CHAPTER 1:

INTRODUCTION

1
 1. INTRODUCTION
1.1 Background
There is a huge increase in consumption of energy with progressing rate of development,
population and the need for daily use equipment’s of all sorts. The equipment’s that are used today
runs mostly on electricity, produced largely from fossil fuels, which increase level of greenhouse
gases and air pollution. It is estimated that the oil reserves of our planet would last 50 to 70 years
from now. There is a paramount need to find sources of energy, which would fulfill the demands of
today without compromising the tomorrow and that too with a clear concept of creating less
pollution as compared to the conventional fuels. Even increasing energy efficiency of the currently
used conventional fuels can do the work.

Air pollution is increasing at an alarming rate every year leading to various outcomes, impacting
health of living beings, polluting water, eating away the infrastructure, reducing visibility and
affecting natural phenomenon which is resulting in acid rain, smog and global warming. The major
causes of air pollution are; firstly, emissions from manufacturing activities and industrial processes
and secondly, emissions from engines of transportation vehicles. There are number of methods
being applied to control the rate of air pollution and it is important to bring new alternative
approaches to reduce air pollution and its effect. This can be done either by increasing efficiency of
the processes or introducing new sources of energy.

Automobile sector is one of the most rapidly changing sectors in the world. Automobiles are,
without a question, important for all. These are run with different types of engines namely diesel
engine, petrol/gasoline engine and engines that run on electricity. The conventional process of an
engine is to convert the chemical energy into thermal energy and then ultimately obtaining
mechanical energy in the end. During the process of combustion i.e. conversion of fuel into heat,
several by products are formed apart from power. These byproducts are HC, CO, CO 2, NOx, etc.
which result from incomplete combustion of fuel. These compounds act as primary pollutants to
the environment and results in formation of secondary pollutants such as ozone, causing
degradation of atmosphere.

This project deals with introduction of a new modified fuel, a combination of mineral diesel and
biodiesels obtained from different plants and tyre pyrolysis oil (TPO) obtained from scrap tyres
which can help out our fossil energy to last longer and provide us with solutions to problems
2
regarding rapid degradation of the fuel and one of the major causes of air pollution i.e. emissions
from automobile engines.

Biodiesel and TPO has been greatly studied and used as an alternative to diesel, due to its similarity
with diesel in many aspects.

Palm Biodiesel- Mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal
fats, irrespective of its link with diesel fuel do not contain any aromatic hydrocarbons, heavy metals
or crude oil residue and have very low sulfur content. Although biodiesel fulfill many standards to
be used in place of diesel fuel, it is not generally used directly in diesel engines; rather it is mixed
with pure diesel in various proportions to be used in a diesel engine.

Biodiesel is a natural and renewable domestic fuel alternative for diesel engines made from
vegetable oils and plant oils. It contains no petroleum, is nontoxic and biodegradable. Biodiesel is
made using an alcohol like methanol and a chemical process that separates glycerin and methyl
esters (biodiesel) from fats or vegetable oils.

Tyre pyrolysis oil - tyre Pyrolysis oil is a synthetic fuel under investigation as substitute
for petroleum. It is extracted by waste tyres to liquid technology of destructive distillation from
tyres in a reactor at temperature of about 500 °C with subsequent cooling. Pyrolysis oil is a kind
of tar and normally contains too high levels of oxygen to be a hydrocarbon .Which results in non-
volatility, corrosiveness, being immiscible with fossil fuels, thermal instability and a tendency to
polymerize with exposure to air. As such it is distinctly different from similar petroleum products.

Pyrolysis is the process of thermally degrading a substance into smaller, less complex molecules.
Pyrolysis produces three principal products: such as pyrolytic oil, gas and char. The quality and
quantity of these products depend upon the reactor temperature and design. A range of different
reactors, such as fixed-bed (batch), screw kiln, rotary kiln, vacuum and fluidised-bed have been
used for pyrolysis of waste tyres.

Alternative fuel’s like Palm Biodiesel and Tyre pyrolysis oil have become more attractive recently
because of its environmental benefits and the fact that it is made from renewable resources. These
are the methods of choice to lower the production cost. Researchers in various countries have
carried out experimental researches using vegetable oils and biodiesel as petroleum fuel substitutes.

3
Moreover, Vegetable oil methyl esters and blends of TPO gave performance and emission
characteristics comparable to that of diesel.

