European Journal of Engineering and Technology Vol. 2 No.

2, 2014
ISSN 2056-5860

RICE BRAN OIL BIODIESEL

Emmanuel I. Bello & Oluwole O. Oluboba

Department of Mechanical Engineering
The Federal University of Technology, Akure, Ondo State
NIGERIA

ABSTRACT

The search for cheap alternative sources of vegetable oil, the need to convert agricultural
wastes to wealth and the desire to solve waste disposal problems has lead to the extraction of
oil from rice bran. The oil was extracted using a soxhlet extractor operated at 60oC and then
transesterified using methanol as reagent and sodium hydroxide as catalyst. No pretreatment
with an acid was necessary as the free fatty acid was a low 0.12%. The oil and biodiesel were
characterized according to American Society for Test and Materials (ASTM) and the
European Norms (EN) protocols. The results obtained shows that the densities and viscosities
of the oil reduced after transesterification, while flash points and cetane number of the
samples increased. Most of the properties are within the limits of ASTM D6751-02 standards
for biodiesel thus making it a suitable alternative fuel for diesel engines.

Keywords: Rice bran oil, transesterification, biodiesel, characterization.

INTRODUCTION

The use of vegetable oil and animal fats for the production of biodiesel has been strongly
criticized because of the possible adverse effects on food security if land used for food
production is diverted to the production of vegetable oils for biodiesel or if oil for
consumption is used for biodiesel production. This concern has led to research in the use of
non-edible oils such as castor oil (Bello and Otu, 2011) and rubber seed oil (Ramadhas et al,
2009) as feedstocks for the production of biodiesel. Jatropha for example, which is inedible,
can be used as hedge crop, can be planted on local dump sites, marginal and semi-arid lands,
and do not require chemical inputs and maintenance. However, if oil from waste products
such as used frying oil (Lague et al.,1987) or fish wastes (Cherng-Yuan and Rong-Jilia, 2008)
are used, they would also solve disposal problems and help to create wealth from apparently
valueless and disgusting farm or factory wastes. Rice bran falls into this category of factory
wastes that for ages have been burnt to dispose off and without any economic value
notwithstanding the fact that it contains triglycerides.

LITERATURE REVIEW

Rice (oryza sativa linn) bran is the outer brown thin layer between the rice and the outer husk
of the paddy that is removed in order to polish the rice and constitutes approximately 8% of
the gross weight of a harvested rice head. The whole rice grain comprises (on dry weight
basis): Endosperm 70-72%, Hull 20%, Bran 7.0-8.5% and Embryo 2-3% while the rice bran
comprises pericarp, tegmen (layer covering endosperm), aleurone and sub – aleurone (Ju and
vali, 2005). Depending on the specie and intensity of milling, the oil content of rice bran has
been reported to be 16 – 32 wt% (Hargrove, 1993), which is much lower than the 55% for
jatropha (Pramanik, 2003), 55% for castor (Conceicao et al., 2007) and 60% for egunsi seeds
oil (Giwa et al., 2010) and 45% for rubber seed oil (Ramadhas et al., 2009).

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When rice is used as feedstock for the production of oil instead of being regarded a waste, it
would have more positive impact on food supplies than when edible crops like Soya beans
and corn are used because it is a by-product and does not require extra land, labour and other
farm inputs for its planting.

Due to the presence of an active lipase in the bran, Free Fatty Acid (FFA) content in Rice
Bran Oil (RBO) has been reported to be much higher than other edible oils and about 60-70%
of the oil produced from this bran is non-edible, due to problems attributable to the stability
and storage of rice bran and the dispersed nature of rice milling (Goffman, 2003; Zullaikah
et al., 2005; Lin et al., 2009). The FFA of the oil usually increase rapidly to 4 - 8%, due to the
active lipase in the bran after milling and constitutes a major hurdle during transesterification
and the dark color during refining (Bhattacharyya, 1983).

RBO has been classified as one of the most nutritious oils due to its favorable fatty acid
composition and a unique combination of naturally occurring biologically active and
antioxidant compounds (Goffman, 2003). the edible part is commonly used as cooking oil in
china, Japan and India, and the bran is used as a fiber component for poultry and cattle feeds
in the United States.

