration C wt% 1 1.5 2
2.2. Determination of oil content and acid value

The significant factors such as oil content and acid value of the as zero reaction time and continued further for desired time
seeds were determined before starting the reactive extractive duration (615 h). Other reaction variables such as, seed quan-
extraction experiments. Oil content of seeds was determined tity (1525 g), mixing speed (6001200 rpm) and co-solvent
by two different methods (i.e Soxhlet and vial method) and hexane (515 vol% of alcohol) were selected to optimise and
compared for their resultant oil contents. The oil content understand the effect of these variables on reactive extraction
(Soxhlet method) and acid value of the extracted oil were of castor seeds. At the end of reaction, the excess methanol
determined according to the procedure reported elsewhere was removed from the product using a rotary evaporator.
(Dasari et al., 2016; Dasari and Goud, 2014). The complete evaporation of methanol leads to the forma-
tion of two liquid layers. The upper yellow layer belongs to the
2.3. Preliminary studies for reactive extraction biodiesel, while the bottom dark brown layer represents the
glycerol. The layers were separated using a separating funnel.
Preliminary studies for reactive extraction of castor seeds were The upper biodiesel layer was washed with warm millipore
carried out in a 500 ml round bottom flask equipped with a water (5060 C) to remove catalyst and residual methanol.
Soxhlet apparatus, reflux system, magnetic stirrer and heater The moisture was removed from methyl ester by drying at
(Fig. 1). The round bottom flask was merged in an oil bath 60 C under vacuum rotary evaporator. The obtained product
placed on the plate of magnetic stirrer. The known amount of weight was recorded for biodiesel yield calculation (Kartika
KOH (0.52 wt% of oil content) was added to the known volume et al., 2013).
of methanol (oil/methanol molar ratio: 1:4001:550) in a round
bottom flask in order to maintain the catalytic activity and to 2.4. Experimental design based on RSM
prevent moisture absorbance. The alkalialcohol solution was
heated to a boiling temperature of methanol (65 C). A three-level, three-factor central composite design (CCD) was
During extraction, a chamber containing pre-treated cas- applied for carrying out the optimization studies to maxi-
tor seeds (20 g) macerated using mixer grinder were placed mize the COME conversion. The factorial levels were fixed
between the drops of re-condensed solvent falling from the based on the results of several preliminary experiments per-
condenser and the boiling solvent solution. When the distilled, formed using conventional optimization study. The coded
re-condensed solvent runs through the castor seed material, and uncoded levels of the independent variables are given in
washing out the oil falls in the reaction flask was considered Table 1.
Process Safety and Environmental Protection 1 0 7 ( 2 0 1 7 ) 373387 375

The following experimental parameters (or independent ments of viscosities have been done in triplicate at the shear
variables) have been chosen for optimization: reaction time rates of 50, 100, 150 and the average values are reported.
(A), oil to methanol molar ratio (B) and catalyst concentra-
tion (C). The reactions were carried out at varied reaction time 2.6.2. FTIR analysis
(612 h), oil to methanol molar ratio (1:4001:500) and cata- An infrared spectrum of castor oil and its methyl esters (with-
lyst concentration (12 wt% of oil content in seeds). A 23 full out co-solvent and with co-solvent) was recorded on FTIR
factorial CCD for three independent variables comprises of 20 spectroscopy (Make Shimandzu IR Affinity1 Model) using KBr
sets of experiments. During the optimization study, six axial pellets. A sample volume of 0.1 ml was uniformly spread
experiments and eight factorial experiments carried out with throughout the crystal surface to obtain the spectra. Each
six extra replications at the centre of design were used for the spectrum was collected at 2030 scans performed in the wave
estimation of pure error. In each set, experiments have been number range 4000500 cm1 . The different functional groups
done in triplicate (3 runs) so as to assess the reproducibility of present in the castor oil and its methyl ester were identified
results. The progress of the reaction was monitored by with- and compared.
drawing the aliquots of the reaction mixtures at regular time
of intervals. 2.6.3. Thermal stability analysis
Thermo gravimetric analysis (TGA) experiments were car-
2.5. Statistical analysis ried out with a TGA system (model-TG/SDTA851e, METTLER
TOLEDO). The sample amount of 6 0.5 mg was loaded into
Design-expert software v.8.0.6 trial version was used for the an aluminium pan and sample amount was kept almost same
regression and graphical analysis of the data. The response throughout the study. An aluminium cap was placed on the
variable, i.e., FAME conversion, was fitted with a full quadratic sample crucible to avoid any vaporization of sample prior
model (given in Eq. (1)) in order to correlate it to the experimen- to starting the temperature ramp. The thermal analysis was
tal parameters or independent variables. The experimental conducted at a heating rate of 10 C/min from ambient temper-
data obtained by the above procedure was analysed by the ature to 700 C in the nitrogen atmosphere (inert atmosphere).
response surface regression using the following second-order Nitrogen gas was purged at a flow rate of 40 ml/min during the
polynomial: analysis. TG curves as well as its derivative curves (DTG) were
used to analyse onset temperature of methyl esters.

