Journal of Energy and Power Engineering 12 (2018) 11-15

doi: 10.17265/1934-8975/2018.01.002
D DAVID PUBLISHING

An Investigation to Assess Storage Stability of Pomelo

Seed Oil Biodiesel

Madhurjya Saikia, Dilip K. Bora and Kalyan Kalita

Mechanical Engineering Department, Assam Engineering College, Guwahati 781001, India

Abstract: Biodiesel is a biomass-based renewable and clean fuel. It can be used directly in existing diesel engines without any
modification. In spite of having so many advantages, it has an issue regarding long-term storage stability. Biodiesel oxidizes when it
comes in proximity of light, temperature, humidity, metals etc. The oxidation causes precipitation and sedimentation in the fuel. Such
biodiesel is unfit to use in engines. Hence, this study aims to assess the storage stability of pomelo seed oil (Citrus maxima) biodiesel
over a period of five months upon storage both in open and closed condition. Storage stability of biodiesel is determined in terms of acid
value, peroxide value and viscosity at regular interval of time. It is observed that there is a strong relationship between oxidation and
outside factors such as light, temperature fluctuations and humidity level. Upon exposure to these factors, oxidation in biodiesel
accelerated greatly.

Key words: Biodiesel, storage stability, acid value, peroxide value, viscosity.

1. Introduction 20].
Hence, quality should be maintained all the time to
Bio-diesel refers to a biomass based fuel having
ensure longevity of engines. Some of the tests based on
short chain alkyl esters, made by transesterification of
which storage stability can be ascertained are peroxide
vegetable oil or animal fat which can be used in
value, acid value and viscosity of the fuel. The present
existing diesel-engines [1-3]. It is considered to be a
study tries to assess storage stability of pomelo seed oil
naturally oxygenated fuel with inherent oxygen in itself
biodiesel (Citrus maxima) over a period of five months
about 9-10% [3, 4]. Recent researches suggest that
both in open and closed condition.
biodiesel is a clean fuel with less contribution to the net
increase of carbon monoxide, carbon dioxide, other 2. Materials and Methods
hydrocarbons and sulphur dioxide [5-7]. Moreover,
The experimental study is carried out in Mechanical
biodiesel from various non-edible oil resources has
Engineering Department Engine Laboratory,
been used successfully without requiring any engine
Dibrugarh University, India.
modification [8-10]. As a fuel, biodiesel is engine
friendly but its storage stability is a concern. When 2.1 Biodiesel Production
biodiesel is stored for a long time, it degrades rapidly in
The vegetable oil from pomelo seeds had been
contact with sunlight, moisture, and humidity. This is a
extracted by using a mechanical expeller. Pomelo seed
common problem faced by all biomass-based liquid
oil is converted to biodiesel via transesterification
fuels [11-19]. Ultimately, oxidized biodiesel becomes
process. Fig. 1 depicts the steps of laboratory scale
unfit to use in modern engines and causes trouble by
biodiesel production steps. Two hundred mL of methyl
clogging fuel injection and multiple another failures
alcohol was mixed with 14.5 gm of KOH (catalyst) to
due to precipitation and sedimentation problem [12, 13,
form a potassium methoxide solution. Then, this
solution of sodium methoxide was mixed with pomelo
Corresponding author: Madhurjya Saikia, research scholar,
ME Deptt., research fields: solid & liquid fuels and biodiesel. oil (1,000 mL). The mixture was held at a temperature
12 An Investigation to Assess Storage Stability of Pomelo Seed Oil Biodiesel

Fig. 1 Biodiesel production process.

Table 1 Physical and chemical properties of pomelo biodiesel samples. The biodiesel samples were stored
biodiesel (Citrus maxima). in sealed glass vessels. One of these glass vessels was
Pomelo placed normally in a room. The other one was placed in
Sl No. Properties Diesel
biodiesel
1 Density (kg/m3) 822 834
a wooden cabinet to resemble closed condition. Storage
Kinematic viscosity stability of the samples is assessed in terms of acid
2 1.92 2.6
(cSt)
value, peroxide value and viscosity at an interval of one
3 Pour point (°C) 15 16
4 Cloud point (°C) 4 4 month for five months.
5
Calorific value
27.1 53.54
2.2.1 Acid Value
(MJ/kg)
It is the mass of potassium hydroxide (KOH) in
6 Flash point (°C) 151 66
7 Fire point (°C) 200 76 milligrams that is required to neutralize one gram of
8 FFA% 0.959 - chemical substance. Precisely, five gram oil was taken
9 Acid number 0.479 - in a conical flask and isopropyl alcohol was added till
of 60 °C for 90 minutes with a constant agitation speed the oil dissolves completely. This solution was titrated
of 300 rpm. Then, the mixture was allowed to cool and against 0.1 N KOH solution after adding 1 or 2 drops of
settle in a separating flask for 12 hours. Two phenolphthalein indicator. The appearance of pink
layers were formed in the separating flask; bottom colour indicates the endpoint. Then, the acid value was
layer of glycerol and top layer of biodiesel. The top calculated using the formula given below.
layer of biodiesel has been separated by using a Acid value = (A B) × N × 56.1/W
separating flask. The properties of biodiesel are listed where, A = amount of 0.1 N KOH required for titration
in Table 1. with oil;
B = amount of 0.1 N KOH required for titration
2.2 Determination of Storage Stability of Biodiesel
without oil;
Storage stability studies were conducted on two W = weight of oil, N = normality of KOH.
 An Investigation to Assess Storage Stability of Pomelo Seed Oil Biodiesel 13

