CHAPTER 1

INTRODUCTION

In the modern day, there is a huge demand for transportation systems, and this demand
is increasing day by day, as a result of the ever-increasing number of vehicles and engines.
However, the conventional sources of fuel have always been limited in quantity and are also
being depleted at an alarming rate.

It also has adverse effect on the planet like climate change global warming etcetera. The issues
faced with the usage of conventional energy sources like fossil fuels are as follows:

1. Environmental Hazards: Environmental pollution is one of the major disadvantage

of conventional fuel sources. It is a known fact that carbon dioxide, NOx and other
harmful gases are released when fossil fuels are burnt, which also is the main reason
constituting to 56% of global climate change.

2. Rising Prices: Organization of the Petroleum Exporting Countries (OPEC) is a

group of 13 and are responsible for 40% of the worlds oil according to the Energy
Information Administration. OPEC constantly monitors the volume of oil consumed
and then adjusts its own production to maintain its desired barrel price. This results in
worldwide price fluctuations, according to the U.S. Department of Energy.

3. Acid Rain: Sulphur dioxide is one of the pollutant that is released when fossil fuels
are burnt and is a main cause of acid rain. Acid rain can lead to destruction of
monuments made up of brickwork or marbles. Even crops can affected due to
acidification of loams. Coal mining results in destruction of ecosystems and also
endangers the lives of mineworkers.

4. Effect on Human Health: Air pollution cause due to coal plans and vehicular
pollution can result in asthma, chronic obstructive pulmonary disorder (COPD) and
lung cancer. Long-term exposure may increase respiratory infections in general
population.

5. Non-Renewable: As of today, fossil fuels are being extracted at an exorbitant rate

to meet the gap between demand and supply and it is estimated that they will be
finished in next 30-40 years.

6. Impact on Aquatic Life by Oil Spill: The impact of this is that crude oil spill
contains some toxic substances which when mixed up with water poses serious
impact on aquatic life. Transportation of crude oil via sea can cause oil spill which
can pose hazard to the aquatic life by lessening the oxygen content of water.

7. Coal Mining: The coal mining destroys wide areas of land and results in ecological
imbalance.

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1.1 ALTERNATE SOURCES OF ENERGY

Fig 1.1: World Energy Production 2017-04-04

Source: US Renewable energy department

Of the above mentioned energy sources nuclear energy, wind energy, solar energy and
biofuels are the most considered alternatives for unconventional energy sources. It is projected
by 2030 the biofuel usage will increase by about 34% of the present value and biofuel is
considered as the most suitable alternative for conventional fuel.

1.2 BIODIESEL

Methyl esters, derived from vegetable oils, are known as Biodiesel. Biodiesel is the
best alternative fuel for Diesel engines. The main advantages of biodiesel are its ability to be
produced domestically and biodegradability. It can be used directly in Diesel engines without
any modifications.

A biofuel is a fuel that is produced through contemporary biological processes, such as

agriculture and anaerobic digestion, rather than a fuel produced by geological processes such
as those involved in the formation of fossil fuels, such as coal and petroleum, from prehistoric
biological matter. Biofuels can be derived directly from plants, or indirectly from agricultural,
commercial, domestic, and/or industrial wastes. Renewable biofuels generally involve
contemporary carbon fixation, such as those that occur in plants or microalgae through the
process of photosynthesis. Other renewable biofuels are made through the use or conversion
of biomass (referring to recently living organisms, most often referring to plants or plant-
derived materials). This biomass can be converted to convenient energy-containing substances
in three different ways: thermal conversion, chemical conversion, and biochemical conversion.
This biomass conversion can result in fuel in solid, liquid, or gas form. This new biomass can
also be used directly for biofuels.

2
Biodiesel can be used as a fuel for vehicles in its pure form, but it is usually used as a diesel
additive to reduce levels of particulates, carbon monoxide, and hydrocarbons from diesel-
powered vehicles. Biodiesel is produced from oils or fats using transesterification and is the
most common biofuel in Europe.

In 2010, worldwide biofuel production reached 105 billion litres (28 billion gallons US), up
17% from 2009, and biofuels provided 2.7% of the world's fuels for road transport. Global
ethanol fuel production reached 86 billion litres (23 billion gallons US) in 2010, with the United
States and Brazil as the world's top producers, accounting together for about 90% of global
production. The world's largest biodiesel producer is the European Union, accounting for 53%
of all biodiesel production in 2010. As of 2011, mandates for blending biofuels exist in 31
countries at the national level and in 29 states or provinces. The International Energy Agency
has a goal for biofuels to meet more than a quarter of world demand for transportation fuels by
2050 to reduce dependence on petroleum and coal. The production of biofuels also led into a
flourishing automotive industry, where by 2010, 79% of all cars produced in Brazil were made
with a hybrid fuel system of bioethanol and gasoline.

This means of alternative energy are derived from plants. These are known as biofuels and
biogas. Biofuels is also called Ethanol and it is derived from the fermentation of sugar. It is
used as an additive to petroleum, since it burns in a cleaner way and the emission of greenhouse
gases is less.

Biogas on the other hand, occurs naturally when biomass or organic waste material decomposes
in the absence of oxygen. The resulting mix of gases is flammable and provides clean energy
when burnt. It is the base of Compressed Natural Gas, which has found a great deal of use in
the transportation sector.

1.3 TYPES OF BIOFUELS

First Generation Biofuels: First generation biofuels are made from sugar, starch, or
vegetable oil. They differ from second generation biofuels in that their feedstock (the plant
or algal material from which they are generated) is not sustainable/green or, if used in large
quantity, would have a large impact on the food supply. First generation biofuels are the
original biofuels and constitute the majority of biofuels currently in use.

Second Generation Biofuels: Second generation biofuels are greener in that they
are made from sustainable feedstock. In this use, the term sustainable is defined by the
availability of the feedstock, the impact of its use on greenhouse gas emissions, its impact on
biodiversity, and its impact on land use (water, food supply, etc.). At this point, most second
generation fuels are underdevelopment and not widely available for use.

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1.4 BIODIESEL BLENDS

Biodiesel can be blended and used in many different concentrations. The most common are:
B6 to B20 (6% to 20% biodiesel blended with petroleum diesel) and B5 (5% biodiesel, 95%
petroleum diesel). B100 (pure biodiesel) is typically used as a blendstock to produce lower
blends and is rarely used as a transportation fuel.

1.4.1 Low-Level Blends:

ASTM International develops specifications for a wide variety of products, including

conventional diesel fuel (ASTM D975). This specification allows for biodiesel concentrations
of up to 5% (B5) to be called diesel fuel, with no separate labeling required at the pump. Low-
level biodiesel blends, such as B5, are ASTM approved for safe operation in any compression-
ignition engine designed to be operated on petroleum diesel. This can include light-duty and
heavy-duty diesel cars and trucks, tractors, boats, and electrical generators.

1.4.2 B20

B20 is a common biodiesel blend in the United States. B20 is popular because it
represents a good balance of cost, emissions, cold-weather performance, materials
compatibility, and ability to act as a solvent. Most biodiesel users purchase B20 or lower blends
from their normal fuel distributors or from biodiesel marketers. Regulated fleets that use
biodiesel blends of 20% (B20) or higher qualify for biodiesel fuel use credits under the Energy
Policy Act of 1992.

B20 must meet prescribed quality standards as specified by ASTM D7467-15ce1. The U.S.
Department of Energys Vehicle Technologies Office has supported work to test and improve
biodiesel quality, helping more fuel meet ASTM standards.

Using B20 and lower-level blends does not require engine modifications. Engines operating on
B20 have similar fuel consumption, horsepower, and torque to engines running on petroleum
diesel. B20 with 20% biodiesel content will have 1% to 2% less energy per gallon than
petroleum diesel but most B20 users report no noticeable difference in performance or fuel
economy. Biodiesel has some emissions benefits, especially for engines manufactured before
2010. For engines equipped with selective catalytic reduction (SCR) systems, the air quality
benefits are the same whether running on biodiesel or petroleum diesel. However, biodiesel
still offers better greenhouse gas (GHG) benefits compared to conventional diesel fuel. The
emissions benefit is roughly commensurate with the blend level; that is, B20 would have 20%
of the GHG reduction benefit of B100.