n

n

n 
n

Y = 0 + ixi + iixi2 + ijxixj (1) 2.6.4. Oxidation stability measurement


i=1 i=1 i=1 j>1 Oxidation stability of COME was quantified by DSC (DSC 1 star
e-system, Mettler Toledo). A sample of less than 10 mg was
where Y is the response (COME conversion), i and j are the placed in an aluminium pan sealed with a pinhole lid and oxi-
linear and quadratic coefficients, respectively, 0 is the regres- dized with air (100 ml/min) in the module with a heating rate
sion co-efficient and k is the number of factors studied and of 5 C/min from ambient temperature to 350 C. Nitrogen gas
optimized in the experiment. Statistical analysis of the model (40 ml/min) was used as purging gas. A computer-generated
was carried out to evaluate the ANOVA (Analysis of Variance). plot of heat flow vs. temperature was used to determine graph-
Confirmatory experiments were also carried out to validate ically the oxidation onset temperature (OOT).
the equation. The goodness and best fit of the model were
evaluated by regression coefficient R2 . Response surface and 2.6.5. Pour point by DSC
counter plots were obtained using the fitted quadratic polyno- Pour point of the COME samples was estimated using differen-
mial equation obtained from regression analysis. tial scanning calorimetry (DSC) technique. DSC experiments
were performed on DSC instrument (model 186 DSC1, stare
2.6. Estimation of physicochemical properties of system, Mettler Toledo), with computer based controller. Typ-
methyl esters ically <10 mg sample was weighed in an open aluminium pan
and placed in the DSC module with a similar empty pan as
The gross conversion of triglycerides and yield of methyl esters reference. The procedure involved heating of the sample from
produced using KOH as catalyst with and without hexane as room temperature to 50 C and then held under an isothermal
co-solvent were estimated and compared. The fuel properties condition for 10 min to allow the dissolution and homoge-
of COME such as density, kinematic viscosity, specific gravity, nization of the waxy material present in the oil. The system
refractive index, acid value, iodine value and saponification was cooled from 50 C to 30 C at a steady cooling rate of
value under optimum condition were determined according 5 C/min using refrigeration system (Huber, TC-45, R290 refrig-
to standard methods reported elsewhere (Dasari and Goud, erant USA). In the heating step, the sample was heated from
2013). Flash point and fire point of methyl ester samples were 30 to 50 C at a heating rate of 5 C/min. Nitrogen (40 ml/min)
measured according to the ASTM D92 method. The procedures was used as purge gas. Pour points of methyl ester samples
for 1 HNMR, TGA and DSC (pour point and oxidative stability) were obtained from the plots of heat flow (mw) versus tem-
were followed according to our previous paper (Dasari and perature ( C) for each experiment.
Goud, 2014). The analytical methods used for COME charac-
terisation have been described in our earlier paper; however, 1
2.6.6. HNMR analysis
we reproduce it here for the convenience of the reader. 1H NMR (Nuclear Magnetic Resonance Spectrometer) analy-
sis of castor oil and its methyl ester samples were performed
2.6.1. Viscosity on 600 MHz NMR spectrometer (Oxford, AS400, China) using a
HAAKE rheometer (Rheostress RS1, Thermo Electron Corpo- 5 mm broad band inverse probe head equipped with shielded
ration) was employed to determine viscosities of castor oil z-gradient accessories. Each oil sample, roughly weighing
methyl ester (COME) samples at 25 and 40 C. The measure- 0.2 g, was dissolved in 400 L of deuterated chloroform CDCl3 .
376 Process Safety and Environmental Protection 1 0 7 ( 2 0 1 7 ) 373387

