Synthesis and Stability Study of Biodiesel From Kachnar Seed Oil
Synthesis and Stability Study of Biodiesel From Kachnar Seed Oil
Synthesis and Stability Study of Biodiesel From Kachnar Seed Oil
Abstract: This study focuses on the introduction of a new biodiesel resource, Kachnar seed oil (KSO). The raw oil was extracted from the
Downloaded from ascelibrary.org by ARIZONA,UNIVERSITY OF on 07/19/18. Copyright ASCE. For personal use only; all rights reserved.
seed by Soxhlet extraction. The composition of fatty acids and physicochemical properties of the raw oil were measured. Methyl ester was
produced from the raw Kachnar seed oil using a transesterification process using an alkaline catalyst. The new biodiesel, Kachnar methyl ester
(KME), meets biodiesel standards and could be a reliable substitute for diesel in diesel engine applications. This paper also investigates a
methodology to improve the oxidation stability of Kachnar biodiesel by blending it with diesel and by using different commercially available
antioxidants, namely butylated hydroxytoluene (BHT), tert-butyl hydroquinone (TBHQ), butylated hydroxyanisole (BHA), propyl gallate
(PG), and pyrogallol (PY), in the produced biodiesel. The antioxidants were dosed in concentrations ranging from 100 to 1,000 parts per
million (ppm). The result of the investigation shows that antioxidants PY and PG demonstrated effective results for improving oxidation
stability of Kachnar biodiesel. TBHQ was the least effective among the investigated antioxidants, whereas the KME10 blend can maintain its
stability without any antioxidant. DOI: 10.1061/(ASCE)EY.1943-7897.0000565. © 2018 American Society of Civil Engineers.
Author keywords: Kachnar seed oil; Kachnar oil methyl ester; Transesterification; Antioxidant; Oxidation stability; Rancimat test.
which was then held for 7 min. As a carrier gas, nitrogen was used at (Metrohm; 873). Rancimat equipment is a computer-controlled de-
an 8 mL=min flow rate. For flame production, the hydrogen and air vice for estimation of biodiesel/blends’ oxidation stability. It mea-
were used at 50 and 400 mL=min flow rates, respectively. The per- sures the induction period of biodiesel samples when they are
centage compositions [% by weight (wt.)] of the individual acids exposed to surrounding air (EN 14214). In the investigation, a
were calculated from the relative peak area. GC analysis of Kachnar 5-g sample of biodiesel was maintained at a fixed temperature
seed oil showed that the major fatty acids were linoleic, followed by of 110°C in a reaction vessel and filtered air was provided at
palmitic, oleic, and stearic acids. Table 1 presents the details of the the flow rate of 10 L=h, as per EN 14112. The result of oxidation
fatty-acid profile of Kachnar seed oil. is a secondary oxidation product highly volatile (organic acids) in
From Table 1, it is clear that Kachnar seed oil (KSO) contains a nature, which was moved to a vessel with air where it could be
lower amount of unsaturated fatty acids (63.58%) and higher absorbed in distilled water. With the help of a pair of immersed
saturated fatty acid (35.41%) in comparison with the other electrodes in the distilled water, the conductivity of the water
oil-bearing seeds. The unsaturated fatty-acid chain in biodiesel was continuously recorded and monitored. The induction period
fuel represents the degree of instability. Therefore, Kachnar (IP) was calculated as a function of the change of slope of the bio-
biodiesel has better storage stability in comparison with other diesel conductivity with variations in time. Five antioxidants,
common oil-bearing seeds. namely BHA, BHT, PG, TBHQ, and PY were used in different
concentrations in the range 100–1,000 parts per million (ppm),
namely 100, 200, 300, 500, 700, and 1,000 ppm.
Transesterification Procedure
The free fatty-acid (FFA) content in KSO was below 2%. Therefore, Results and Discussion
single-stage base transesterification was used for biodiesel produc-
tion from KSO through optimization of the process parameters. In
Effect of Molar Ratio (Methanol:Oil) on Biodiesel Yield
transesterification reaction, 100 mL of the heated oil was mixed with
methanol in proportions from 4∶1 to 7∶1 with a constant stirring speed The impact of molar ratio on biodiesel yield at various reaction
of 500 revolution per minute (rpm); for a duration of 30–150 min, the durations, keeping a fixed value of catalyst concentration (1%)
biodiesel yield was measured at 15-min intervals. Again, experiments and a reaction temperature of 60°C, is shown in Fig. 1. It was found
were performed by varying the concentration of catalyst from 0.5 to that the yield of biodiesel increases with reaction time for all molar
1.25 % by weight to examine the effect on biodiesel yield, and levels ratios, and the reaction time corresponding to maximum yield was
were recorded at various time intervals. The effect of reaction temper- the same (120 min) for all molar ratios. After a reaction duration of
ature on yield of biodiesel was also investigated at four different tem- 120 min, a negligible influence of reaction time on the yield of bio-
peratures of 50, 55, 60, and 65°C in order to measure biodiesel yield diesel was observed at all methanol:oil ratios. Maximum biodiesel
as a function of reaction duration at each temperature. On completion yield was 94%, which was obtained with 6∶1 methanol:oil ratio.
of the reaction, the reaction product was transferred to a 250-mL
separating conical funnel. After 4 h, a heavy layer of glycerol
was observed to be settled at bottom of the funnel, and this was later
removed through a drainage valve. The unreacted methanol, cata-
lysts, and impurities remaining in crude biodiesel produced from
KSO were removed by gently washing with distilled water at 60°C.