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However, not all diesel engine manufacturers approve the use of B20 (see the National
Biodiesel Board's OEM Information for those that support the use of biodiesel blends). Users
should always consult their vehicle and engine warranty statements before using biodiesel.

1.4.3 B100 AND HIGH-LEVEL BLENDS

B100 and other high-level biodiesel blends are less common than B20 and lower blends due to
a lack of regulatory incentives and pricing. B100 can be used in some engines built since 1994
with biodiesel-compatible material for certain parts, such as hoses and gaskets. B100 has a
solvent effect, and it can clean a vehicle's fuel system and release deposits accumulated from
petroleum diesel use. The release of these deposits may initially clog filters and require
frequent filter replacement in the first few tanks of high-level blends.

When using high-level blends, a number of issues should be considered. The higher the
percentage of biodiesel (above 20%), the lower the energy content per gallon. High-level
biodiesel blends can also impact engine warranties, gel in cold temperatures, and may present
unique storage issues. B100 use could also increase nitrogen oxides emissions, although it
greatly reduces other toxic emissions.

B100 requires special handling and may require equipment modifications. To avoid engine
operational problems, B100 must meet the requirements of ASTM D6751-15ce1, Standard
Specification for Biodiesel Fuel (B100) Blend Stock for Distillate Fuels (summary of
requirements). ASTM Specification D6751-15ce1 includes a No.1-B and a No.2-B grade. The
No.1-B grade has stricter limits on mono - glycerides and filterability than the No.2-B grade.
The No.1-B grade is a special purpose biodiesel grade for use in applications where low
temperature operability is needed.

5
 CHAPTER 2
LITERATURE REVIEW

2.1 SOURCES FOR BIODIESEL:

TABLE 1: BIODIESEL SOURCES

Vegetable oils Animal Fats Other sources

Cottonseed oil Tard Poultry fat

Jatropha oil Tallow

Sunflower oil Fish oil

Neem oil

Corn oil

Soyabean oil

2.2 TRANSESTERIFICATION:
Vegetable oil, when used as a neat fuel, has the following drawbacks:

i. High viscosity
ii. High density
iii. Poor fuel properties (physical and chemical)
iv. Poor performance, combustion and emission characteristics.
Biodiesel is prepared through a process called transesterification, in which alkyl esters are
extracted from vegetable oil by making them react with alcohol. Transesterification gives
two byproducts:

i. Methyl esters that are used as biodiesel

ii. Glycerin, a valuable byproduct that is used in the production of commercial
products such as soaps, shampoos, etc.
Though transesterification can go about by just mixing the reactants due to it being an
equilibrium reaction, the reaction is speeded up by using a strong acid or base as a catalyst. In

6
order to ensure that the methyl ester yield is high, alcohol is to be used in excess. The general
mechanism of transesterification is given as follows:

REA 2.1: GENERAL TRANSESTERIFICATION MECHANISM

Schuchardt et al explained that based on the catalyst used in the reaction, transesterification
can be classified as:

i. Acid catalyzed transesterification: Sulfonic/sulfuric acids

ii. Base catalyzed transesterification: KOH/NaOH
iii. Lipase catalyzed transesterifcation: Hydrolitic enzymes
iv. Non-ionic catalyzed transesterification : Organic bases

2.3 TRANSESTERIFICATION OF HIGH FFA FEEDSTOCKS:

Alkaline metal oxides such as KOH and NaOH require moisture-free conditions to give a high
yield of biodiesel from transesterification. However, due to the hydroxide reacting with
alcohol, some water is produced even if a moisture-free oil/alcohol mixture is used. Due to
this, high FFA feedstocks, which are high in FFA content and low on moisture content, use
this produced water to give rise to hydrolysis of some of the produced ester, giving rise to soap
formation. The mechanism of this reaction is given as follows:

REA 2.2: SAPONIFICATION SIDE REACTION.

This undesirable saponification reaction results in low methyl ester yield and forms an
emulsion with glycerol, thereby making its recovery difficult. To overcome this, methyl esters
are extracted from neem oil by a 2-step process, as suggested by S. Ram Kumar et al, as
follows:

i. Acid catalyzed esterification

ii. Base catalyzed transesterification.

7
For corn oil, methyl esters are obtained only through base catalyzed transesterification.

2.4 BIODIESEL BLENDING:

Though biodiesel can be used as a straight fuel, some engines will need modifications to run
pure biodiesel. In order to overcome this, biodiesel is blended with petrodiesel in specific
compositions by volume. Biodiesel-diesel blends are denoted by Bxy, B representing biodiesel,
xy representing the % composition of biodiesel in the blend. For example, B30 represents 30%
biodiesel, 70% diesel. There are different methods by which biodiesel can be blended:

i. Splash blending: Biodiesel and diesel are loaded in two separate tanks, mixing of
products are done during delivery to the end user.
ii. In-tank blending: Biodiesel and diesel are loaded simultaneously. At high enough
fill rate the fuels sufficiently mix and require no further agitation.
iii. In-line blending: Biodiesel is added to a stream of diesel as it flows through a pipe,
and blending occurs when both fuels move across in the pipe.
There are several types of biodiesel blends, as follows:

a. Low level blends:

i. B2 (2% biodiesel, 98% diesel)
ii. B5 (5% biodiesel)
iii. B20 (6-20% biodiesel)
b. High level blends:
i. B98 (98% biodiesel)
ii. B100(100% biodiesel)
Low level blends are used as vehicular fuels, and high level blends are very rarely used. B100,
in most cases, is only used to make other blends.

2.5 SELECTION OF BLEND:

Biodiesel can be blended in any percentage with diesel. However in certain cases, engine
modifications may be required when biodiesel content in the blend goes beyond 30%.

Yadav et al noted the following results from their performance test using palm methyl ester
blends:

i. B-20 blend had a BSFC of 3.8 kg/kWhr, while B-40 had 4kg/kWhr, B60 had 5
kg/kWhr, B80 had 5,9kg/kWhr, B100 had 7 kg/kWhr, clearly indicating that B-20
blend had the least BSFC indicating decent fuel economy.
ii. The Brake thermal efficiency vs BP curve of B-20 had the highest values compared
to other blends, and the maximum efficiency was 28% while B-40 had 24.9 %, B60
had 24. 7% B80 had 24.8%, B100 had 24%.

8
 iii. B-20 produced the least amount of NOx (1760 ppm at peak brake power (BP), i.e.
3.7 kW) at all conditions while B-40 had 1990 ppm, B60 had 2000ppm, 2000 ppm
B80 had 2100ppm, B100 had 2200 ppm.
iv. B-20 and B40 produced the least amount of CO2 (0.05%vol at peak BP) at all
conditions while other blends produced 0.06%.
v. B-20 produced the most amount of Hydrocarbons (12ppm) at peak BP, while other
kWblends had values ranging from 8.5-10 ppm at peak load.