Table 2 COME yields and conversions obtained for the list of preliminary experiments conducted with respective
parameters.
Catalyst
Co-
Oil to concentrati COME
Seed Mixing solvent
Reaction methano on (wt.% COME Conver
quantity speed (vol. %
time (h) l molar of oil Yield (%) sion
(g) (rpm) of
ratio content of (%)
alcohol)
seed)
6 1:450 1 20 1000 - 65.15 89.28
9 1:450 1 20 1000 - 67.34 91.8
12 1:450 1 20 1000 - 70.08 87.13
15 1:450 1 20 1000 - 71.15 76.25

9 1:400 1 20 1000 - 64.13 84.75


9 1:450 1 20 1000 - 67.34 91.8
9 1:500 1 20 1000 - 68.13 82.64
9 1:550 1 20 1000 - 70.08 80.25

9 1:450 0.5 20 1000 - 61.82 91.37


9 1:450 1 20 1000 - 65.15 91.8
9 1:450 1.5 20 1000 - 71.36 95.07
9 1:450 2 20 1000 - 72.21 92.76

9 1:450 1.5 15 1000 - 65.61 94.54


9 1:450 1.5 20 1000 - 71.36 95.07
9 1:450 1.5 25 1000 - 74.22 95.36

9 1:450 1.5 20 600 - 65.68 94.7


9 1:450 1.5 20 1000 - 71.36 95.07
9 1:450 1.5 20 1200 - 72.42 93.73

9 1:450 1.5 10 600 5 70.66 95.03


9 1:450 1.5 15 600 10 72.44 94.37
9 1:450 1.5 20 600 15 74.57 93.39

Note: Yellow colour boxes indicate variables range of interest. Orange boxes indicate highest conversion of COME. Reaction temperature was
maintained at boiling point of alcohol (65 C).

The deuterated chloroform chemical shift peak at 7.26 ppm value of castor oil extracted with methanol was found to be
was taken as an internal reference. The conversion of castor oil 0.925 mg KOH/g. The half of the acid value (0.462 mg KOH/g)
was calculated directly from the integrated areas of relevant was calculated as free fatty acid (FFA) content. In general,
peaks of methylene and methyl ester protons and followed the FFA content of oil should be <3% for alkali transesterifica-
according to our previous paper (Dasari et al., 2016). tion (Kartika et al., 2013). Low FFA content in the oil suggests
that oil is suitable for biodiesel production in single step alkali
2.7. Biodegradation evaluation of COME catalysed transesterification.

Bio kinetic model, ASTM method D7373-12 was used to predict


the biodegradability of COME without using micro-organisms. 3.2. Preliminary studies in reactive extraction
This method was used to evaluate the effective composition
of biodegradation (ECB) products and predicts the cumulative Protocol of reactive extraction was designed on the basis of
biodegradation of prepared esters. The biodegradation test results published by Madankar et al. (2013). Single parame-
was carried out for COME and the ECB was calculated as per ter optimisation technique was followed, in order to optimize
the standard method. The biodegradation tests were repeated the reactive extraction process. Madankar et al. (2013) car-
twice and average values were recorded. ried out their study on reactive extraction of castor seeds by
non-integrated approach using KOH as catalyst. Although the
3. Results and discussion paper has experimental rigor using non-integrated approach,
no attempt has been made by author to explore the reac-
3.1. Oil content and acid value of castor seed tive extraction by integrated approach. The current study
investigates reactive extraction of castor seeds by integrated
Oil content in the seeds and acid value of oil are significant approach using KOH as catalyst. Castor seed was selected
parameters for reactive extraction particularly when alkali is as a feedstock for the study because of its several advan-
used as the catalyst. For that reason, oil content in the seeds tages such as cheap, non-edible, and resistant to grow in
was estimated by two different methods (i.e. Soxhlet and Vial drought conditions and cultivated mainly in India (Madankar
method). The oil content estimated using vial method for a et al., 2013). Most of the literature published in the area of
single castor seed was found to be 56.2% (0.112 g oil/0.199 g reactive extraction employs higher oil/alcohol molar ratios
single seed) and was comparable to the oil yield of 55.2% to achieve higher conversions. Therefore, higher molar ratios
(11.04 g oil/20 g seed) obtained by Soxhlet method reported (1:4001:550 oil/methanol) are used in the present study. Rela-
elsewhere (Dasari et al., 2016; Dasari and Goud, 2014). The acid tively acid catalysed transesterification is slower than alkali
Process Safety and Environmental Protection 1 0 7 ( 2 0 1 7 ) 373387 377