The product was then exposed to a temperature of 110°C for 30 min
to reduce its moisture content. The biodiesel yield percentage was
calculated by the formula given in Eq. (1)
Grams of methyl ester produced
Biodiesel yieldð%Þ:Y ¼ × 100
Grams of oil used in reaction
ð1Þ
Stability Analysis
yield increases with time up to 120 min, beyond which there was no
influence of reaction duration on biodiesel yield. Moreover, biodie- Fig. 3. Yield versus reaction time at different reaction temperatures.
sel yield was found to increase with an increase in NaOH concen-
tration, and the maximum yield was achieved at the concentration
of 1%. Beyond this concentration, there was a significant reduction
in the yield. Excess NaOH causes undesirable side reactions seen that biodiesel yield was maximum (93%) at 60°C, which was
(saponification) that reduces the ester yield and makes glycerol obtained at an optimum reaction duration of 120 min. Biodiesel
recovery difficult due to soap formation. Increased saponification yield is lower at low temperatures due to poor mixing between
with excess base catalyst was also reported in previous studies (Cao the raw seed oil and methoxide mixture because at low tempera-
and Zhang 2015; Chakraborty and Baruah 2013). The lower tures, oil viscosity is high.
yield of biodiesel at a lower concentration of NaOH was due to
incomplete conversion of triglycerides into esters. It was found that
at 6∶1 [volume by volume (v/v)] molar ratio and 1.0% [weight by Physicochemical Properties of Kachnar Biodiesel
volume (w/v)] NaOH in oil with a 120-min reaction duration gave Physicochemical properties of Kachnar oil and its biodiesel were
maximum biodiesel yield (94%) from KSO. determined by standard methods [EN ISO 3675 (ISO 1998a); EN
ISO 3104 (ISO 1998b); D93 (ASTM 2016); D97 (ASTM 2017e);
Effect of Reaction Temperature on Biodiesel Yield D2500 (ASTM 2017b); D6371 (ASTM 2017c); D664 (ASTM
2017a); D240 (ASTM 2017d)]. Average values of the physico-
Fig. 3 shows the impact of reaction temperature on biodiesel yield
chemical properties of Kachnar biodiesel and its blend of diesel
during transesterification at various reaction durations, keeping a
are presented in Table 2. It was observed that after transesterifi-
6∶1 molar ratio and amount of catalyst (NaOH) fixed at 1 % by
weight. It was found that the yield of biodiesel increases with cation, the density of KSO decreased from 0.91 to 0.86 g=cm3 ,
reaction time during transesterification at 50 and 55°C. At 60°C, which was within the acceptable limit. The viscosity of Kachnar
initially, the yield increases with time up to 120 min. After that, oil is reduced from 2.143 × 10−5 m2 =s to 4.3 × 10−6 m2 =s (21.43
however, there is no effect of reaction duration on biodiesel yield, to 4.3 cSt) if an oil still exists after transesterification. The flash
which was also observed earlier as shown Figs. 2 and 3. However, point of Kachnar biodiesel was higher than that of diesel (57°C),
there was an exception at 65°C, in which the biodiesel, after attain- and this property ensures safe handling and storage of Kachnar
ing a maximum yield of 86% at 90 min, reduced thereafter on biodiesel. It was also found that the heat of combustion of
further increases in reaction duration. This could be due to saponi- Kachnar biodiesel (39.15 MJ=kg) is lower than that of conven-
fication of glycerides by the alkaline catalyst before completion of tional diesel (43.8 MJ=kg).
methanolysis because the reaction temperature is higher than the
boiling point of methanol. Similar observations at higher reaction
temperatures above the alcohol boiling point were reported in pre- Antioxidant Effects on the Oxidation Stability
vious studies (Meher et al. 2006; Takase et al. 2014). Further, it was of Pure Biodiesel
Oxidation stability of Kachnar biodiesel does not meet with speci-
fication limit of 8 h (as per EN 14214). Therefore, the biodiesel
sample was treated with five assessed antioxidants in different con-
centrations, as stated previously. The different biodiesel induction
periods with different antioxidants were evaluated and are pre-
sented in Fig. 4, which shows a rising trend of IP for all antioxi-
dants. Fig. 4 illustrates the effectiveness of different antioxidants on
neat biodiesel. The study indicates that to keep the induction period
in line with specification of 20 h, a large amount of antioxidant PG
at a dose of 800 ppm or PY at a dose of 500 ppm is required in the
biodiesel. Fig. 4 also indicates that the most effective antioxidant
for all ranges of concentrations for a sample of Kachnar biodiesel is
PY. Among other antioxidants, PG proved highly effective for
better enhancement of oxidation stability of biodiesel. The antiox-
idants for Kachnar methyl ester (KME) in the order of decreasing
effectiveness are PY, PG, BHA, BHT, and TBHQ. Similar trends
Fig. 2. Yield versus reaction time at different NaOH concentrations.
were reported by Polavka et al. (2005).
Conclusions