1.2 Objective
It is proved that biodiesel can be used as fuel additive as well as fuel. In this work Tyre pyrolysis oil
is obtained from Tpo plant and biodiesel obtained from two different plants are mixed together to
form a hybrid biodiesel and then it is mixed in different proportions with pure diesel. The main
objectives of this project work are:
1. To study the physical characteristics of newly formed fuel to understand the effect of
biodiesel and Tyre pyrolysis oil on performance and exhaust emissions parameters of diesel
engine.
2. Assess the exhaust emissions and performance characteristics of the diesel engine, which
would be running with similar proportions of blends of biodiesels and diesel.

1.3 Justification of work

The present work is based on determining a diesel fuel alternative. Since the petroleum reserves of
the world is depleting day by day and its consumption is increasing day by day. It is imperative to
find a solution to this problem or otherwise huge problems regarding fuel deficiency may come in
coming few years. There is also one big issue about environmental degradation caused by currently
used conventional fuels. There is need to find a solution to this problem otherwise it would be
difficult to control the environmental responses if the limits of its degradation are crossed. Overall,
there is need to find a fuel alternative which can work as diesel substitute and cause less harm to
environment as compared to the currently used conventional fuels. Biodiesel, obtained from waste
palm oil or cooking oil sources has the potential to do the work, which makes it suitable for the
current study and TPO is another oil obtained from heating the waste tyres and obtaining oil that
can be used in a diesel engine.

This alternative will not only save environment but also reduce the cost of fuel.

1.4 Definition of Terms

Some common technical terms that are used throughout the course of work are:
Brake Power is the useful power obtained at output shaft.

4
Brake Specific Fuel Consumption is a measure of the fuel efficiency of any prime mover that
burns fuel and produces rotational, or shaft, power. It is typically used for comparing the efficiency
of internal combustion engines with a shaft output.
Cetane Number is an indicator of the combustion speed of diesel fuel.  The CN is an important
factor in determining the quality of diesel fuel. The higher the CN the smoother is the combustion.
Dynamic Viscosity of a fluid expresses its resistance to shearing flows, where adjacent layers move
parallel to each other with different speeds.
Kinematic Viscosity of a fluid is ratio of dynamic viscosity to its density.
Thermal efficiency indicates how well an energy conversion or transfer process is accomplished.
Thermal stability of a fuel is defined as the capability of the fuel to withstand high temperature
stress for a reasonable time period without noticeable deterioration. Such deterioration may include
color change, formation of solid deposits, changes in physical properties, chemical properties and
combustion properties, etc.

5
 CHAPTER 2:
PALM BIODIESEL

6
 2 PALM BIODIESEL

2.a.1 Palm oil -

Palm oil is an edible vegetable oil derieved from the mesocrap (reddish pulp) of the fruits of the oil
palms, primarily the African oil palm Elaeis guineensis, and to a lesser extend from the American
oil palm Elaeis oleifera and the maripa palm Attalea maripa.

Palm oil is naturally reddish in colour because of a high beta-carotene content. It is not to be
confused with palm kernel oil derieved from the kernel of the same fruit, or coconut oil derieved
from the kernel of the coconut palm. Palm mesocarp oil is 49% saturated, while palm kernel oil and
coconut oil are 81% and 86% Saturated fats, respectively.

The major advantage of palm oil is its high stability during frying that produced minimum amount
of breakdown products in an acceptable level.

But the problem with the oil is that it cannot be reused for cooking or frying after used once.The
problem with reusing oil is that it can create free radicals which cause ailments in the long run.
According to diet consultant Naini Setalvad, ‘Free radicals attach themselves to healthy cells and
lead to diseases. These free radicals can be carcinogenic i.e. can cause cancer and also
atherosclerosis which can lead to increase in bad cholesterol levels, blocking the arteries.’

Some other potential health risks of reusing oil include:

 Acidity
 Heart disease
 Alzheimer’s and Parkinson’s disease
 Irritable throat (due to inhalation)

But neither is it environmental friendly to dispose used cooking oil just like that. The best solution
is to used it for industrial purposes, namely to reproduce into biodiesel.

2.a.2 Literature review -

Biodiesel is an alternative diesel fuel derived from vegetable oils or animal fats.
The main components of vegetable oils and animal fats are composed of 80–90% triglycerides with
small portion of mono and di-glycerides, which contain oxygen in their structure.