Table 3 Experimental design matrix by CCD technique Table 4 ANOVA for response surface quadratic model.
for reactive extraction.
Source Sum of df Mean F value p-Value
Run no A: time (h) B: oil to C: catalyst COME squares square
methanol concentration conversion
Model 310.43 9 34.49 28.15 <0.0001
molar ratio (wt%) (%)
ATime 0.45 1 0.45 0.37 0.5562
1 9 450 2.34 85.94 BMolar ratio 0.59 1 0.59 0.48 0.5018
2 9 450 1.5 95.07 CCatalyst conc. 24.48 1 24.48 19.99 0.0012
3 9 450 1.5 95.07 AB 2.11 1 2.11 1.72 0.2185
4 3.95 450 1.5 95.79 AC 36.67 1 36.67 29.94 0.0003
5 6 500 1 90.98 BC 8.22 1 8.22 6.71 0.0269
6 9 450 0.65 81.22 A2 3.58 1 3.58 2.93 0.1177
7 9 365.9 1.5 96.04 B2 5.75 1 5.75 4.69 0.0555
8 12 400 1 88.92 C2 213.76 1 213.76 174.51 <0.0001
9 9 534 1.5 96.48 Residual 12.24 10 1.22
10 9 450 1.5 95.07
11 14 450 1.5 95.98 C.V: 1.18%, R2 model : 0.96, R2 Adj : 0.927, predicted R2 model : 0.9.
12 12 500 2 95.92
13 12 500 1 88.94
14 9 450 1.5 95.07 The use of an adjusted coefficient of determination (adj-R2 )
15 9 450 1.5 95.07
is to estimate the model accuracy fitness as well as to cor-
16 9 450 1.5 95.07
rect the coefficient of determination value for the sample size
17 6 400 1 96.85
18 6 500 2 93.23 and for the number of terms in the model. The high value of
19 12 400 2 95.68 coefficient of determination (adj-R2 : 0.92) represents the sig-
20 6 400 2 91.21 nificance of the model. The value of coefficient of variation
(CV) was low as (1.18%), there by indicates the reliability of
the fitted model (experimental and predicted values) results
(Goyal et al., 2012). Moreover, p-values are used to check the
as catalyst; hence reactions were performed with alkali as
significance of the corresponding coefficient.
catalyst.
The smaller the p-values are, the bigger the significance of
The influence of six parameters such as reaction time, oil
the corresponding coefficient. In the present study, p-value
to methanol molar ratio, catalyst concentration, seed quan-
of the model (found by ANOVA) was 0.001 which indicates
tity, mixing speed and volume percentage of co-solvent on the
that the model terms are significant. In this case, A (reaction
reactive extraction of castor seeds were studied and the results
time), B (oil to methanol molar ratio), C (catalyst concentra-
of COME yields and conversions are presented in Table 2. From
tion), interaction effects of AC (reaction time with catalyst
the table, it can be observed that among the studied param-
concentration), BC (oil to methanol molar ratio) and quadratic
eters, reaction time, oil to methanol molar ratio and catalyst
effects of A2 (time), B2 (oil to methanol molar ratio), C2 (cata-
concentration showed significant effect on the process com-
lyst concentration) have shown significant effect on the COME
pared to other variables such as seed quantity, mixing speed
conversion in the range of these parameters considered in the
and co-solvent percentage. The optimization parameters for
experiments.The regression equation for the determination of
the reactive extraction process (integrated) were time 9 h, 1:450
predicted values of output parameter in terms of coded factors
molar ratio, 1.5 wt% catalyst concentration, 20 g seed quantity,
as follows (i.e., COME in this study):
1000 rpm and 5 vol% of co-solvent. At this optimum condition
maximum COME conversion was found to be 95%. Results of
COME conversion (%) = 95.03 - 0.18A - 0.2B + 1.33C
this preliminary study were used as a basis to further optimize
the process by RSM design technique. +0.5AB + 2.14AC + 1BC+ 0.49A2 + 0.63B2 3.8C2 (2)