A survey of the use of rice bran in rice mills in Nigeria shows that it is used as furnace fuel
for drying, fish and cattle feeds and in the majority cases it constitutes a waste. Whereas in
countries such as India and Thailand where rice is widely cultivated, it has been researched
extensively (Yi-Hsu J. and Shaik Ramjan V., 2005; Venkanna et al., 2009; Syed Altaf et
al.,2009) and reported.

The aim of this study is to extract oil from the rice bran and characterize the oil and its
biodiesel.

MATERIALS AND METHODS

Rice bran was obtained from rice mills located in Ikogosi in Ekiti states of Nigeria.
The powdery form of bran was procured immediately after milling and stabilized into flakes
and dried as it has been reported that it allows for 96% oil extraction within 5 minutes and
after 1 hour the residual oil was about 0.7% (dry weight basis) (Bender, 1999). The oil was
extracted in a soxhlet extractor using n-hexane as the solvent. The oil was leached for 8 hours
with the mantle heater set at 60o C and the residual hexane in the mixture was removed using
a vacuum rotary evaporator operated at 75o C.

The oil obtained was weighed and the percentage oil yield was calculated by the equation 1.

1.

The Free Fatty Acids (% oleic acid) content of the oil were first measured to determine if
pretreatment was necessary or not before alkaline transesterification as it has been reported
that too high acid content during alkaline transesterification can react with the catalyst to
form soap which can inhibit biodiesel yield (Ramadhas et al., 2009). This was found to be
0.12%, which was lower than the minimum of 3% often reported (Ramadhas et al., 2009;
Sahoo et al., 2007) hence no pretreatment was done.

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Transesterification
Procedure

Transesterification was carried out using a laboratory scale biodiesel processor in the Fuel
Laboratory of the Federal University of Technology, Akure. The optimum reaction
conditions for the transesterification of rice bran oil using the orthogonal analysis of
parameters in a four-factor and three-level test, obtained by Ju and Vali (2005) were used.
The alkaline transesterification was done using anhydrous methanol at a molar ratio of 6 to 1
and 0.9 % w/w of sodium hydroxide. The processor was stirred at 600 rpm and at a
temperature of 60 oC for 4 hours after which the mixture was poured into a decanter and
allowed to settle for 3 hours so that the reaction can be driven to completion and for the
mixture to separate into methyl ester and for the glycerol at the bottom to be drained off by
gravity. The excess methanol in the ester was removed in a flash evaporator. To remove any
impurity, the methyl ester was washed in distilled water of volume ratio 3 to 1 three times.
The biodiesel yield was calculated from the biodiesel and oil weights using equation 2:

Fatty Acid Profile

The fatty acid profile of rice bran oil (RBO), the B100 and the standard sample of free fatty
acid were determined using the HP 6890 Gas Chromatography analyzer that used HP
ChemStation Rev A 09.11 [1206] software for data collection. It was equipped with a Flame
Ionization Detector (FID) and used nitrogen as the carrier gas. The initial oven temperature
was set at 60 oC and the procedure was as reported by (Bello and Otu, 2011).

Characterization

The rice bran oil and its methyl ester (B100), where characterized according to ASTM and
EN protocols as listed in Table 1. Measurements were made in triplicate and the mean
reported.

Table 1. Biodiesel properties test methods

Property Unit Protocol ASTM EN
Limits Limits
D6751 14214
Density at 15oC kg/m2 ASTM D1298 860-900 860-900
o
Pour point C ASTM 2500 - -
o
Cloud point C ASTM2500 - -
o
Flash point C ASTM D93 130 min 120 min
Kinematic viscosity mm2/s at 40 oC ASTM D445 1.9-6.0 3.5-5.0
Lower heating value kJ/kg ASTM D240 - -
Cetane index - ASTM D613 47 min -
Iodine value g/100g EN14111 120 -
Peroxide value meq/kg EN14111 - -
Oxidation index hours ASTM D2709 3 min 6 min
Saponification value mg KOH/g of oil EN14111 - 120 max
Free fatty acid % oleic acid - - -

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Acid value mgKOH/g ASTM D664 0.05max -

Soap content Ppm EN14111 - -
Water and residue % ASTM D2709 0.05 max -
Moisture content % ASTM D2709 - 360 max
Sulphur % ASTMD5453 0.05%
Copper strip Corrosion ASTMD130 No.3 max

RESULTS AND DISCUSSION

The fatty acid profile of the oil and B100 are shown in Table 1 while the characterization
results are in Table 2. The percentage free fatty acid value was surprisingly very low, thus
making pretreatment with an acid unnecessary [Ramadhas, 2009]. The oil yield was 15%,
which is comparable to the 13 - 23 % reported by Houston (1972) and it had a brownish
green colour with very pungent smell.