2.6 EFFECTS OF BIODIESEL ON CI ENGINES:

a. ENGINE POWER:
Biodiesel has a much higher cetane number than petrodiesel, due to which it has a significantly
lower ignition delay time and thus burns more completely. However, biodiesel has a lower
energy content per volume, and thus using it without any modification to the fuel injection
system will result in a slight loss in engine power. However, due to it being hard to exactly
determine a fuels impact on an engines power and torque, several tests have been controlled
environments, and the results obtained have not been constant. For example, Niehaus et al.
observed a power loss ranging from 5-7% using B100 whereas the results of the test conducted
by Schumacher et al. on a Cummins 5.9L turbocharged direct ignition engine indicated a 3%
power increase.

b. ENGINE DURABILITY:
Biodiesel, due to its lubricity, has shown a noticeable decrease in the rate of engine wear when
compared to petrodiesel. A research that is being conducted at the University of Saskatchewan
since the early 1990s has shown that biodiesel has decreased engine wear by 10 times. A
research project based on biodiesel conducted at the University of Idaho included several new
tractors and trucks, showed that various blends of biodiesel produced the same rate or a
considerably less rate of engine wear. However, in the long run, due to its tendency to absorb
moisture due to the presence of esters and also the presence of natural gums of certain oils,
biodiesel clogs the fuel filter and it would have to be replaced earlier than its slated period,
which is not the case in petrodiesel.

c. FUEL ECONOMY:
Schumacher et al conducted a study on 5 B20 buses and 5 petrodiesel fueled buses at St.
Louis, and concluded by saying that there was no significant difference between the fuel
economy of petrodiesel and B20. Another research project conducted by the University of
Missouri on a Dodge pick-up truck with different blends of biodiesel indicated similar results.

d. VISCOSITY:
Biodiesel and biodiesel blends are known to have greater viscosity than petrodiesel. This leads
to poor atomization of fuel spray and less accurate operation of the fuel injectors. As
temperature decreases, the viscosity increases, making it harder for biodiesel to be properly
atomized and injected. Certain impurities may also contribute to the increase in viscosity.

9
2.7 COBALT OXIDE NANOFLUID:
Ganesh et al conducted performance and emission tests on a CI engine with neat jatropha
methyl ester. The obtained results were compared with diesel and a drop in performance but
improvement in emissions was seen. To try and improve the results, the following
nanoadditives were used:
i. Cobalt oxide
ii. Magnalium
When additive was just added and ultrasonicated, the nanopowder just settled down after
sometime. Therefore, the obtained dispersion was not stable. To overcome this, a surfactant,
i.e. a compound charged oppositely to the particle to be suspended should be added, as it forms
a shield-like layer to ensure that agglomeration does not occur. Since both additives are
positively charged, a negatively charged organic surfactant was used.

The results obtained when additives are added to JME are tabulated as follows:
PARAMETER CHANGE
BSEC Co3O4 2% reduction
Al-Mg 3% reduction
BTHE Co3O4 0.35% increase
Al-Mg 1.1% increase
Hydrocarbon emission Co3O4 83% reduction
Al-Mg 70 % reduction
NOx emission Co3O4 - 47% reduction
Al-Mg -30% reduction
Carbon monoxide emission Co3O4 66% reduction
Al-Mg 50% reduction

2.8 INFERENCE FROM LITERATURE SURVEY:

i. According to the biodiesel magazine, B20 requires no engine modifications to be
used in a CI engine.
ii. Transesterification is to be done to ensure that vegetable oil is useable in a diesel
engine.
iii. From S. Ramkumar et al.s study, high FFA feedstocks will need acid pretreatment
to improve methyl ester yield.
iv. From Yadav et al.s study, biodiesel gives the best results when it was blended with
diesel in a 20:80 ratio.
v. Biodiesel engine performance tests have always shown erratic results: for example,
there has been a boost in power in certain cases, while there has been a power loss
in certain cases.
vi. From Schumacher et al. and the University of Missouris study, it can be concluded
that fuel economy of biodiesel blends and diesel are nearly the same.

10
 vii. From Ganesh et al.s study, Co3O4 showed higher emission reduction potential
while Al-Mg showed better performance improvement.
viii. Therefore, methyl esters will be blended in a 20% composition with diesel, and
cobalt oxide will be used as the fuel additive to test its emission reduction and
performance improvement potential.

11
 CHAPTER 3

TRANSESTERIFICATION

3.1 INTRODUCTION:
In general, transesterification is defined as the process by which the organic group of
an ester (say R) is exchanged with the organic group (say R) of an alcohol. These reactions
are always done in the presence of a suitable catalyst, as explained in Chapter 2. Strong acids
catalyse the reaction by donating a proton to the carbonyl group, thus making it a more
potent electrophile, whereas bases catalyse the reaction by removing a proton from the alcohol,
thus making it more nucleophilic. Esters with larger alkoxy groups can be made from methyl
or ethyl esters in high purity by heating the mixture of ester, acid/base, and large alcohol and
evaporating the small alcohol to drive equilibrium. In the transesterification mechanism, the
carbonyl carbon of the starting ester (RCOOR1) undergoes nucleophilic attack by the incoming
alkoxide (R2O) to give a tetrahedral intermediate, which either reverts to the starting material,
or proceeds to the transesterified product (RCOOR2). The various species exist in equilibrium,
and the product distribution depends on the relative energies of the reactant and product. The
basic reaction is illustrated as follows.

REA 3.1: TRANSESTERIFICATION

3.2 TRANSESTERIFICATION OF NEEM OIL:

Neem oil, due to its low moisture and high fatty acid content, produced a significant amount
of soap due to the saponification side reaction, illustrated as follows:

REA 3.2: SAPONIFCATION SIDE REACTION.

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This gave a significant amount of soaps, and the methyl ester yield was quite low. Therefore,
the two step process: acid catalyzed esterification and base catalyzed transesterification are
employed according to the method of Berchmans and Hirata.

3.2.1 ACID CATALYZED ESTERIFICATION:

REA 3.3: ACID CATALYZED ESTERIFICATION

Due to the low moisture and high ffa content of crude neem oil, it is subject to giving rise to
the saponification side reaction due to it being significantly hydrophilic. Due to this, it absorbs
the slightest amount of moisture, causing the formation of a carboxylic acid. This carboxylic
acid then reacts with NaOH, creating a soap molecule and water, which causes the process to
go on and on, since water is being regenerated. This severely affects the methyl ester yield, and
therefore acid catalyzed esterification is done.

The mechanism of the acid catalyzed esterification is as shown in Fig. The protonation of the
carbonyl group of the ester leads to the carbocation II which, after a nucleophilic attack of the
alcohol, produces the tetrahedral intermediate III, which eliminates glycerol to form the new
ester IV, and to regenerate the catalyst H+. According to this mechanism, carboxylic acids can
be formed by reaction of the carbocation II with water present in the reaction mixture. This
suggests that an acid-catalyzed transesterification should be carried out in the absence of water,
in order to avoid the competitive formation of carboxylic acids which reduce the yields of alkyl
esters.

The procedure followed for NME extraction is as follows:

i. 1 litre of crude neem oil is taken

ii. It is heated for 20 minutes at 60oC
iii. After it is heated, it is mixed with 300ml methanol as shown in Fig 1.
iv. Then 12 ml of concentrated sulphuric acid is then added to the mixture.
v. The mixture is then kept @ 50oC and stirred for 90 minutes.

13
 vi. The mixture is then poured into a separating funnel, and then the pretreated oil is
separated from the water methanol phase at the top, as shown in Fig 2.

Fig 3.1Adding methanol Fig 3.2 Separating pretreated oil

3.2.2 BASE CATALYZED TRANSESTERIFICATION:

REA 3.4: TRANSESTERIFICATION MECHANISM

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The mechanism of the base-catalyzed transesterification of vegetable oils is shown in Fig 4.4.
The first step (Eq. 1) is the reaction of the base with the alcohol, producing an alkoxide and the
protonated catalyst. The nucleophilic attack of the alkoxide at the carbonyl group of the
triglyceride generates a tetrahedral intermediate (Eq. 2)11,40, from which the alkyl ester and the
corresponding anion of the diglyceride are formed (Eq. 3). The latter deprotonates the catalyst,
thus regenerating the active species (Eq. 4), which is now able to react with a second molecule
of the alcohol, starting another catalytic cycle. Diglycerides and monoglycerides are converted
by the same mechanism to a mixture of alkyl esters and glycerol.

