Synthesis and Stability Study of Biodiesel From Kachnar Seed Oil

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Synthesis and Stability Study of Biodiesel

from Kachnar Seed Oil


Ashok Kumar Yadav, Ph.D. 1; Ashish Dewangan 2; and Ashis Mallick, Ph.D. 3

Abstract: This study focuses on the introduction of a new biodiesel resource, Kachnar seed oil (KSO). The raw oil was extracted from the
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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.

Introduction glycerol separation difficult (Demirbas 2008; Sahoo and Das


2009). The function of the catalyst is to improve the rate of reaction
Energy plays an important role in the economic growth of any and the yield, and it should be used in an appropriate amount. Spe-
nation. Demand for and consumption of energy are continuously cifically, an inadequate amount can cause an incomplete reaction
increasing worldwide. Most such requirements are fulfilled by whereas an excess amount is not that favorable in the biodiesel pro-
petroleum or fossil-fuel sources. The rapid depletion of fossil-fuel duction process (Demirbas 2008). The other important factors that
sources together with environmental concerns have encouraged the influence biodiesel production are reaction temperature and time,
search for an alternative fuel source. For compression engines, which are directly linked. A given yield of biodiesel can be obtained
plant oils proved to be best renewable source, and they are carbon either by carrying out the reaction at high temperature or by extending
neutral (Demirbas 2009). For transportation purposes, the best- the reaction time while performing the reaction at low temperature
suited alternative fuel is biodiesel, which is an alkyl ester of fatty (Sivastava and Prasad 2000).
acids. To convert vegetable oil or animal fat into biodiesel, trans- The foremost hindrance for commercial use of biodiesel is its ox-
esterification is the most economical method among the different idation stability; due to high susceptibility to oxidation, the fuel be-
process available, and it is done with methanol and ethanol comes acidic and form sediments and insoluble gums, which can
(short-chain alcohols) (Chhetri et al. 2008). In transesterification, plug fuel filters (Kerschbaum and Rinke 2004). The standard and
the reaction takes place between triglycerides (fat/oil) and alcohol test methods for determining storage stability for B100 (pure biodie-
(methanol/ethanol) with the addition of catalyst to form a fatty-acid sel) are still in the development stage within the ASTM process (Lin
ester and glycerol (Barnwal and Sharma 2005). Transesterification et al. 2009). As per the norms set by European Committee of Stand-
reactions can be influenced by variables such as amount of catalyst, ardization 34, the lowest level required for the stability of biodiesel
reactant ratio of alcohol to vegetable oil, reaction temperature, and oxidization is 6 h at a temperature of 110°C [EN 14214 (BSI 2013)]
time (Sahoo and Das 2009). (Sarin et al. 2009). The high percentages of oleic and linoleic acids in
An optimum ratio of alcohol to oil is very crucial in the process of Kachnar oil make it very susceptible to oxidation.
biodiesel production because an amount of alcohol higher than the Biodiesel feedstock has some natural antioxidants, which provide
stoichiometric is favorable for reaction and products formation. some initial oxidation stability. But during the production process,
On the other hand, excessive alcohol makes alcohol recovery and some of these natural antioxidants are removed; therefore, newly
prepared biodiesel does not match the stability norm of 8 h set
1
Associate Professor, Dept. of Mechanical Engineering, Raj Kumar by EN 14112 (BSI 2016). Some synthetic antioxidants are supple-
Goel Institute of Technology, Ghaziabad 201003, India (corresponding mented to increase the biodiesel induction period (Liang et al. 2006).
author). Email: [email protected] The effectiveness of an antioxidant is reciprocal to its concentration,
2
Ph.D. Scholar, Research Scholar, Dept. of Mechanical Engineering, i.e., antioxidants are most effective at lower concentrations, and as
Indian Institute of Technology (Indian School of Mines), Dhanbad the concentration increases, the effectiveness of some antioxidants
826004, India. decrease (Liang et al. 2006). Antioxidants such as butylated hydrox-
3
Associate Professor, Dept. of Mechanical Engineering, Indian Institute
yanisol (BHA), butylated hydroxytoluene (BHT), gallic acid, di-tert-
of Technology (Indian School of Mines), Dhanbad 826004, India.
Note. This manuscript was submitted on September 4, 2017; approved
butyl hydroquinone (di-TBHQ), propyl gallate, pyrogallol, and
on March 27, 2018; published online on July 17, 2018. Discussion tert-butyl hydroquinone (TBHQ), are frequently reported in the
period open until December 17, 2018; separate discussions must be sub- literature, but only some are suitable for biodiesel.
mitted for individual papers. This paper is part of the Journal of Energy In last decade, most research work on biodiesel in India has
Engineering, © ASCE, ISSN 0733-9402. focused on the area of biodiesel production from various plant

© ASCE 04018053-1 J. Energy Eng.