Fatty Acid Profile

Table 2. Fatty Acid Profile of Rice Bran Oil (RBO) and B100.
Acid Form RBO B100
Myristic C14:0 0.112 0.078
Palmitic C16:0 14.991 15.926
Palmitoleic C16:1 0.146 0.1009
Margaric C17:0 0.028 0.019
Stearic C18.0 1.288 1.275
Oleic C18:1 41.513 40.914
Linoleic C18:2 38.652 38.474
Linolenic C18:3 1.416 1.429
Arachidic C20:0 0.765 0.778
Arachindonic C20:4 0.243 0.168
Behenic C22:2 0.588 0.615
Erucic C22:1 0.034 0.023
Lignoceric C24:0 0.222 0.199
Total Saturation 17.406 18.275
Total 82,592 81.929
unsaturation

Table 2. Fatty Acid Profile of different Rice Bran Oil17.406 biodiesel

Acid Form RBO Nigeria *B100 **B100

B100
Lauric C12:0 - - - 0.2
Myristic C14:0 0.112 .078 0.40 0.8
Palmitic C16:0 14.991 15.926 15.60 17.7
Palmitoleic C16:1 0.146 0.1009 - 0.23
Margaric C17:0 0.028 0.019 - -
Stearic C18.0 1.288 1.275 2.00 2.2
Oleic C18:1 41.513 40.914 41.00 40.6
Linoleic C18:2 38.652 38.474 33.5 35.6
Linolenic C18:3 1.416 1.429 0.50 1.8

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Arachidic C20:0 0.765 0.778 0.2 0.2

Arachindonic C20:4 0.243 0.168 -
Behenic C22:2 0.588 0.615 - 0.3
Erucic C22:1 0.034 0.023 - -
Lignoceric C24:0 0.222 0.199 - 0.6
*Zullaihikah et al., 2005 **Houston, 1972

Biodiesel Analysis

The main components of the fatty acid profile of the RBO and B100 were analyzed
qualitatively and quantitatively using GC-MS and GC-FID and the results are shown in
Table.2. The oil contains 14.991% palmitic and 1.288% stearic acids both of which are
saturated, and 41.513% oleic, 38.652% linoleic and 1.416% linolenic acids. The profile for
the methyl ester followed the same pattern, but the mass of the fatty acids with double and
triple bonds in B100 decreased while that of the monounsaturated fatty acid increased. Of
particular significance is the oleic acid of 41.513% for the oil which is just below the average
value of 45% for vegetable oils [Bello and Agge, 2011]. Oleic acid value gives the balance
between favorable cold flow properties, high oxidation stability and tendency for soap
formation during transesterification. However, The fatty acid profile does not meet the quality
specification of Schenk et al. 2008, that suggested that a good quality biodiesel should have a
5:4:1 mass fatty acid ratio of C16:1, C18:1 and C14:0, but it agrees with the chemical
structure of biodiesel proposed by Li et al., (2005) in the form C19H36O2. Since C18 fatty acid
methyl ester constituted 82.869 % of the biodiesel. The results obtained in this study are
comparable to those reported by Zullaihikah et al., 2005 and Houston, 1972 as shown in
Table 2.

Table 3. Properties of bran oil, its biodiesel and blends.