The procedure for transesterification is as follows:

i. The oil is measured and taken in a beaker.

ii. Methanol is then measured and added to the beaker.
iii. The mixture is then heated at 60oC and continuously stirred.
iv. The agitation rate is kept at 1500 rpm.
v. The amount of KOH (potassium hydroxide, a basic catalyst) is then measured
correctly and added.
vi. The reaction is then allowed for a period of 1.5h.
vii. The resulting mixture is then poured into separating funnel and allowed to settle
under gravity for 24h for separation of biodiesel.
viii. The lower glycerol layer is then tapped off.
The products formed during transesterification were methyl ester and glycerol. The lower layer
was glycerol and it was separated. The ester is then washed with 10% volume-by-volume warm
water (70C) and kept for about 24 hours for removal of catalyst by dissolution in water. This
is done even in the case of pretreated neem oil.

The amount of methanol and catalyst used, and the biodiesel yield obtained for corn oil and
pretreated neem oil is shown in the table.

TABLE 2: METHYL ESTER YIELD

Type of Oil: Corn oil Pretreated neem oil

Amount of oil taken 1L ~1L

Methanol used 250 ml 250 ml

Amount of KOH used 6.2 gms 9 gms

Methyl ester yield 986 ml 860 ml

15
 CHAPTER 4

TESTING AND PROPERTIES

4.1 PENSKY MARTENS CLOSED CUP APPARATUS

The Pensky Martens apparatus (Fig) is used to determine the flash point and fire
point of a given fuel. The term Flash point refers to the temperature at which a particular fuel
gives off a sufficient amount of vapor to ignite air, and the term Fire point refers to the
temperature at which the fuel burns continuously for at least 5 seconds.

Fig 4.1 PENSKY MARTENS APPARATUS

4.1.1 COMPONENTS OF PENSKY MARTENS APPARATUS

It consists of three parts:

i. Oil cup: the fuel is filled up to the mark in the cup.

ii. Shutter, to open and close the oil cup whenever needed to introduce the flame.
iii. Stove.

The specifications of the oil cup are given as follows:

i. Material brass
ii. Height 55 mm
iii. Diameter 50 mm

4.1.2 FLASH POINT AND FIRE POINT MEASUREMENT

The fuel is heated @ 1oC/min and continuously stirred. The test flame is introduced for every
1oC rise in the fuel temperature. At a certain temperature, the test flame causes a distinct flame
in the cup, and this is recorded as the flash point. Upon further heating, at a certain
temperature, the temperature at which the vapors of the fuel give a clear and distinct blue flash
for at least 5 seconds is recorded as the fire point.

16
 TABLE 3: FLASH POINT AND FIRE POINT

Fuel Flash point (oC) Fire point (oC)

Diesel 75 80

CME 110 116

NME 120 132

C20 66 76

N20 67 77

4.2 REDWOOD VISCOMETER

The Redwood Viscometer is an industry standard apparatus that is used to determine the
kinematic viscosity of liquids. It is shown in Fig 5.2.

4.2.1 TYPES OF REDWOOD VISCOMETER

Type 1 Redwood viscometer : used for fluids with lesser viscosity

Type 2 Redwood viscometer : used for highly viscous fluids

Fig 4.2 REDWOOD VISCOMETER

There is no difference between the 2 viscometers, except in the orifice diameter and length:
type 2 has a diameter of 3.8 mm and length 50 mm while type 1 has a diameter of 1.62 mm
and length 10mm.

17
4.2.2 DETERMINATION OF KINEMATIC VISCOSITY

The formula to determine the kinematic viscosity of a fluid using redwood viscometer
is as follows:

Kinematic viscosity = (A*t) (B/t)

A 0.26, B 171 (orifice constants)

t Time taken for 50ml of the fuel to collect when the fuel is let to flow through the orifice.

The Redwood viscometer comprises of vertical cylindrical cup with an axial jet at the bottom.
The jet can be opened/closed by a ball valve. Thermometers are used to measure the
temperature of both the fuel and the surrounding water bath that is used to heat the oil. The
water can be heated by an electric coil, and it in turn heats the fuel inside very uniformly.

First, the fuel is filled in the cup of the viscometer, and then heated to a certain temperature.
Care must be taken so that the fuel just touches the mark on the viscometer cup. Then, ball
valve is removed, and then the time taken for 50 ml of the fluid to collect in the flash kept
below the orifice is noted, and then the kinematic viscosity is calculated using the above
mentioned formula. The experiments were carried out @ 40oC and the results are tabulated as
follows:

TABLE 4: KINEMATIC VISCOSITY

Fuel Time taken for 50ml of Kinematic viscosity

fuel to collect in the (cSt) at 40oC
flask (s)
Diesel 31.59 2.8

Corn Oil Methyl Ester 36.21 4.69

Neem Oil Methyl Ester 37 5

C20 31.61 2.81

N20 31.65 2.82

4.3 BOMB CALORIMETER

A bomb calorimeter is a type of constant-volume calorimeter used in measuring the heat of
combustion of a particular reaction and thus in turn the calorific value. Calorific value is
defined as the amount of heat that is released by a substance when 1kg of it is burnt. Bomb
calorimeters have to withstand the large pressure within the calorimeter as the reaction is being
measured. Electrical energy is used to ignite the fuel; as the fuel is burning, it will heat up the
surrounding air, which expands and escapes through a tube that leads the air out of the

18
calorimeter. When the air is escaping through the copper tube it will also heat up the water
outside the tube. The change in temperature of the water allows for calculating calorie content
of the fuel.

Fig 4.3 BOMB CALORIMETER

Basically, a bomb calorimeter consists of a small cup to contain the sample, oxygen, a stainless
steel bomb, water, a stirrer, a thermometer, the dewar or insulating container (to prevent heat
flow from the calorimeter to the surroundings) and ignition circuit connected to the bomb. By
using stainless steel for the bomb, the reaction will occur with no volume change observed.

The following formula is used to determine the calorific value of a fuel using the bomb
calorimeter.

Gross calorific value (GCV) = (W*(dT)max E1 E2)/m

(dT)max Maximum temperature rise

W Heat equivalent of calorimeter = 9719 J/oC

m mass of fuel consumed: 1g

E1 - correction for heat of combustion of wire ~ 20.58

E2 correction for heat of combustion of thread ~ 0.175 J

The GCV of the fuels is represented in the table below.

19
 TABLE 5: GROSS CALORIFIC VALUE

Fuel Maximum temperature Gross calorific value

rise (oC) (kJ/kg)
Diesel 4.428 43015

CME 4 38855

NME 3.8 37000

C20 4.38 42597

N20 4.35 42380

4.4 PROPERTIES
Therefore, all the properties of the fuels are summarized as follows in the table below:

TABLE 6: PROPERTIES OF NME AND CME

Fuel Flash Fire Density @ GCV Kinematic

point(oC) point(oC) 30oC (kJ/kg) viscosity
(kg/m3) @40oC
(cSt)
Diesel 65 75 830 43015 2.8

CME 110 116 870 38855 4.69

NME 120 132 854 37000 5

C20 66 76 834.5 42597 2.81

N20 67 77 830.2 42380 2.82

20
 CHAPTER 5

SELECTION OF ADDITIVES

5.1 NEED FOR ADDITIVES IN BIOFUEL

1. COLD STARTING: At very low temperature or at sub-zero temperature the fuel gets
gelled up and requires more oxygen to initiate the combustion process. In such cases
additives with excess oxygen could be added to the fuel so that the combustion process
is enhanced. During the first two minutes after starting the engine the amount of
emissions can be very high and is due to the following reasons

Rich air-fuel ratio requirement in cold engines: When a cold engine is

started, the fuel does not vaporize completely, creating higher emissions of
hydrocarbons, nitrogen oxides and carbon monoxide, which diminishes only as
the engine reaches operating temperature. The duration of this start-up phase
has been reduced by advances in materials and technology, including computer-
controlled fuel injection, shorter intake lengths, and pre-heating of fuel and/or
inducted air.
Inefficient catalytic converter under cold conditions: Catalytic converters
are very inefficient until up to their operating temperature. This time has been
much reduced by moving the converter closer to the exhaust manifold and even
more so placing a small yet quick-to-heat-up converter directly at the exhaust
manifold. The small converter handles the start-up emissions, which allows
enough time for the larger main converter to heat up. Further improvements can
be realised in many ways, including electric heating, thermal battery, chemical
reaction preheating, flame heating and superinsulation.