3.3. Model fitting


The graph between the predicted versus actual COME con-
According to the central composite design (CCD), total twenty version (%) and the plot of perturbation are shown in Fig. 2(a)
experiments were performed in order to find out the opti- and (b) indicates that the predicted values are quite close to the
mum combination and study the effect of process parameters experimental values and thereby confirming the persistence
on FAME content using the reactive extraction process, and of the model developed for establishing a correlation between
the results are given in Table 3. The regression mathematical the process variables and the COME conversion.
model was tested for statistical significance using the analy-
sis of variance (ANOVA) and results are presented in Table 4. 3.4. Interactions between the process variables
The ANOVA of the quadratic regression model has demon-
strated that the model is significant with a low probability The response surface and contour plots indicates the inter-
value (p < 0.0001). The coefficient of determination is another active effect of any two process variables on the COME
(R2 ) measure of significance of regression i.e. R2 = 96%, which conversion of reactive extraction are shown in Figs. 35.
indicated that more than 96% of experimental data were com- The contour plots essentially are graphical representation
patible and only 4.0% of the total variation was not explained of regression Eq. (2). The plots represent interaction effects
by the model. A high value of predicted R2 (0.9) is an indi- between the independent and dependent variables for differ-
cation of accuracy of fitted model. The more the value of R2 ent fixed parameters as shown in Figs. 35. The interaction
approaches 1, the better the model which fits an experimental of reaction time and oil/methanol molar ratio on COME con-
data. version at 1.5 wt% catalyst concentration, 1000 rpm and 65 C
378 Process Safety and Environmental Protection 1 0 7 ( 2 0 1 7 ) 373387

Fig. 2 (a) Predicted versus actual COME conversion (%) values (b) Perturbation.

is shown in Fig. 3(a) and (b). Increase in the molar ratio and Fig. 4(a) and (b) establishes the interaction of reaction time
reaction time shown insignificant effect on COME conversion. and catalyst concentration on the COME conversion at 400
The optimum conversion of COME was obtained by using oil/methanol molar ratio, 1000 rpm and 65 C and indicates
oil/methanol ratio of 1:400 at 6.3 h. that the COME conversion increased with the increasing cata-
This shows that reactive extraction can reduce the time lyst concentration up to 1.5 wt% and then decreased. Whereas,
required for biodiesel production for oil bearing material increasing of reaction time results in decreased COME conver-
compared to the conventional method, and thus eventually sion. This may be due to the formation of soap with increasing
decrease the price of biodiesel production (Shuit et al., 2010). reaction time and simultaneous increase in the catalyst con-
Process Safety and Environmental Protection 1 0 7 ( 2 0 1 7 ) 373387 379

Fig. 3 Effect of reaction time and oil/methanol molar ratio on COME conversion at 1.5 wt% catalyst and 65 C temperature:
(a) Response surface plot; (b) Contour plot.

centration (Dasari et al., 2016). The combined interaction effect on COME conversion and these results are analogous
effect of catalyst concentration and time shows the saddle to the result reported by Goyal et al. (2012), whereas in case
trend (raised at front and rear). However, an optimum conver- of catalyst concentration opposite trend was observed. The
sion was obtained at 6.3 h with 1.5 wt% catalyst concentration. conversion of COME substantially increased up to a certain
Fig. 5(a) and (b) shows the interaction effect of oil/methanol level, beyond this point further increase in the concentration
molar ratio and catalyst concentration on the COME conver- of the catalyst results in the formation of soap and gel which
sion at 6 h, 1000 rpm and 65 C. From the plot, it could be seen significantly reduces the COME conversion. This is because,
that oil/methanol molar ratio practically had insignificant side reaction called saponification which occurs during reac-
380 Process Safety and Environmental Protection 1 0 7 ( 2 0 1 7 ) 373387

Fig. 4 Effect of reaction time and catalyst concentration on COME conversion at 1:400 molar ratio and 65 C temperature: (a)
Response surface plot; (b) Contour plot.

tive extraction in the presence of higher catalyst concentration 3.5. Optimization of the process parameters
(Kasim and Harvey, 2011).
The combined effect of oil/methanol molar ratio and cata- After regression analysis, optimization study was performed
lyst concentration on the COME conversion was found saddle based on the of desirability function to determine the opti-
trend which is similar to that of interaction effect of reaction mal synthesis conditions for maximum COME conversion.
time and catalyst concentration. The optimum conversion The optimum conditions to maximize COME conversion cal-
was found at 1:400 oil/methanol molar ratio and 1.5 wt% cat- culated from Eq. (2) were: reaction time equal to 6.3 h,
alyst concentration. 1:400 oil/methanol molar ratio, 1.5 wt% catalyst concentration.
Process Safety and Environmental Protection 1 0 7 ( 2 0 1 7 ) 373387 381

Fig. 5 Effect of oil/methanol molar ratio and catalyst concentration on COME conversion at 6 h time and 65 C temperature:
(a) Response surface; (b) Contour plot.