Property RBO B100
2)
Density (kg/m 906 885
Pour point ( oC) 13 2.5
o
Cloud point( C) 16 3.3
2 o
Kinematic viscosity (mm /s at 40 C) 38.2 4.54
Flash point ( oC) 184.0 162.8
Lower heating value (kJ/kg) 40.85 41.60
Cetane index 51.02 56.95
Iodine value (g/100g) 103.17 112.15
Peroxide value (meq/kg) 1.02 1.24
Oxidation index (Hrs) 16 9
Saponification value (mg KOH/g of oil) 186.51 204.24
Free fatty acid (% oleic acid) 0.12 0.14
Acid value (mgKOH/g) 0.06 0.08
Soap content (ppm) 0.002 10.20
Water and residue (%) 2.00 0.005
Moisture content (%) 0.020 0.010
Sulphur 0.25 0.009
Copper strip Corrosion 4 2
pH value 5.76 6.92

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Reflective index 1.48 1.353

Colour Brownish green Dark brown
Odour Pungent

Density

This is the mass per unit volume and hence affects the fuel mass flow rate into the engine and
the power output from the engine. It affects the pressure of the fuel being injected into the
engine and the resulting penetration distance of the injected fuel, the atomization and the
combustion process. The density of the oil of 906 kg/m3 reduced to 885 kg/m3 for the B100.
Low density has been reported to require advancing the injection timing (Gamus, 2010) to
enhance the engine operation.

Cloud point

The cloud point is the temperature at which wax would first appear on the surface of the fuel
when being cooled. This test is of importance because the presence of wax can affect fuel
flow, volatility, uniformity of property and usability in cold region. The cloud point of the oil
was 16 oC and reduced to 3.3 oC after transesterification.

Pour point

The pour point is the temperature to which the wax in the fuel is enough to turn the fuel to a
mass of gel. The pour point reduced from 13 oC to 2.5 oC. The pour point is much lower than
that of diesel fuel thus limiting their used in cold regions without the use of antifreeze
additives. Biodiesel with high proportion of saturated fatty acids tends to have high pour
point because many saturated fatty acids are solid at room temperature.

Kinematic viscosity

The kinematic viscosity is a measure of the resistance of the fuel to flow. It affects the
performance of fuel pumps, the atomization of injected fuel, lubricity and the impinging
distance upon injection. Biodiesel generally has a higher viscosity than diesel, and thus
exhibit inferior atomization and spray characteristic, resulting in a larger mean liquid droplet
diameter and a longer ignition delay of the fuel [Hoekman et al., 2012]. When viscosity very
high, it makes atomization more difficult, it affects combustion efficiency, lower the
performance of fuel pumps and adversely affect exhaust emissions because of incomplete
combustion. The kinematic viscosity of the oil was 38.2 mm2/s and it reduced to 4.52 mm2/s
for B100 and although slightly higher than that of diesel is within the ASTM limits for
biodiesel.

Flash Point

The flash point of the oil was 184 oC and reduced to 162oC for B100. this makes it a much
safer fuel in storage and use than diesel. It is about three times higher than that of diesel thus
making it a safe fuel from the point of view of safety and fire risk. It will consequently, ignite
at a much higher temperature which will result in shorter delay period, better engine
performance and reduced exhaust emissions.

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Heating value

This is the amount of heat that can be liberated from a kg of the fuel. The heating value of the
oil and B100 are 48.44 kJ/(kg.k) and 41.62 kJ/(kg.k) respectively and consistent with the
trend for biodiesel. Heating value affects the engine power output, thermal efficiency, fuel
consumption, exhaust emissions, cleanliness of the engine, time between service and vehicle
performance.

Cetane numbers

The cetane number for the raw oil of 51.2 and increased to 56.95 after transesterification. It is
a measure of the ignition quality of diesel fuels. It reduces the chemical phase of the ignition
delay time for the fuel to seek out the necessary oxygen upon injection into the combustion
chamber, it influences ease of starting because of its oxygen content and intensity of the
characteristic diesel knock during idling. Biodiesels usually have a higher cetane index than
diesel fuel because of its oxygen content and also because some of the fatty acids present in
the fuel have very high octane number.

Free fatty acid

The free fatty acid was 0.12% which is surprisingly very low compared to 3% threshold
suggested by (Ramadhas et al., 2009) that would not lead to soap formation that can inhibit
biodiesel yield during transesterification. RBO does not require pretreatment before
transesterification because of the low FFA content. This is a great advantage as under
industrial condition, pretreatment constitute a significant part of the cost of production.

Iodine value

The iodine value of the oil of 103.17 (g/100g) increased to 112.15 (g/100g) after
transesterification both of which are below the 120 (g/100g) limit for biodiesel. Iodine is a
measure of the degree of saturation of a fuel. High unsaturation can lead to the free molecules
combining with oxygen to cause the fuel to polymerize or after combustion lead to excessive
carbon deposits in the engine combustion chamber.