2. NOX EMISSIONS: Air is a mixture of nitrogen and oxygen. When the fuel in an
engine ignites, there are areas where the temperature is hot enough (above about
1500C/ 2700F) to oxidise some nitrogen to NOx gases. Diesel engines operate at a
higher temperature and pressure. These conditions favour the production of NOx gases.
The quantity depends on the volume and duration of the hottest part of the flame.

Nitrous oxide (N2O), also known as 'laughing gas'.

It is a serious greenhouse gas, and is defined as being 298 times

as bad as CO2 because of its radiative effect, and the time taken
to break it down.
non-toxic. It does react with vitamin B12, which may be a
problem for those who are deficient.

Nitric oxide (NO).

Readily oxidised in the atmosphere to nitrogen dioxide.

Non-toxic in small quantities, infact it serves a vital role as a
regulator within the human body.

21
 Nitrogen dioxide (NO2).

A major pollutant and component of smog. Its brown fumes may

be familiar from school chemistry experiments.
It reacts with water to produce nitric acid, which is why it is so
irritating to the eyes and respiratory tract.

3. POOR OXIDATION STABILITY: Oxidation stability tests have been developed for
estimation of the long term storage stability of diesel fuels. Currently, several oxidation
stability test methods (eg. ENISO12205, Rancimat (EN15751), PetroOXY (EN16091))
are used for this purpose. It is common for these tests to have an elevated temperature
and to add oxygen or air to accelerate the oxidation of the test fuel, and hence accelerate
conduction of the test. Usage of additives improves the oxidation stability of the fuel.

5.2 COBALT OXIDE:

Cobalt (II, III) Oxide [Co3O4] is a nonstoichiometric mixture of the following compounds:

i. Cobalt (II) oxide [CoO], which has Cobalt in Co2+ state

ii. Cobalt (III) oxide [Co2O3] which has cobalt in Co3+ state

Cobalt oxide is synthesized by heating CoO at 600-700oC in air, wherein it reacts with oxygen.

REACTION 5.1: COBALT OXIDE FORMATION

When cobalt oxide is used in its normal form, it has the following disadvantages:

i. Difficulty in creating a stable suspension with diesel

ii. High particle size, therefore it will be held in the injector.
In order to overcome these drawbacks, commercially available cobalt oxide is used as a
nanofuel additive. It is synthesized in one of the following methods that are explained below.

22
 5.2.1 PHYSICAL METHOD:

Fig 5.1 PHYSICAL METHOD

The ball mill method is a top-down process in which a macro scale powder is broken down
into nanopowder by mechanical crushing forces. It consists of a hollow cylindrical shell
rotating about its axis, horizontally. The grinding balls are usually made of chrome steel or
silicon carbide, and the inner surface of the cylinder is coated with rubber to prevent abrasion
from the rotating balls. Fig illustrates the motions that are followed by the cobalt oxide powder
and the ball. The direction of rotation of the milling bowl and turn disc to ensure that centrifugal
forces are alternately synchronized. The material to be ground is fed through the slot on the
right at an angle of 60o and the ground material is discharged through a cone on the left at an
angle of 30o. As the cylindrical shell is rotated, the grinding balls begin to get lifted up in the
direction at which the rotating shell rises and they drop down on the powder when they reach
the top of the shell. This results in high forces acting on the material to be ground, and hence,
its size reduces dramatically, in the four stages as explained below:

i. Initial stage: The powders are flattened by the collisional forces of the milling balls.
However, there is no change in mass.
ii. Intermediate stage: There are significant changes in property, size of the powder is
now in microns. Powder diffusion is not possible.
iii. Final stage: There are considerable changes in particle sizes and microstructure.
The microstructure is now homogeneous. True nanoparticles may have already
been formed.
iv. Completion stage: All changes are irreversible. Cobalt oxide nanopoweder is now
physically available. All mechanical energy supplied by the balls has been used as
physical and chemical energy by cobalt oxide to get converted into nanopowder.

5.2.2 CHEMICAL METHOD:

There are several chemical methods that are used in preparing nanomaterials. However, the
most common one of them is called sol-gel. This method is a bottom up one because it
builds nanomaterial by a molecular dispersion. Theoretically, a sol is a colloidal dispersion

23
of a solid ions in a solvent, whereas gel is a semi-rigid mass which is formed when the sols
solvent evaporate, leading to the left out particles to join together in a continuous network. The
diagrammatic representation of the sol gel method is shown below:

Fig 5.2 CHEMICAL METHOD

In the sol-process of synthesizing nanoparticles, two chemicals are used:

i. Co(NO3)2.6H2O
ii. Oxalic acid

The metal salt is added to double distilled water and mixed continuously for 1 hr. And in
another beaker, the same is done for oxalic acid, for half an hr. The oxalic acid is then added
drop by drop to the metal salt solution with continuous stirring for 3 hours. The resultant pink
precipitate obtained is washed and then dried in an oven @100oC for 5 hours, and then @500oC
in a muffle furnace. Black colored cobalt oxide (Co3O4) particles are then obtained.

5.3 CATALYIC MECHANISM OF COBALT OXIDE:

Due to it being a cobalt compound, Co3O4 is naturally an excellent catalyst. Its catalytic
mechanism is explained as follows:

Co3O4 has a spinal structure in which Co3+ is in octahedral configuration and Co2+ is in
tetrahedral configuration. Since Co3+ is highly unstable due to its oxidation state, it readily
becomes an active site for the oxidation of CO, which in turn is dependent on the two types of
oxygen species:

i. Active oxygen on the surface of CoOx

ii. Lattice oxygen on the surface of Co3O4

24
 Fig 5.3: COBALT OXIDE CATALYTIC MECHANISM

Higher the temperature, the more mobile the active oxygen becomes, thereby making oxidation
of CO easier. The lattice oxygen, however, is more active than the active one and thus forms
an intermediate bidentate carbonate, which could also oxidize CO to CO2. The catalytic
mechanism of Co3O4 is shown in Reaction 5.2, and the star marks (*) represent the active
adsorption sites on Co3O4.

5.4 CREATING THE NANOCOLLOID:

Due to its high surface area and therefore its high surface energy, when cobalt oxide is
suspended in biodiesel, it will begin to agglomerate and thus settle down due to sedimentation.
To prevent this, a surfactant is used. Surfactants are compounds that lower the surface tension
between a liquid and solid and keep the solid suspended in the liquid. Due to cobalt oxide being
anionic, an organic cationic surfactant called cetyl trimethyl ammonium bromide (CTAB,
chemical formula: C19H42BrN), whose chemical formula is C19H42BrN, is used. The structure
of CTAB is illustrated below.

FIG 5.4: CTAB STRUCTURE

5.5 ULTRASONICATION
Ultrasonication is the process by which sound energy is applied to agitate particles in a solution,
using frequencies greater than 20 kHz.

25
 5.5.1 TYPES OF ULTRASONICATORS

i. Probe type
ii. Bath type, and this was used to create the nanofluid.

5.5.2 ULTRASONIC BATH

FIG 5.5: ULTRASONIC MIXER

In this method of ultrasonication, cavitation bubbles (vapor cavities in the liquid) are
created by the high frequency sound, and this agitates the liquid. An ultrasound
generating transducer built into the chamber, or lowered into the fluid, produces ultrasonic
waves in the fluid by changing size in concert with an electrical signal oscillating at ultrasonic
frequency. This creates compression waves in the liquid of the tank which tear the liquid
apart, leaving behind many millions of microscopic voids or partial vacuum bubbles
(cavitation). These bubbles collapse with enormous energy; temperatures and pressures on the
order of 5,000 K and 20,000 psi are achieved. However, they are so small that they do no more
than suspend the particles in the solution by pushing them up. The higher the frequency, the
smaller the nodes between the cavitation points, which allows for mixing of more intricate
detail. The following image depicts the operation of the ultrasonic bath.