J. Energy Eng., 2018, 144(5): 04018053


resources, their characterization, and testing of biodiesel fuel (Ravindra et al. 2007). It is a small evergreen medicinal and avenue
blends in a compression ignition (CI) engine. Jatropha curcas, tree. It is a deciduous tree with maximum height up to 15 m with
Madhuca indica, and Pongamia pinnata (Agarwal and Agarwal short bole and spreading crown. It has angled slender twigs with
2007; Jain and Sharma 2010; Jindal et al. 2010; Puhan et al. light-green and brownish-gray hair. The inner bark is fibrous and bit-
2005; Schinas et al. 2009) are some nonedible oils available in ter, and outer bark is slightly fissured and scaly. Its leaves are bilobed
many parts of India that have been investigated by several authors glabrous on the upper surface. Their flowers make their first appear-
for determining their suitability as diesel engine fuel. Many works ance in late winter, when the tree is bare of leaves. Fruit is a dehiscent
are available in the literature related to biodiesel production from pod, strap-shaped, that contains various flat seeds. The flowers of this
plant resources and engine performance evaluation. Attia and plant, which are approximately 15–30 cm long, are the richest source
Hassaneen (2016) worked on biodiesel from waste cooking oil of vitamin C. In India, it is mostly used as a medicinal plant, and it is
and reported that appropriate properties of fuels are attained at popular in the various indigenous system of medicine like Ayurveda,
30% waste cooking oil methyl ester (WCOME), and the WCOME Unani, and homoeopathy. The bark has been traditionally used for
tonics, strains, ulcers, skin diseases, worm infestations, lymphadeni-
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blending ratio for best fuel economy and emission characteristics


are achieved at 10% and 30–50%, respectively. Muralidharan and tis, scrofula, and wounds. This herb is antibacterial, antifungal,
Govindarajan (2011) used Pongamia pinnata oil to produce biodie- cytotoxic, anti-inflammatory, pain- and fever-alleviating, and thyroid
sel by transesterification process, tested it in a CI engine, and re- regulating. The roots are also used as an antidote for snake poison.
ported that at full load, blend B5 showed a lower amount of unburnt Chemical compounds found in the herb are beflavone, flavonolgly-
hydrocarbons, carbon monoxide, oxides of nitrogen, and carbon coside, triterpine, saponin, phenanthraquninone, and flavonoids.
dioxide in engine emissions. Similarly, Srivastava and Verma
(2008) reported that the Karanja biodiesel has better maximum
thermal efficiency than diesel, which was approximately 24.9% Materials and Methods
with Karanja biodiesel, whereas that of the diesel was 30.6% at
maximum power output. Mature Kachnar (Bauhinia verigata) seeds were collected in the
Research on discovering new biodiesel feedstock, its production, summer season from the campus of Delhi Technological University
and characterization are in progress in many countries (Fadhil et al. (DTU) Delhi (India). By opening, the pod’s seeds were dried in the
2015; Hajinezhad et al. 2015; Souza et al. 2016). A number of re- exposure to sunlight, then the shells were removed. Before oil ex-
search works have been done on oxidation stability and storage of traction, the kernel was crushed in a grinder. Five antioxidants,
biodiesel derived from vegetable oil, and much investigation is still namely BHT, PY, BHA, PG, and TBHQ, and other chemicals used
required in the area of blending effects of biodiesel on its oxidation were of analytical grade and they were procured from commercial
stability. The Rancimat and differential scanning calorimetry (DSC) sources and used as such without further treatment.
method were used to determine the influence of BHT and pyrogallol
(PY) on the biodiesel oxidation stability derived from waste frying oil
and rapeseed oil (Polavka et al. 2005). Karavalakis and Stournas Oil Extraction from Kachnar Seeds
(2010) investigated the stability behavior of biodiesel and diesel/ A Soxhlet extraction system was used to extract the brownish-yellow
biodiesel blends using a modified Rancimat method [as per EN oil from Kachnar seeds. Some dried Kachnar seeds were properly
15751 (BSI 2014)]. That study includes the effect of different syn- crushed, and 30 mg of ground seeds was placed in the thimble of
thetic phenolic antioxidants on oxidation stability of neat biodiesel. the Soxhlet extraction system with a round-bottomed flask (0.5 L)
Karavalakis et al. (2010) examined the factors affecting the stability and a condenser. A known quantity of the dried seeds was extracted
of diesel/biodiesel blends and discussed the influence of sulfur and in a Soxhlet extractor for 6 h using n-hexane as a solvent by under-
cracked stocks present in pure diesel on the oxidation stability of bio- going a cycle of repeated evaporation and condensation for oil ex-
diesel. The propyl gallate (PG) antioxidant effectiveness on the sta- traction. For solvent separation, the thimble was detached from the
bility of biodiesel derived from safflower has been reported by Xin Soxhlet. The oil–solvent mixture was heated to the temperature of
et al. (2009). Karavalakis et al. (2011) experimentally proved that the 60°C for vaporizing and collecting the n-hexane after condensation
tested antioxidants are effective in improvement of oxidation stability in the condenser. The oil content of the seeds was measured by
of biodiesel and reported that BHA and BHT exhibit the minimum weighing the oil left in the flask. Extracted oil was further dried over
effectiveness in pure biodiesel but have greater stabilizing potential anhydrous sodium sulfate for removal of moisture. For 1 kg of seeds,
when used in biodiesel blends. 190 mL oil was obtained. Thus the percentage of oil content obtained
In the literature, it is found that due to food security, many re- is 19%. The oil content from Kachnar seeds is comparable with that
searchers have focused their recent research work on a nonedible of other oil-bearing tree seeds like Roselle (Hibiscus sabdariffa L.)
source that is a suitable alternative to edible feedstock for production (18%) (Nakpong and Wootthikanokkhan 2010) and Chikku seeds
of biodiesel. Among nonedible oils, only some of the feedstock has (23–30%) (Pawar and Hole 2017), but has lower oil content than
been explored well, such as Jatropha, Karanja, and Mahua. However, Jatropha (37%) (Jain and Sharma 2010).
Kachnar has not yet considered for biodiesel production. So, in the
present investigation, Kachnar seed oil has been explored as possible
fuel in a CI engine. The primary objectives of the present research Fatty-Acid Composition of Kachnar Seed Oil
study are production and characterization of biodiesel from Kachnar
seed oil and investigation of its oxidation stability. The fatty-acid composition (FAC) of oil from Kachnar seeds was
The genus Kachnar, consisting of more than 250 species, be- determined using an Agilent Technologies GC-6890 gas chroma-
longs to the family Leguminosae (Caesalpinioideae). The Kachnar tographer (GC) (Ghaziabad, Uttar Pradesh, India) equipped with a
tree is also known as camel’s foot tree, butterfly ash, orchid tree, flame ionization detector and a capillary column for injecting the
and mountain ebony. It is found in South and Southeast Asia, sample, which is available from the Indian Pharmacopoeia Com-
Sri Lanka, Pakistan, Nepal, India, Burma, and Southern China. mission (IPC) (Ghaziabad, India). The initial temperature was
It is distributed in the sub-Himalayan tract from the Indus eastward set to 100°C, which was maintained for 2 min. Then, the heat
and also in dry forests over eastern, central, and southern India was increased by 10° C=min until the temperature reached 240°C,