These values have been selected from the optimum solutions dicted, and experimental value confirmed that the formulated
proposed from the multiple solutions given by RSM optimiza- model believed to be precise and authentic.
tion tool. The anticipated maximum COME conversion from
the model at this condition is 96%. The model verification was 3.6. Characterization of COME
carried out by performing the experiments in triplicate at iden-
tical condition and the maximum COME conversion of 95% The physicochemical properties for COME synthesized at
was obtained. The good agreement between the model pre- optimal condition using KOH as a catalyst (with and with-
382 Process Safety and Environmental Protection 1 0 7 ( 2 0 1 7 ) 373387

Fig. 6 FTIR spectra of castor oil and its methyl esters using KOH (with co-solvent and without co-solvent).

Table 5 Physico-chemical properties of COME.


Properties KOH catalyst Biodiesel standards Standard method

Without co-solvent With co-solvent

COME yield (%) 74.44 74.57


COME conversion (%) 95 95
Density (kg/m3 ) 886 892 860900 EN14214-2008
Specific gravity 0.896 0.921 0.8600.900 ASTM D 4052
Acid value (mg KOH/g) 0.64 0.7 0.8max. ASTM D 6751-09
FFA(mg KOH/g) 0.32 0.35
Refractive index at 30 C 1.459 1.459
Kinematic viscosity (cSt) @40 C 10.39 10.72 1.96 ASTM D 6751-09
Kinematic viscosity (cSt) @25 C 18.94 19.36
Iodine value (g I2 /100 g oil) 83.24 82.94 120 EN14214-2008
Saponification value (mg KOH/g) 103.2 102
Pour point ( C) 19 19 15 ASTM D97
Oxidative stability ( C) 209 182
Thermal stability ( C) 240 222
Flash point ( C) 202 130170 ASTM D92
Fire point ( C) 212
Calorific value (MJ/kg) 39.43 34.43 37.27

out co-solvent) were determined as per ASTM standards and esters (Madankar et al., 2013). But, the higher viscosity of
reported in Table 5. Conversions of COME obtained also shown biodiesel leads to poor atomization of the fuel and result in
in the same table. From the table, it can be seen that highest incomplete combustion including formation of deposits in
COME conversion of 95% was obtained at optimum condition the fuel injector of the diesel engine. Moreover, being more
with KOH as catalyst. The effect of co-solvent (hexane) has not viscous hardware modifications are essential before using
shown any significant effect on the COME conversion. Density in existing engine (Deka and Basumatary, 2011; Koc et al.,
of castor oil methyl ester was found to be 886 (without co- 2011). Acid value of the COME sample was within the range
solvent) and 892 kg/m3 (with co-solvent) which are within the of standard limits (0.8 mg KOH/g max) and signifying that
acceptable range of ASTM standard specification. The density there will not be any problem like deterioration or pump
values are also used in determination of COME viscosity. The plugging during usage (Porwal et al., 2012). The iodine value
kinematic viscosity of methyl ester samples were found to be of biodiesel implies the un-saturation content. Iodine value
10.39 cSt (without co-solvent) and 10.72 cSt (with co-solvent), can be directly correlated with viscosity, cetane number and
respectively. cold flow properties (Schinas et al., 2009). The iodine value
The kinematic viscosity of methyl ester obtained is well of COME found to be 83.24 and 82.94 gI2 /100 g oil, which are
above the standard limit, but agrees well with that of liter- far lower than the maximum limit, prescribed in EN 14214
ature (14.85 cSt) (Encinar et al., 2010). The higher viscosity standards.The saponification values of COME were found to
of COME may be due to the presence of hydroxyl group on be 103.2 and 102 mg KOH/g, respectively. The flash and fire
its fatty acids chain. This makes COME more advantageous points of COME (without co-solvent) were found to be 202 C
for preparing lubricant over other vegetable oil based methyl and 212 C which are higher than fossil diesel. A higher flash
Process Safety and Environmental Protection 1 0 7 ( 2 0 1 7 ) 373387 383

Fig. 7 TGA and DTG curves of COME using KOH (a) with co-solvent, (b) without co-solvent under inert gas atmosphere.