26
 FIG 5.6: ULTRASONIC BATH OPERATION

5.6 NANOFLUID FUEL

1. 700 ml of N20/C20 was measured and poured into ultrasonicators container.
2. 140 mg of Co3O4 nanopowder and 140 mg of CTAB were measured and added to the
container.
3. The container was then closed and but in its slot in the ultrasonicator.
4. The machine was turned on and the mixture was ultrasonicated for 2 hours.
5. After ultrasonication, the mixture was poured into a beaker and left untouched for 24
hours to study dispersion stability.
6. There was no settling, and thus a stable nanofluid was made, and run in an engine.

These ultrasonic have large piezoelectric transducer areas and tanks that produce a high-
powered ultrasonic intensity throughout the entire oscillating tank. Constant power and
automatic frequency control ensure optimum distribution of ultrasonic energy and reproducible
results.

27
 CHAPTER 6

ENGINE CHARACTERISTICS

6.1 EXPERIMENTAL SETUP:

FIG 6.1 ENGINE SETUP

FIG 6.2 ENGINE

A single cylinder, four-stroke, water cooled, constant speed of 1500 rpm, direct injection diesel
engine with a rated power of 5.2 kW is used as a test engine for this study. Fig shows the
schematic diagram of the experimental setup. The technical specifications of the engine are
given in the table. An automatic solenoid controlled type burette was used to measure the fuel

28
consumption. An air box fitted between the engine intake manifold and the exhaust pipe is used
to accumulate sufficient air. A manometer fitted in the air box shows the readings of the water
head, which is used to calculate the air consumption of the engine. AVL444 exhaust gas
analyzer is used to measure unburnt hydrocarbon (HC), Carbon monoxide (CO) and Nitric
oxide (NO) emissions. An AVL437C diesel smoke meter is used to measure the smoke density
of the engine exhaust. Initially, the engine is operated with diesel for obtaining the reference
data. Then, the experiments were conducted with C20, N20 and the results were compared with
the diesel data of the same engine. Then the additive was added to C20 and N20 and the
previous results were compared.

TABLE 7: ENGINE PARAMETERS

Engine Make Kirloskar TV1

Type 4 stroke, single cylinder Diesel engine

Cubic capacity 661 cc

Rated power 5.2 kW @ 1500 rpm

Bore x stroke 87.5 x 110 mm

Compression ratio 17.5:1

Orifice diameter 20 mm

Dynamometer type Eddy Current

Dynamometer arm length 185 mm

6.2 EDDY CURRENT DYNAMOMETER:

The working principle of the eddy current dynamometer is shown in Fig 6.3.

FIG 6.3 EDDY CURRENT DYNAMOMETER

29
It consists of a stator on which are fitted a number of electromagnets and a rotor disc made of
copper or steel and coupled to the output shaft of the engine. When the rotor rotates eddy
currents are produced in the stator due to magnetic flux set up by the passage of field current
in the electromagnets. These eddy currents are dissipated in producing heat so that this type of
dynamometer requires some cooling arrangement. The torque is measured exactly as in other
types of absorption dynamometers, i.e. with the help of a moment arm, whose length is 220
mm in this case. The load to be exerted on the IC engine during testing is controlled by altering
the current in the electromagnets.

6.3 EXHAUST GAS ANALYZER

An exhaust gas analyzer, as the name suggests, is used to determine the amount/concentration
of the following gases that come out of the exhaust of an engine:

i. Carbon monoxide (CO)

ii. Nitrogen oxides (NOx)
iii. Unburnt hydrocarbons (HC)
iv. Particulate matter / smoke
Though other gases such as oxygen and carbon dioxide are also emitted, they are neglected in
this case because they are not considered pollutants. To determine the amount of the above
mentioned exhaust gases, several different methods and principles are used. The AVL 444
exhaust gas analyzer used in this project is represented in Fig

FIG 6.4: 5 GAS ANALYZER

The different methods used in determining the amount of exhaust gas in each case is explained
as follows:

i. NDIR for CO & CO2

ii. FID for HC
iii. CLD for NOx
iv. Light extinction meter For smoke measurement.

30
6.4 NON DISPERSIVE INFRARED DETECTOR (NDIR)
The NDIR detector is the industry standard method that is used to determine the percentage of
carbon oxides such as CO and CO2 in the exhaust gas. Its construction and principle is
explained as follows:

FIG 6.5 NON DISPERSIVE IR DETECTOR

This analyzer works on the principle that hetero atomic gases absorb infrared energy at various
wavelengths. Each gas has a unique absorption spectrum in the infrared range of 2.5 12 .
Therefore the absorption of one component in a gas mixture can be selectively measured, the
amount of absorption being a function of concentration of the component and the length of the
absorption path. A chopper wheel mounted in front of the detector continually corrects the
offset and gain of the analyzer, and allows a single sampling head to measure the concentrations
of two different gases.

6.5 FLAME IONIZATION DETECTOR (FID)

The flame ionization detector is the standard engineering apparatus that is used to measure the
concentration of unburnt hydrocarbons (ppm) in the exhaust gas mixture. Its principle is
illustrated in Fig and is explained as follows.

FIG 6.6: FLAME IONIZATION DETECTOR

31
Electric field is applied to a pure hydrogen flame burning in air free that has 0 ppm of
hydrocarbons and a small but measurable ionization current is generated. The addition of
hydrocarbons to the flame results in an increase of the ionization current proportional to the
number of hydrocarbon molecules supplied per unit time. The ionization current order is from
10-14 A to 10-18 A which depends on the measuring span and which is also electronically
amplified. The ionization process is very rapid, so the slow time response of conventional FIDs
is mainly due to sample handling. A typical slow analyzer might have a response time of 1-2
seconds.

6.6 CHEMI-LUMINESCENCE DETECTOR (CLD)

The CLD method is the industry standard apparatus that is used in the measurement of the
oxides of nitrogen that are present in the exhaust gas mixture. Its working principle is illustrated
as shown in Fig.

Nitric oxide (NO) is an unstable molecule which will oxidize to NO2 in the presence of ozone,
as per the following photochemical reaction.

NO + O3 NO2 + O2 + hv (light)

REACTION 6.1 PHOTOCHEMICAL REACTION

If the volumes of the sample gas and excess ozone are carefully controlled, the level of light
emitted during this reaction is directly proportion to the NOx concentration in the gas sample,
and can be measured when the CLD is coupled with a photomultiplier tube or solid state device.

FIG 6.7: FID REACTION

32
6.7 SMOKE DETECTOR
Smoke detectors are measuring instruments that are used to determine the amount of soot
present in the exhaust gas mixture based on its opacity. The AVL 437C light extinction
smoke meter used is shown in Fig.

FIG 6.8: SMOKE DETECTOR

6.8 LIGHT EXTINCTION SMOKE METER

The light extinction smoke meter is shown in Fig. Here the photoelectric cell is used to measure
the smoke. An extinction of light is passed through the sample stream of exhaust gas. Here the
photoelectric cell is lightened by a tungsten filament bulb after traversing a 45 cm column of
exhaust gas. Zero reading on the scale of the output meter occurs with clean air tube and a
reading of 100 on the scale corresponding to the complete observation of light, 1% of light
absorbed is represented as a Hartidge smoke unit.