7
Diesel fuels from petroleum sources have chemical structure different from chemical structure of
vegetable oils. A Diesel fuel has no oxygen compound, it contains carbon and hydrogen arranged in
straight and/or branched chain structures. Further research is desired before substituting diesel fuels
with vegetable oils. Researchers recognized different complications related to the use of oil in diesel
engine, due to their high viscosity and low volatility so they form deposits in the fuel injector of the
engine.
These problems can be solved by dilution, micro emulsion, pyrolysis, and transesterification.
Transesterification is the reaction of oil with an alcohol in presence of catalyst to form ester and
glycerol. The methyl esters produced by transesterification are called biodiesel, which has a low
viscosity and high cetane number.
Dilution of diesel with vegetable oil is conducted by mixing and stirring. No negative effect has
been observed because of shortterm engine tests using diesel and biodiesel blends. The carbon
deposits observed with diesel/vegetable oil mixture on combustion chamber parts are similar to that
observed when operating with 100% diesel fuel triglycerides or also known as ester of fatty acid
attached to glycerol.
Clark et al. reported that rapeseed methyl esters of soybean and other seed oils showed a similar
performance to diesel fuel in diesel engines.
Peterson et al. used rapeseed ethyl esters in truck’s operation and reported that no difficulties or
unusual behavior was observed.Peterson et al. also mentioned that the biodiesel can be used in a
blend with diesel fuel in a diesel engine.
However, the properties of oil/biodiesel–diesel blends fuels are changing as a function of volume
fraction of oil/bio diesel in mixture.There are several key properties, which need to be characterized
before using oil/biodiesel–diesel fuel blends in a diesel engine.These properties are kinematic
viscosity, density, and flash point of the blend.
It is important to figure out if the properties of the blended fuel meet the standard properties of
diesel fuel requirements.
To better predict fuel properties, mixing rules are developed as a function of oil/biodiesel volume
fraction in the blend.
The term waste cooking oil (WCO) refers to vegetable oil has been in food production and which is
no longer viable for its intended use.
WCO arises from many different sources, including domestic, commercial and industrial.

8
WCO is a potentially problematic waste stream which requires proper management.
The disposal of WCO can be problematic when disposed incorrectly.
Any fatty acid sources may be used to produce biodiesel. Therefore, any animal or plant lipid
should be ready substrate for the production of biodiesel.
The use of edible vegetable oils and animal fats for biodiesel production has recently been of great
concern because they compete with food material- the food versus fuel dispute. There are concern
that biodiesel feedstock may compete with food supply in the long term. From an economic point of
view; the production of biodiesel is very feedstock sensitive. The cost of feedstock accounted for
88% of total estimated production cost. In all cases, more than 80% of the production cost is
associated with the feedstock, such as recycled cooking oils. Reusing of these waste greases not
only reduce the burden of the government in disposing the waste, maintaining public sewers, and
treating the oily wastewater, but also lower the production cost of biodiesel significantly.

2.a.3 Production of Biodiesel

Ghaly et al. (2010) reported that the research on the production of biodiesel has increased
significantly in recent years because of the need for an alternative fuel, which endows with
biodegradability, low toxicity and renewability.

In today’s scenario, the most appropriate method to use the vegetable oils in CI engines is through
its conversion into fatty acid methyl ester by the process of trans-esterification, Agarwal and Dhar
(2013).

Theansuwan and Triratanasirichai (2011) concluded that the biodiesel produced by

transesterification showed similar properties to the standard biodiesel. Agarwal et al.
(2008) investigated that the process of transesterification is found to be an effective method of
reducing viscosity of vegetable oil.

As discussed there are number of researches, which shows that biodiesel can be used as a substitute
as well as an additive to the conventional fuels. There also occurs change in properties of the fuel
when biodiesel is mixed with diesel like change in thermal stability, cetane number, dynamic and
kinematic viscosity, density, calorific value, etc.

2.a.4 Experimental Analysis of Biodiesel

9
Abedin et al. (2014) explained that high kinematic viscosity and density fuels with lower calorific
value tend to increase the brake specific fuel consumption and lower the brake power as it results in
poor atomization of fuel during spraying of fuels inside the combustion cylinder. Due to presence of
high amount of oxygen molecules in biodiesel resulting in complete combustion of fuel, it was
found that the hydrocarbons and carbon monoxide emission were lower than diesel. For nitrogen
oxides emission, the in-cylinder temperature is an important factor, as high temperature results in
higher emission. In many experiments, there has been decrease in nitrogen oxides emission with
biodiesel perhaps due to the fact that in-cylinder temperature is lower which can be due to low
calorific value of the fuel.