2.2.2 Peroxide Value (2) A = 0.59, B = 0.00247 for t ≥ 100.

Peroxide value is a measure of the concentration of
peroxides and hydroperoxides formed in the initial
stages of lipid oxidation. Milliequivalents of peroxide
per kg of fat are measured by titration with iodide ion.
To measure peroxide value, 5 gm of oil was taken in a
flask. A mixture of 20 mL of acetic acid and 10 mL of
chloroform was added to oil sample. The mixture was
swirled at low speed. After proper mixing, 0.5 mL of
freshly prepared potassium iodide solution was added
to the solution and stirred at a low speed. Then, the
solution was treated with 30 mL of distilled. This
solution was titrated against 0.1 N sodium thiosulphate,
using 0.5 mL starch solution as indicator. The amount
of sodium thiosulphate solution required for titration
was recorded. Peroxide value was determined by the
following method:
S = Titration of sample;
B = Titration of blank;
N = Normality of sodium thiosulphate solution.
Peroxide value:
2.2.3 Determination of Viscosity
The viscosity was measured in redwood viscometer.
Precisely, 50 mL of biodiesel was heated at 80 ºC in the
viscometer. By opening the aperture at the bottom of
the viscometer, the oil was allowed to flow and the time
was recorded. The kinematic viscosity was determined
by using the formula,
Kinematic viscosity = At B/t.
The constants:
(1) A = 1.79, B = 0.00260 for 34 ≤ t ≤ 100;
3. Results and Discussions
The acid values, peroxide values and viscosities had
been determined both conditions at an interval of one
month for five month duration. During the
experimentation period, the average ambient
temperature and humidity had been recorded and given
in Table 2.
The variations of acid values, peroxide values and
viscosities with storage time have been shown in Figs.
2-4 for both open and closed conditions. The results
were distinctly divided in two phases; first from
September to November 2016 and second from
December 2016 onwards till the end of the experiment.
During the first phase, the acid values, peroxide
values and viscosities for both conditions tended to
decrease as the ambient temperature, humidity and
sunlight tended to fall progressively on the advent of
winter. This indicated the slowing of oxidations
reactions and improvement in stability. The lowest acid
values, peroxide values and viscosities reached by both
the open and close samples had been 1.22 & 0.561, 20
& 2 mEq/kg and 1.26 cSt & 0.85 cSt respectively for
the month of November 2016. In the second phase, the
ambient temperature and humidity levels rose. This
expedited oxidation reactions in biodiesel samples. As
result, acid values, peroxide values and viscosities had
increased with storage time for both the samples in
open and closed conditions. Another important
observation during this phase was that the biodiesel in
close condition degraded at a higher rate than that of

Table 2 Stability status.

Peroxide value
Acid Value Viscosity (cSt)
Days (mEq/kg) Temp (°C) Humidity (%)
Open Close Open Close Open Close
30/09/2016 2.95 2.95 40 40 1.27 1.27 32.2 57
30/10/2016 2.24 2.44 30 30 1.50 1.50 28.2 48
30/11/2016 1.22 0.561 20 2 1.32 0.85 23.5 35
30/12/2016 1.875 2.453 27 27 1.47 1.05 24 64
30/01/2017 2.287 3.927 22 22 1.46 1.32 26 47
14 An Investigation to Assess Storage Stability of Pomelo Seed Oil Biodiesel

Acid value open Acid value close

4.5
4.0
3.5
3.0
Acid value

2.5
2.0
1.5
1.0
0.5
0.0
30/9/2016 30/10/2016 30/11/2016 30/12/2016 30/1/2017
Days

Fig. 2 Acid value vs. Days.

45
Peroxide value open Peroxide value close
40
35
Peroxide value (mEq/kg)

30
25
20
15
10
5
0
30/09/2016 30/10/2016 30/11/2016 30/12/2016 30/01/2017
Days
Fig. 3 Peroxide value vs. Days.