FIG 6.9: SMOKE METER

6.9 EXPERIMENTAL PROCEDURE:

C20 and N20 were prepared by taking Corn oil Methyl Ester (CME) and Neem oil Methyl
Ester (NME) on a 20% basis by volume and blending them with diesel in separate beakers.
Experiments were initially carried out in an engine using diesel as a fuel in order to provide
base line data, subsequently experiments were conducted, with C20 and N20 blends. Then, a
stable cobalt oxide nano-fluid was made by adding cobalt oxide to and ultrasonicating both
N20 and C20 separately. Then, experiments were carried out. All tests were conducted at

33
optimized conditions of 17.5 compression ratio, 220 bar injector opening pressure and at 23o
CA BTDC injection timing for entire load range at rated engine speed of 1500rpm. The engine
was stabilized before taking all measurements.

34
 CHAPTER 7
PERFORMANCE CHARACTERISTICS

7.1 BRAKE THERMAL EFFECIENCY:

Fig 7.1: LOAD vs BRAKE THERMAL EFFICIENCY

TABLE 8: LOAD AND BTHE TABULATION

Load (kg) Diesel (%) C20 (%) C20 + N20 (%) N20 +
Cobalt Oxide Cobalt Oxide
(%) (%)

0 0.6 0.65 0.8 0.8 0.6

5 20.96 22.17 24.38 22.06 23.87

10 28.95 30.09 30.88 29.79 33.09

15 32.85 34.74 35.32 34.79 37.17

18 35.10 36.53 37.61 36.19 37.63

35
The brake thermal efficiency (BTHE) of the fuels is plotted as a function of load on the engine,
as shown in the figure above. The BTHE was seen to increase with load, and the efficiency of
the biodiesel blends was benchmarked with diesel. Without cobalt oxide, C20 and N20 had
similar efficiencies that were higher than that of diesel due to higher oxygen content, resulting
in a diffusive combustion phase. Upon addition of cobalt oxide, the BTHE of both C20 and
N20 increased notably and was more than that of diesel due to the metal oxide nano-additive
reduced the fuel vaporization time and thus the ignition delay, along with significant reductions
in density and viscosity, thus improving atomization of fuel.

7.2 SPECIFIC FUEL CONSUMPTION:

Load (kg) Diesel C20 C20 + Cobalt N20 N20 +

(kg/kWhr) (kg/kWhr) oxide (kg/kWhr) Cobalt
(kg/kWhr) oxide
(kg/kWhr)

0 1.5 1.396 1.0124 1.305 0.97

5 0.4 0.37 0.38 0.37 0.38

10 0.29 0.28 0.28 0.28 0.28

15 0.25 0.24 0.25 0.25 0.24

18 0.25 0.24 0.24 0.24 0.23

TABLE 9: LOAD AND SFC

36
The brake specific fuel consumption (SFC) for each fuel is plotted with respect to load on the
engine as shown above. At no load condition, SFC is highest because the mixture is rich. Diesel
has the highest SFC when compared to C20 and N20 since the biodiesel blends use up lesser
amount of fuel to produce the same amount of power that the engine would produce when
diesel is the fuel, due to higher oxygen content. After load is increased to 5 kg, there is no
significant difference in SFC values between all blends. When cobalt oxide is added, SFC
decreases even more during starting condition because of the improvement of combustion due
to the catalytic chemical oxidation caused by the nano fuel additive.

COMBUSTION CHARACTERISTICS

7.3 NET HEAT RELEASE RATE:

Fig 7.3: CRANK ANGLE vs HRR

The term combustion is defined as the process in which there is a rapid chemical
combination of a substance with oxygen involving the production of light and heat. The figure
above represents the net heat release (HRR) vs crank angle plot, taken for crank angle between
350 400o to represent the subtle nuances in the plot that cannot be seen when the plot is taken
over the entire cycle. It can be seen that without additive, C20 and diesel have similar curves,
except that C20 ignites at 360o and diesel at around 362o, indicating a crank angle delay. N20
has a higher heat release curve. Neat biodiesel cannot be atomized properly due to its high
molecular weight and viscosity and therefore the HRR will be less. However, when it is taken
in proper proportions and blended with diesel, combustion will greatly improve. This is
because the methyl ester-diesel blend has better volatility due to higher flash and fire points,

37
thereby improving fuel atomization and mixture preparation with air during the ignition delay
period thus giving good combustion characteristics and a higher HRR. Upon addition of nano
additive, the viscosity of the biodiesel blend dropped to 2.57 cSt for C20 and 2.64 cSt for C20
and N20, which further improved atomization and mixing of the fuel. Moreover, the nano
additive is basically a combustion catalyst as explained in the BSFC section and thus it caused
the amount of heat released by C20 to increase, and reduced the delay period for N20 by
approximately 5o when compared to the other fuels, and thus more heat is utilized from the fuel
when cobalt oxide is present in the blend.

7.4 PRESSURE CRANK ANGLE:

Fig 7.4(A): CRANK ANGLE vs PRESSURE

Fig 7.4(B): CRANK ANGLE vs PRESSURE (ENLARGED)

38
The cylinder pressure vs crank angle is a plot that is made between the cylinder pressure and
crank angle for the entirety of all 4 strokes, that is, it is made from a 0-720o, demonstrating the
rise and fall of pressure in the cylinder for each stroke. It is an indicator of the following for a
diesel engine:

i. Ignition delay, and hence cetane number.

ii. Peak pressure developed, and hence the ability of the fuel to mix with air.
C20 and N20 blends have higher peak pressures than that of diesel due to their higher oxygen
content and cetane number which keep ignition delay as low as possible, and the peak pressure
as high as possible, thus indicating good combustion results. When cobalt oxide additive is
added, its lattice oxygen acts as a buffer source which further enhances the combustion
properties of the fuel, thus increasing peak pressures and reducing ignition delays. In <figure>,
diesel has the lowest peak pressure of ~63 bar, while C20 and N20 both have approximately
the same peak pressure of around 66 bar. Upon addition of cobalt oxide, their peak pressures
increase to 68 bar and 69 bar respectively, indicating that ignition delay is quite low, and that
the amount of power developed is higher.

39
 CHAPTER 8
EMISSION CHARACTERISTICS
8.1 CARBON MONOXIDE (CO):

Fig 8.1: LOAD vs CO

TABLE 10: CO EMISSION

Load (kg) Diesel (%) C20 (%) C20 + N20 N20 +

Cobalt oxide Cobalt oxide
(%) (%)

0 0.01 0 0 0 0

5 0.02 0 0 0 0

10 0.057 0 0 0.024 0.008

15 0.11 0.051 0.017 0.06 0.006

28 0.163 0.112 0.088 0.117 0.086

The figure above shows the plot for CO vs load. CO is an indication of incomplete combustion.
Diesel lacks oxygen and thus it does not combust completely. Upon blending with methyl
esters, it receives an oxygen boost and thus shows excellent combustion properties. Higher
oxygen supplied by methyl esters oxidizes CO to CO2.

2CO + O2 2CO2

40
 REA 8.1: CO EMISSION

Upon addition of nano additive, CO emissions reduce due to reduction in soot oxidation
temperature and secondary atomization. Furthermore, there is oxygen enrichment in oxygen
content due to surface and lattice oxygen, which facilitates oxidation of CO into CO2. N20 with
cobalt oxide has the least CO emissions due to it already having higher oxygen content.