point guarantees safety during usage and storage (Conceicao The bands of a, b, signify OH group of ricinoleic acid
et al., 2007). The estimated calorific values of methyl esters (3450 cm1 ), C C (3008 cm1 ) and C O (1742 cm1 ), corre-
were close to the biodiesel standards. The lower calorific value spondingly. The bands c and d corresponds to CH-stretching at
of COME than diesel may be due to the oxygen content in 2928 cm1 and 2855 cm1 respectively. From the figure, it can
biodiesel. The presence of oxygen in biodiesel helps for com- be observed that the bands a, b, c, d and e are general in both
plete combustion of fuel in the diesel engine (Ramadhas et al., castor oil and methyl ester spectra. Whereas, the band peak
2005). of f at 1438 cm1 (O-CH3 group of methyl ester) indicates
the methyl ester spectrum which was absent in the castor oil
sample. (Islam et al., 2014) reported that castor methyl ester
3.6.1. FTIR analysis
contains oxygen functional group such as C-O and C O at 400
The FTIR spectra of castor oil and its methyl esters with KOH
to 1500 cm1 . But, the conventional diesel does not have oxy-
(with and without co-solvent) are compared and shown in
gen functional group. The fuel with oxygen group promotes
Fig. 6.
384 Process Safety and Environmental Protection 1 0 7 ( 2 0 1 7 ) 373387

Fig. 8 Oxidative stability of COME using KOH (a) with co-solvent (b) without co-solvent under oxygen environment.

complete combustion with a lesser amount of black smoke gle step decomposition was noticed in DTG curves of both the
(Islam et al., 2014). COME samples and was in agreement with the reported data
(Borugadda and Goud, 2014). Thermal onset temperature of
3.6.2. Thermal stability COME samples were found to be 240 C (without co-solvent)
Thermal stability of COME samples (with co-solvent and and 222 C (with co-solvent), respectively. The reason behind
without co-solvent) was determined by thermo gravimetric variation in the onset temperatures might be owing to differ-
analysis (TGA) machine under nitrogen environment. ence in the viscosity or either moisture content of the samples.
Fig. 7 describes TG and DTG thermo gram of both the The samples were stable up to respective onset temperatures,
samples. From the figure it can be seen that both the beyond that sample started to decompose which was evident
COME samples followed similar decomposition pattern. Sin- from the weight loss data. The TG curves of samples showed
Process Safety and Environmental Protection 1 0 7 ( 2 0 1 7 ) 373387 385

Fig. 9 Pour of COME (by DSC) using KOH catalyst with co-solvent and without co-solvent.

mass loss in three steps. In the first step, 10% weight loss values indicate more stability of COME towards oxidation. The
was observed for COME-without co-solvent at 260 C,whereas higher oxidative stability of COME samples could be attributed
in case of COME-with co-solvent, it was at 226 C which is to higher mono-unsaturation content (i.e. ricinoleic acid, 84%)
due to decomposition of mono, poly-unsaturated fatty acids in its composition. An improvement of oxidative stability can
(oleic, ricinoleic, linoleic and linolenic) (Borugadda and Goud, be done by using vegetable oil based antioxidant additives
2014). In the second step, 50% weight loss was decomposed at or synthetic antioxidants available in the market (Borugadda
304 C (without co-solvent) and 271 C (with co-solvent) which and Goud, 2014). This evaluation reveals that it is possible to
was attributed to the breakdown of saturated fatty acids (i.e. estimate the oxidative stability of the samples quickly using
palmitic and stearic). Approximately, 90% of weight loss was minimum sample amount.
observed at 323 C for COME- without co-solvent and in case
of COME- with co-solvent, it was at around 296 C. In the third
step, remaining 10% weight loss was mainly pyrolysis products 3.6.4. Pour point by DSC
which were highly viscous liquids and undergoes secondary Poor low temperature flow properties is one of the major prob-
decomposition up to 330700 C for COME-without co-solvent lems associated with the biodiesel/methyl ester and because
and 300700 C for COME- with co-solvent, respectively. From of that operating engine at cold climate regions is often chal-
the above discussion, it can be conclude that thermal stability lenging (Edith et al., 2012). The cloud point is the temperature
of COME-without co-solvent was superior to COME-with co- at which the first solids become visible when cooling a fatty
solvent. Thus it could be authenticate that COME can act as acid methyl ester sample; the pour point is the temperature
an apt potential fuel alternative to diesel. at which the fuel ceases to flow. Pour point values of castor
oil methyl ester samples prepared with and without the use
of co-solvent were estimated by using DSC technique in the
3.6.3. Oxidative stability of COME by DSC nitrogen atmosphere using standard methods described in
Oxidative stability of COME samples (with co-solvent and our earlier paper (Borugadda and Goud, 2014). Pour point of
without co-solvent) was analysed by using DSC under air methyl esters sample has been noticed as a sharp increase in
atmosphere in the temperature range of 25350 C. the heat energy flow due to exothermic nature of increasing
The oxidative stability was measured in terms of oxidation reaction. The temperature at which exothermic peak occurs
onset temperature (OT). The onset temperature is defined as that has been considered as a pour point (Borugadda and
the temperature at which a rapid increase in the rate of oxida- Goud, 2014). DSC thermo gram of COME samples are shown
tion was observed. The DSC thermo grams of COME samples in Fig. 9.
with KOH (with and without co-solvent) are shown in Fig. 8. The pour points of both castor oil methyl ester samples
The oxidation onset temperature of COME samples prepared were found to be 19 C which are within the ASTM biodiesel
with and without the use of co-solvent was found to be 182 and standards. From the results, it can be seen that prepared
209 C, respectively. These results indicate that COME- pre- methyl ester has superior cold flow properties compared to
pared without the use of co-solvent is more oxidative stabile specified ASTM limits (Table 5). COME with higher percent-
compared to COME-with co-solvent. The end temperatures age of total unsaturated fatty acids showed lower pour point
of oxidative degradation were observed to be 240 C (without and qualifying COME as a perfect substitute for diesel fuel for
co-solvent) and 232 C (with co-solvent). The oxidative onset its use in cold countries. Edith et al. (2012) also reported that
temperatures of castor oil methyl ester obtained in this study the fuel with high unsaturated fatty acids show better cold
are superior to those reported (120 C) in the literature which flow properties. Results of the study reveal that DSC provides
was estimated by using TGA (Sruthi et al., 2013). The higher OT accurate means of monitoring the crystallization of biodiesel.
386 Process Safety and Environmental Protection 1 0 7 ( 2 0 1 7 ) 373387