Jain and Sharma (2011) reported that the vegetable oil, fats and their biodiesel suffer with the
drawback of deterioration of its quality during long-term storage unlike petroleum diesel due to
large number of environmental and other factors making the fuel stability and quality questionable.
There are various types of stabilities like oxidation, storage and thermal, playing key roles in
making the fuel unstable. Their attempt was to review the work done so far on the thermal stability
of biodiesel and their blends with diesel under different conditions. TGA/DTA has been found as an
effective method to check the deterioration of oil with respect to temperature using activation
energy and order of reaction as the parameter to monitor the deterioration of oil.

Silva et al. (2014) reports on the synthesis of methylic and ethylic biodiesels from pequi oil using
the transesterification reaction process via alkaline homogeneous catalysis. Thermo gravimetric
studies helped to evaluate the thermal stability of the biodiesels. A methanol/ethanol 20:80 (w/w)
alcoholic solution furnished the ethylic biodiesel and allowed for straightforward optimization of
the biodiesel–glycerin phase separation. Classic physicochemical analyses, gas chromatography–
mass spectrometry (GC–MS), infrared spectroscopy (FT-IR), and proton nuclear magnetic
resonance (1H NMR) aided characterization of the synthesized biodiesel samples.
Thermogravimetric analysis (TGA) provided information about the thermal decomposition kinetics
of pequi biodiesels. The biodiesels showed satisfactory thermal stability and qualified as potential
substituents of conventional mineral diesel.

Ladommatos and Goacher (1995) studied that the standard measure of the ignition quality of a
diesel fuel is the cetane number (CN). The aniline point is correlated very highly with the cetane
number. This is thought to be because the aniline point reflects well the balance of the different

10
hydrocarbon compounds in the fuel. In particular, it is a good indication of the balance between the
easy to ignite long-chain paraffins, and the more stable branched and cyclic compounds in the fuel.

2.a.5 Biodiesel Blends in Diesel Engine

Wang et al. (2006) confirmed that, the vegetable oils possess almost the same heat values as that of
diesel fuel. The engine power output and the fuel consumption of the vegetable oil and its blends
are almost the same when the engine is fueled with diesel.

Lawrence et al. (2011) revealed that prickly poppy methyl ester (PPME) blended with diesel could
be conveniently used as a diesel substitute in a diesel engine. The test further showed that there was
an increase in break thermal efficiency, brake power and reduction of specific fuel consumption for
PPME and its blends with diesel.

Deepanraj et al. (2011) described that the lower blends of biodiesel (palm biodiesel) increased the
brake thermal efficiency and reduced the fuel consumption. In addition to this, biodiesel blends
produce lower engine emissions than diesel.

Muralidharan and Govindarajan (2011) prepared biodiesel from non-edible pongamia pinnata oil by
transesterification and used as a fuel in C.I engine. The authors reported that blend B5 exhibits
lower engine emissions of unburnt hydrocarbon, carbon monoxide, oxides of nitrogen and carbon
dioxide at full load.

Venkatraman and Devaradjane (2011) performed the experiments in a single cylinder DI diesel

engine fueled with a blend of pungam methyl ester for the proportion of PME10, PME20 and
PME30 by volume with diesel fuel for validation of simulated results. The authors observed that
there is a good agreement between simulated and experimental results.

Srivastava and Verma (2008) carried out the experiments using methyl ester of karanja oil. The
authors reported that, the maximum thermal efficiency with methyl ester of karanja oil was about
24.9%, whereas that of the diesel was 30.6% at maximum power output. The authors concluded
that, the methyl ester of karanja oil is a suitable substitute of diesel.

Kumar et al. (2003) conducted the experiments using pure jatropha oil, jatropha methyl ester,
blends of jatropha and methanol and dual fuel operation (0–80% methanol by volume is inducted

11
and jatropha acts as pilot fuel). The authors reported that, brake thermal efficiency for jatropha
esters, dual fuel operation and diesel was 29%, 28.7% and 30.2% respectively.

Ramadhas et al. (2008) studied the dual fuel mode operation using coir-pith derived producer gas
and rubber seed oil as pilot fuel. The authors reported that, non-edible oils can be used as pilot fuel,
which eliminates the use of petroleum diesel.