© ASCE 04018053-2 J. Energy Eng.

J. Energy Eng., 2018, 144(5): 04018053


Table 1. Fatty-acids composition of Kachnar seed oil (% by weight)
Chemical Degree of Kachnar Jatropha Karanja
Fatty acid formula unsaturation KSO (Prakash et al. 2001) (Jain and Sharma 2010) (Jain and Sharma 2010)
Palmitic C16 H32 O2 16∶0 20.10 21.5 16.0 11.65
Stearic C18 H36 O2 18∶0 15.31 18.3 6.5 7.50
Oleic C18 H34 O2 18∶1 25.92 14.2 43.5 51.59
Linoleic C18 H32 O2 18∶2 37.11 43.4 33.4 16.46
Linolenic C18 H30 O2 18∶3 0.55 — 0.8 2.65
Arachidic C20 H38 O2 20∶0 — 1.7 — —
Total saturated fatty acid 35.41 39.8 22.5 19.15
Total unsaturated fatty acid 63.58 59.3 77.7 70.7
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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

A Rancimat instrument was used for evaluation of samples of bio-


Fig. 1. Yield versus reaction time at different molar ratios.
diesel oxidation stability with different antioxidant concentrations

© ASCE 04018053-3 J. Energy Eng.

J. Energy Eng., 2018, 144(5): 04018053


Biodiesel yield from KSO greatly reduced at a molar ratio of 7∶1
after every reaction duration. With excess methanol beyond a cer-
tain limit, separation of glycerine and esters becomes difficult due
to increased solubility, and this reverses the reaction equilibrium,
resulting in a lower yield of biodiesel. Lower biodiesel yield at
higher methanol concentrations was also reported by previous stud-
ies (Cao and Zhang 2015; Kafuku and Mbarawa 2010).

Effect of NaOH Concentration on Biodiesel Yield


The impact of NaOH concentration on the yield of biodiesel at vari-
ous reaction durations at a fixed molar ratio at 6∶1 is presented in
Fig. 2. It was observed that for all NaOH concentrations, biodiesel
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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).