Peroxide value

Peroxide values of RBO and B100 of 1.02 and 1.24 meq/kg respectively are moderate and
reduced with blending after transesterification. Peroxide value is generally used to determine
the degree of rancidity and extent of fuel oxidation The peroxide values are within the limits
for biodiesel.

Oxidative stability index

The oxidative index of 11 hr for the oil reduced to 9 for B100 but increased with blending.
During these periods, the presence of double bonds in the fuel causes reversible reactions in
the fuel that can lead to the formation of insoluble sediments and gums that are deposited in
fuel tanks and filters, and cause corrosion.

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Saponification value

The saponification value for the oil was 186.51(mg KOH/g of oil) and less than the average
of 200 (mg KOH/g of oil) for vegetable oils. The saponification value of 186 (mg KOH/g of
oil) compares with the value obtained by (Muhammad et al., 2008) for the oil. The values are
all above the maximum EN limits for biodiesel. A small amount of saponification will help
in reducing friction between moving parts in the pump and injectors. But when high can have
adverse effect on fuel properties and can also inhibit biodiesel yield during transesterification.

Acid value

The acid value and FFA value are surprisingly low compared to other results [Bello and Otu,
2011] and would not require pretreatment with acid. The acid value for the oil was 0.06
mgKOH/g which is very much lower than the 23 mgKOH/g by (Muhammad et al., 2012)
High acid value can increase fuel density, change fuel colour, and result in the formation of
acidic solution which can lead to increased corrosion and deterioration of fuel properties.

Soap content

The soap content of the oil increased after transesterification as a result of the residual soap
formed that escaped purification. The soap content of 0.002% for the oil increased to 10.20%
for B100 because of the imperfection of the washing process that allows for residual soap.
High soap content can cause the fuel to burn irregularly thus decreasing thermal efficiency
and opacity, and increasing exhaust emissions.

Water and residue, and moisture contents

The water and residue contents reduced from 2% for the oil to 0.005 % after
transesterification and washing which is within the limit for biodiesel. Water has high latent
heat of evaporation and a small quantity can help in lowering the combustion temperature but
excessive can freeze under certain conditions and block the flow of fuel to the engine, can
promote microbial growth and accelerate corrosion in fuel systems. The higher density of
water can cause adversely affect fuel metering while excessive residue can block filters and
nozzles.

Sulphur content

The sulphur content reduced from 0.25% to 0.009% after transesterification and reduced
further with blending. Sulfur is added to diesel to reduce friction but the amount in diesel has
been limited by regulation because the sulfur oxide emitted in the exhaust gas can result in
acid rain that can affect vegetation and degrade the environment. It can also damage the
catalytic converter elements. Biodiesel spreads when poured on a surface and penetrates
pores, cracks and crevices thus making it a very good lubricant. In diesel engine, the fuel
lubricates the fuel pump, fuel injection systems and the piston rings. The diesel engine is
about 30% efficient with about 20% of the power developed lost to friction and another 7.5%
wasted in the engine. The naturally occurring sulfur in RBO which along with the high
lubricating properties of biodiesel when used for blending will contribute to reducing friction
and hence improved fuel economy, mechanical efficiency and engine durability.

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Copper strip Corrosion

The corrosion value of the copper strip in RBO was 4 out of a scale of maximum value of 5.
The value however reduced to 2 after transesterification. This test is important because many
components of the fuel system are made from copper alloys and are liable to rust when in
contact with RBO.

Colour

The brownish green colour of the raw oil changed to dark brown after transesterification due
to the removal of the colour imparting pigments in the oil after transesterification and
purification.

Refractive index

The refractive index of RBO was 1.48, it decreased to 1.353 after transesterification For the
oil the result is similar to that reported by (Muhammad et al., 2012) for the oil. Refractive
index is an indicator of impurities in the fuel and the presence of high molecular weight
components in the fuel.

pH values

pH is a measure of the acidity and alkalinity of the oil. The raw oil and biodiesel are acidic.

CONCLUSIONS

RBO has a low free fatty acid content and can be transesterified without pretreatment with an
acid and this will reduce the cost of production when produced on industrial scale. The
properties of B100 are close to those of diesel fuel hence it can be used as alternative fuel for
diesel engines.

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