8.2 UNBURNT HYDROCARBONS (HC):

Fig 8.2: LOAD vs HYDRO-CARBON EMISSION

TABLE 11: HC EMISSION

Load (kg) Diesel (ppm) C20 (ppm) C20 + N20 (ppm) N20 +
Cobalt Oxide Cobalt Oxide
(ppm) (ppm)

0 1 4 2 6 5

5 8 8 5 7 8

10 27 17 10 23 19

15 75 71 65 73 68

18 106 98 84 100 9

The plot above shows the proportions of unburnt hydrocarbons plotted as a function of load.
As load increases, amount of HC in the exhaust emissions also increases in a non-linear fashion.
At no load, diesel has the lowest HC emission among all other fuels, but however the overall
HC emission is lower for other fuels. This is because the fuel rich zones in the chamber during

41
combustion are reduced due to higher fuel bound oxygen. The following are the main reasons
for HC production:

i. Flame quenching
ii. Fuel rich zones
iii. Misfiring.
Methyl esters have higher cetane numbers due to which they have lower ignition delay.
This, along with improvement in atomization reduces reducing fuel quenching and
misfiring. When cobalt oxide is added, it gives its lattice oxygen and acts as an auxiliary
oxygen source, thus reducing fuel rich zones & further improving atomization and hence a
further drop in HC emissions is seen. Furthermore, fuel droplet containing cobalt oxide
results in secondary atomization, and thus the fuel burns completely, reducing the HC
emission even more. C20 with cobalt oxide gives the least overall HC emission, followed
by N20 with cobalt oxide.

8.3 OXIDES OF NITROGEN (NOX):

Fig 8.3: LOAD vs NOx

42
 TABLE 12: NOx EMISSION

Load (kg) Diesel (ppm) C20 (ppm) C20 + N20 (ppm) N20 +
Cobalt oxide Cobalt oxide
(ppm) (ppm)

0 155 184 188 208 191

5 535 516 577 452 484

10 1119 1230 1154 1205 1163

15 1672 1762 1663 1808 1698

18 1903 2073 2052 2063 1989

In diesel engine exhaust, NOx primarily consists of NO with a small amount of NO2. Other
oxides such as N2O, NO3 are considered negligible. There are three types of mechanisms by
which NOx is formed:

i. Fuel NOx high nitrogen content

ii. Thermal NOx high temperatures in the combustion chamber
iii. Prompt NOx
In diesel engines, thermal NOx is the major contributor to emissions due to high cylinder
temperature because of combustion. Due to this, N2 and O2 react to give NO through the
following reaction:

N2 + O2 2NO

REA 6.2: NOx EMISSION

The rate at which NOx forms increases as temperature increases. The figure shows NOx vs load
plot, and the ppm of NOx emitted shows an increasing trend with load. It is observed that the
biodiesel blends have higher NOx emissions due to better combustion which causes higher
cylinder temperatures than that of diesel, and also due to their higher oxygen content which
further promotes NOx production. N20 produces the overall highest amount of NOx. When
nano additive is added, there is an effective reduction in NOx and it shows better results at all
loads. Since it is an active metal oxide catalyst, it promotes the decomposition of NOx. The
results obtained upon addition of additive are better than that of N20 and C20 with additive,
but still diesel has the best NOx emissions since the temperature reached during combustion
are lesser than the temperatures achieved when methyl ester blends are used.

43
 8.4 OPACITY

Fig 8.4: LOAD vs SMOKE OPACITY

TABLE 13: SMOKE OPACITY

Load (kg) Diesel (%) C20 (%) C20 + N20 (%) N20 +
Cobalt oxide Cobalt oxide
(%) (%)

0 2.4 2.4 1.8 2.6 1.5

5 5.5 5.5 3.5 4.4 3.7

10 9.5 9.5 4.8 8.2 5.7

15 27.2 26 15.6 20.7 16.1

18 48.9 42.7 37.8 43.1 34.1

Smoke is nothing but soot suspended in the exhaust due to improper combustion of fuel. It is
produced due to the following reasons:

i. Incorrect air-fuel ratio

ii. Low cetane number
iii. Ignition delay
iv. Higher injection nozzle dia
v. Low quality lubricating oil
vi. Poor engine maintenance.

44
 Diesel gives the highest amount of smoke, while biodiesel gives significantly lesser amounts.
Therefore the addition of methyl ester to diesel gave a reduction in overall smoke emission.
The amount of smoke was determined by opacity method. The plot is shown above, and opacity
is plotted against load. Upto 50% of the load, C20 and diesel had similar opacity, after which
C20 had lesser opacity. N20 had lesser opacity than C20 and diesel. This is because of the
following reasons:

i. Improved oxidation due to higher oxygen content

ii. Higher combustion temperature
iii. Longer combustion duration
iv. Rapid flame propagation
Upon addition of cobalt oxide, the smoke content in the exhaust goes down even more. This is
once again due to both lattice and active oxygen of cobalt oxide, which further enhances the
reasons listed above. Moreover, cobalt oxide reacts with carbon in the soot to give carbon
dioxide, therefore giving very small amounts of smoke. N20 with cobalt oxide has the least
opacity.

45
 CHAPTER 9
CONCLUSION & FUTURE SCOPE

9.1 CONLUSION
In todays energy and pollution crisis, biodiesel has proved to be a valuable alternative.
It can virtually be made from any source of oil, be it poultry fat, used cooking oil or fresh
vegetable oil. The results of the engine test are summarized below:

i. Vegetable oils, in their raw form are highly viscous, and to solve this,
transesterification is a simple solution.
ii. The acid treatment of Neem oil improved its yield by approximately
20%.
iii. The fuel properties of both C20 and N20 are closer to that of diesel.
iv. Corn methyl esters and neem methyl esters serve as an excellent
blending agent with diesel due to their higher oxygen content, and thus
C20 and N20 give good results except one drawback: NOx emissions,
which are one of todays major problems.
v. The experimental investigation of the nano-fuel additive cobalt oxide
added in 200 ppm quantity gave positive results, giving higher BTHE,
BSFC, HRR and reducing all emissions, including NOx. However, even
though NOx emissions reduced, diesel still has lesser emissions. Some
more research may be done by increasing the concentration of the
additive in the biodiesel blend, or doing some modifications to the
engine, which may result in lesser NOx emissions.

9.2 FUTURE SCOPE

The World Energy Information Administration's (EIA) recently released report projects that
world energy consumption will grow by 48% between 2012 and 2040. Most of this growth will
come from countries that are not in the Organization for Economic Cooperation and
Development (OECD), including countries where demand is driven by strong economic
growth, particularly in Asia. Non-OECD Asia, including China and India, accounts for more
than half of the world's total increase in energy consumption over the projection period. India
still in the stage of development will be the hub for energy in the future and production of
biodiesel will account to GDP growth of the country and also will meet the norms accepted by
climate change G20 summit.

Concerns about energy security, effects of fossil fuel emissions on the environment, and
sustained, long-term high world oil prices support expanded use of non-fossil renewable energy
sources and nuclear power. Renewables and nuclear power are the world's fastest-growing
energy sources over the projection period. Renewable energy increases by an average 2.6% per
year through 2040; nuclear power increases by 2.3% per year.

46
Even though nonfossil fuels are expected to grow faster than fossil fuels (petroleum and other
liquid fuels, natural gas, and coal), fossil fuels still account for more than three-quarters of
world energy consumption through 2040

Fig 9.1: 2040 NON FOSSIL FUEL GROWTH PRODUCTION

Although liquid fuelsmostly petroleum-basedremain the largest energy source, the liquids
share of world marketed energy consumption is projected to fall from 33% in 2012 to 30% in
2040. As oil prices rise in the long term, many energy users adopt more energy-efficient
technologies and switch away from liquid fuels when feasible.

Fig 9.2: GLOBAL RENEWABLE DIESEL PRODUCTION

SOURCE: US ENERGY ADMINISTRATION (DEPARTMENT OF RENWABLE

ENERGY)

47
Coal is the world's slowest-growing energy source, rising by only 0.6% per year through 2040.
Throughout the projection period, the top three coal-consuming countries are China, the United
States, and India, which together account for more than 70% of world coal consumption. China
alone currently accounts for almost half of the world's total coal consumption, but a slowing
economy and plans to implement policies to address air pollution and reduce carbon dioxide
emissions mean that coal use in China will begin to decline in the later years of the projection
period. Coal use in India continues to rise and surpasses U.S. coal consumption after 2030.
This brings about a need for alternative fuels or renewable sources of energy and biodiesel can
solve this need.

Fig 9.3: CLEAN ENERGY GROWTH

48
 CHAPTER 10

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