Viscosity open Viscosity close

1.6
1.4
Viscosity(cSt)

1.2
1.0
0.8
0.6
0.4
0.2
0.0
30/09/2016 30/10/2016 30/11/2016 30/12/2016 30/01/2017
Days
Fig. 4 Viscosity vs. Days.
 An Investigation to Assess Storage Stability of Pomelo Seed Oil Biodiesel
open one. Unlike the open condition, the temperature
and humidity level were intact in the closed condition
and were slightly higher than that of open one. This
small temperature gradient resulted higher oxidation
that sample.
4. Conclusions
In this study, storage stability of pomelo seed oil
biodiesel is evaluated on terms of acid value, peroxide
value and viscosity. The behaviour of parameters can
be divided into two phases. During the first phase
(September to November 2016), the parameters
showed a decreasing trend indicating lower oxidation
due to low ambient temperature and humidity level. As
the surrounding temperature and humidity increased
slightly in the second phase, there was rapid oxidation
in biodiesel and acid values, peroxides values and
viscosities rose with storage time. The oxidation of
biodiesel can be reduced by applying antioxidants such
as TBHQ, PrG, BHA and BHT.
References
[1] Peterson, C. L., Feldman, M., Korus, R., and Auld, D. L.
1991. “Batch Type Transesterification Process for Winter
Rape Oil.” Applied Engineering in Agriculture 7 (6):
711-6.
[2] Ma, F., Clements, L. D., and Hanna, M. A. 1998. “The
Effects of Catalyst, Free Fatty Acids, and Water on
Transesterification of Beef Tallow.” Trans. Am. Soc. Agric.
Eng. 41 (5): 1261-4.
[3] Balaji, G., and Cheralathan, M., 2013. “Potential of
Various Sources for Biodiesel Production.” Energy
Sources, Part A 35: 831-9.
[4] Ilkilic, C., and Behçet, R. 2010. “The Reduction of
Exhaust Emissions from a Diesel Engine by Using
Biodiesel Blend.” Energy Sources, Part A 32 (9): 839-50.
[5] Canakci, M., and Van Gerpen, J. H. 2003. “Comparison of
Engine Performance and Emissions for Petroleum Diesel
Fuel, Yellow Grease Biodiesel, and Soybean Oil
Biodiesel.” ASAE 46 (4): 937-44.
[6] Karaosmanoglu, F. 1999. “Vegetable Oil Fuels: A
Review.” Energy Sources 21 (3): 221-31.
[7] Canakci, M., and Hooz, M., 2006. “Energy and Exergy
Analyses of a Diesel Engine Fuelled with Various
Biodiesels.” Energy Sources, Part B 1 (4): 379-94.
15
[8] Rajan, K., and Kumar, K. R. S. 2009. “Improvement of
Performance and Emission Characteristics of a DI Diesel
Engine with Turbulence Induced Piston (Internal Jet
Piston) Using Biodiesel Blends.” SAE International 28
(December): 35-40.
[9] Bora, D. 2009. “Performance of Single Cylinder Diesel
Engine with Karabi Seed Biodiesel.” Journal of Scientific
& Industrial Research 68 (11): 960-3.
[10] Bora, D. 2014. “Biofuel Production from Mesua Ferrea L
Seed Oil.” International Journal of Engineering and
Technical Research (IJETR) 2 (9): 45-50.
[11] Du Plessis, L. M., De Villiers, J. B. M., and Van der Walt,
W. H. 1985. “Stability Studies on Methyl and Ethyl Fatty
Acid Esters of Sunflower Seed Oil.” Journal of the
American Oil Chemists Society 62 (4): 748-52.
[12] Bondioli, P., Gasparoli, A., Lanzani, A., Fedeli, E.,
Veronese, S., and Sala, M. 1995. “Storage Stability of
Biodiesel.” Journal of the American Oil Chemists Society
72 (6): 699-702.
[13] Bondioli, P., Gasparoli, A., Della Bella, L., and Tagliabue,
S. 2002. “Evaluation of Biodiesel Storage Stability Using
Reference Methods.” European Journal of Lipid Science
and Technology 104 (12): 777-84.
[14] Bondioli, P., Gasparoli, A., Della Bella, L., Tagliabue, S.,
and Toso, G. 2003. “Biodiesel Stability under Commercial
Storage Conditions over One Year.” European Journal of
Lipid Science and Technology 105 (12): 735-41.
[15] Middlemarch, M., and Schober, S. 2003. “The Influence
of Antioxidants on the Oxidation Stability of Biodiesel.”
Journal of the American Oil Chemists Society 80 (8):
817-23.
[16] Serrano, M., Bouaid, A., Martinez, M., and Aracil, J. 2013.
“Oxidation Stability of Biodiesel from Different
Feedstocks: Influence of Commercial Additives and
Purification Step.” Fuel 113 (November): 50-8.
[17] Serrano, M., Martinez, M., and Aracil, J. 2013.
“Long-Term Storage Stability of Biodiesel: Influence of
Feedstock, Commercial Additives and Purification Step.”
Fuel Processing Technology 116 (December): 135-41.
[18] Knothe, G., and Dunn, R. O. 2003. “Dependence of Oil
Stability Index of Fatty Compounds on Their Structure
and Concentration and Presence of Metals.” Journal of the
American Oil Chemists Society 80 (10): 1021-6.
[19] Dilip, B. 2009. “Storage Stability of Mahua Oil Methyl
Ester.” Journal of Scientific & Industrial Research 68 (2):
149-52.
[20] Madhurjya, S. 2017. “Effect of Antioxidant on Storage
Stability of Citrus Maxima Biodiesel.” International
Journal of Mechanical and Production Engineering 5 (2):
49-51.