© ASCE 04018053-4 J. Energy Eng.

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Table 2. Physicochemical properties of Kachnar seed oil and its biodiesel in comparison with biodiesel specification standards
Property KSO KME Diesel Test method ASTM 6751 EN 14214 Measurement apparatus/method
Density at 15°C (g=cm3 ) 0.91 0.86 0.83 EN ISO 0.86–0.90 0.85 Stabinger viscometer SVM 3000
3675 (Anton Paar India, Gurgaon,
Haryana, India)
Kinematic viscosity 2.143 × 10−5 4.3 × 10−6 2.9 × 10−6 EN ISO 1.9 × 10−6 m2 3.5 × 10−6 m2 = Stabinger viscometer SVM 3000
at 40°C m2 =s (cSt) m2 =s (21.43) m2 =s (4.3) m2 =s (2.9) 3104 =s–6 × 10−6 m2 =s s–5 × 10−6 m2 =s
(1.9–6.0) (3.5–5.0)
Flash point (°C) 200 187 57 D93 Minimum 130 Minimum 120 Pensky-Martens closed-cup
apparatus (Norma lab, France)
Pour point (°C) −2 −6 −15 D97 −15 to −16 — Automatic NTE 450
(Norma lab, France)
Cloud point (°C) 5 3 2 D2500 −3 to −12 — Pour point apparatus
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Norma lab, France


CFPP (°C) 6 4 −9 D6371 — — Automatic NTL 450
(Norma lab, France)
Acid value (mg KOH=gm) 2.2 0.14 0.09 D664 Maximum 0.5 Maximum 0.5 Titration method
Saponification 183.5 164.7 — — — — Titration method
value (mg of KOH=g oil)
Calorific value (MJ=kg) 37.12 39.15 43.8 D240 — — Parr 6100 calorimeter
(IKA, United Kingdom)
Oxidation stability (h) — 7 — EN Minimum 3 Minimum 8 873 Rancimat (Metrohm,
14112 Switzerland)

Effect of Blending of Biodiesel with Petro-Diesel on Its


Oxidation Stability
With the addition of antioxidants in biodiesel, the EN specification
can be achieved, but the only drawback is the high cost of the
antioxidant. Kachnar biodiesel was blended with diesel and used
in a CI test engine. Different blends (KME5, KME10, KME20,
KME40, KME60, KME80, and KME100) was prepared, and
the effect on oxidation stability was evaluated. According to the
modified Rancimat method of EN 15751, the IP was estimated
for various biodiesel blends. The results are shown in Fig. 5. It
is clear from Fig. 5 that as the diesel percentage increases in the
blend, the IP increases, which leads to improved oxidation stability
of biodiesel, which in turn leads to reductions of unsaturated fatty
acid in the biodiesel blend. The experiment indicates that to meet
the 20 h norms of European standard EN 590 (BSI 2017), the mini-
Fig. 4. Effect of various antioxidants on the oxidation stability of mum amount of diesel is a ratio of 9∶1 with Kachnar biodiesel
Kachnar oil methyl ester. (KB10). However, on increasing the biodiesel percentage beyond
KB10 in blends, the induction period continuously drops below
20 h and cannot meet the norms of EN 590. Therefore, it is neces-
sary to evaluate the effect of antioxidant PYon oxidation stability of
Kachnar biodiesel beyond KB10.

Conclusions

A new biodiesel with good yield (94%) and compatible properties


with ASTM D6751 (ASTM 2015) and EN 14214 standards was
achieved at optimum process parameters of 1% (w/v) catalyst
[Potassium hydroxide (KOH)] concentration, and molar ratio of
6∶1 (methanol:oil) at a temperature 60°C for 120 min. The exper-
imental investigation showed that blending with diesel and use of
an antioxidant improves the stability characteristics of Kachnar bi-
odiesel significantly. Among the different evaluated antioxidants,
PY proved the most effective in all ranges of concentrations (from
100 to 1,000 ppm). BHA and BHT antioxidants were found to be
useful in higher concentrations in the KME. Even TBHQ at a con-
Fig. 5. Variation of induction period with blending ratio. centration level of 1,000 ppm was not able to enhance the oxidation
stability of KME sample of biodiesel up to the specification limits

© ASCE 04018053-5 J. Energy Eng.

J. Energy Eng., 2018, 144(5): 04018053


set by EN 14214. From the aforementioned results, it is concluded Convers. Manage. 99: 132–140. https://doi.org/10.1016/j.enconman
that Kachnar seeds could be a potential renewable source for .2015.04.034.
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leum and liquid petroleum products—Laboratory determination of
density—Hydrometer method. EN ISO 3675. Geneva: ISO.
ISO (International Organization for Standardization). 1998b. Petroleum
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