confirmed by comparing 1 H-NMR spectra of castor oil and its


methyl ester.

3.7. Biodegradability of COME

The biodegradability of COME has been studied using bio-


kinetic model. According to the biodegradability screening
tests, any substance which meets the OECD ready biodegrad-
ability pass levels (either 60% CO2 evolution, 60% BOD/ThOD
or 70% dissolved organic carbon (DOC) removal within twenty
eight days test period) are considered as readily biodegradable
(OECD, 1992). The biodegradability of COME was 51% within
28 days. Corseuil et al. (2011) have reported similarly about
40% biodegradability of castor oil biodiesel within 90 days.
The lower biodegradability attributed due to the higher vis-
cosity and lower bioavailability (Corseuil et al., 2011). Al-Darbi
et al. (2005) reported that various oils respond in different
rates and extents to biodegradation which mainly depends on
their viscosity, structure and composition. Lisiecki et al. (2014)
observed that blending of biodiesel with diesel has not shown
impact on the long-term biodegradation. However, the fuels
with established biodegradability in the range of 70100% are
not expected to cause environmental concern because its high
biodegradability will leave very little residual and therefore is
not toxic to aquatic organisms (Aluyor et al., 2009). Though
the biodegradability of natural and vegetable oils are not in
doubt, the lower biodegradability of COME in the present study
is may be due to the higher viscosity (10.39 cSt) or other rea-
sons as discussed. With this, it can be conclude that COME
is biodegradable and eco-friendly. Therefore, castor oil based
methyl esters can be considered as a biodegradable ester.

4. Conclusions

Optimization of an integrated castor seed reactive extraction


process was investigated by three-factorial CCD using RSM.
ANOVA results indicate that these variables (catalyst concen-
tration, reaction time and oil/methanol molar ratio) have a
significant impact on COME conversion. The optimum COME
conversion of 95% was achieved with oil/methanol molar ratio
of 1:400, catalyst concentration of 1.5 wt% and 6.3 h reaction
time. The comparative analysis of effect of co-solvent (hexane)
on conversion and properties of COME reveals that co-solvent
has insignificant effect on the conversion, but the proper-
ties of COME such as thermal and oxidative stability obtained
Fig. 10 NMR spectrum of (a) castor oil; Methyl ester using with the use of co-solvent are slightly inferior as compared to
KOH (b) with co-solvent (c) without co-solvent. without co-solvent systems. The prepared COME properties
were confirmed to the ASTM standards. The biodegradability
1
of COME was 51% within 28 days, which may be due to its
3.6.5. H NMR analysis of oil and its methyl ester
1H
higher viscosity and lower bioavailability. From the present
NMR spectroscopy analysis of castor oil methyl ester sam-
study results, it could be conclude that integrated approach
ples have been carried out to estimate the gross conversion of
is an effective process for methyl ester production in a single
triglycerides. Fig. 10 shows 1 H-NMR spectra of castor oil and
step.
methyl esters prepared with and without the use of co-solvent
using KOH as catalyst.
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