Rahimi et al. (2009) used Diesterol (combination of diesel fuel, bioethanol and sunflower methyl
ester) as a fuel for diesel engines. The authors revealed that, as the percentage of bioethanol in the
blends is increased, the percentage of CO concentration in the emission is reduced. This trend is
because bioethanol has less carbon than diesel. 

Mani et al. (2009) investigated the diesel engine runs with waste plastic oil as fuel. The authors
concluded that, the smoke was reduced by 40% than diesel.

Nwafor (2004) studied the potential of rapeseed methyl ester and its blends with diesel fuel as
alternative substitute for diesel fuel. The author described that, the fuel consumption of rapeseed
methyl ester was little higher than diesel fuel operation. Forson et al. (2004) found that, jatropha oil
could be conveniently used as a diesel substitute, in a diesel engine.

Ozsezen and Canakci (2011)experimented that in six cylinder engine running with palm biodiesel,
the brake power decreased about 2.5% and bsfc increasing 7.5% with reports of lower smoke,
hydrocarbons and CO emission but higher NOx emission compared to diesel fuel. 

From the review of literatures, numerous works in the utilization of biodiesel as well as its blends in
engines have been done. However, most of the literatures focused on single biodiesel and its blends.
From previous studies, it is evident that single biodiesel offers acceptable engine performance and
emissions for diesel engine operation.

2.a.6 About the Present Work

It is found that there have been many researches regarding biodiesel and its blends but there are
very few researches on blending of two biodiesel to form a dual biodiesel having properties of both
kinds of biodiesel. This experiment introduces a dual biodiesel, mixture of two different kinds of
biodiesel, having attributes of both the biodiesels. The two biodiesels used for this purpose are of

12
palm and jatropha. It is imperative to understand the physical properties of newly formed biodiesel
mixture and the changes in properties when mixed with diesel in different proportions..
Determination of physical characteristics of fuel is required as it is combination of different fuels.
For determination of physical characteristics of mixture of fuels, viscosity and density test, calorific
value test thermo gravimetric analysis and aniline point test carried out. These tests and analysis
would provide the sufficient information regarding expected behavior of the mixture of fuels. The
major part of work is concluded when the mixture of fuels is tested on a direct injection, four
stroke, single cylinder, compression ignition engine. It provided the data regarding the performance
of modified fuel and exhaust emissions of CO, CO2, NOx, echaust gas temperature, etc. from the
engine when used with the dual biodiesel blends i.e. biodiesel-biodiesel and diesel blends.

13
CHAPTER 2(b):
METHODOLOGY

14
 2.b METHODOLOGY

Based on Fig. 1 it is recognized that the production of waste cooking oil will be the function of the
frying temperature and length of use as well as the material used for frying.

WCO is collected from local Factory’s. The oil sample is assumed to be representative as it is
collected from the oil stored for 8-10 weeks from several batches of waste oil. The temperature is
observed during the use of oil collected.However, it was found difficult to read the temperature in
boiling oil which gives approximately 5-10% error. Depending on the quantity of food used for
frying or other cooking works, the oil was discarded sometimes at the end of each day and
sometimes once in two or three days.

15
2.b.2 Free Fatty Acids -
Flow chart in Fig. 1 shows the relation between FFA and process. Which FFA less than 2%, the
process can directly to transesterification process and while FFA more than 2% it need to start from
esterification process to reduce FFA. The acid value of the waste cooking oil was determined in
order to estimate the free fatty acid content and give an idea of how much acid catalyst and
methanol would be needed to push the acid esterification chemical towards methyl ester production.
In earlier published research it was recommended that 0.5 - 1.5% (based on the weight of free fatty
acid in the oil) of pure (95-98%) sulphuric acid should be used as a catalyst. Acid value titration
method was used according to BP monograph.

2.b.3 Processing in Biodiesel –

Biodiesel has two main stage process is esterification and tranesterification process. Separation was
used to separate two layer between catalyze and oil. Washing process to produce the neutral
biodiesel and remove catalyzes glycerol, soap and methanol.

2.b.3.1 Esterification -
Based on flow chart in Fig. 1 esterification is one of process in biodiesel. It work to reduce FFA if
FFA more than 2%. An acid-catalyzed esterification process before the base-catalyzed
transesterification process will eliminate most of the free fatty acids from the vegetable oil.
Sulphuric acid (95 – 98%) is used by 1% in esterification process depend from waste cooking. In
these experiments the sulphuric acid was first mixed with methanol before adding to the waste
cooking oil. After adding the methanol / sulphuric acid and waste cooking oil the agitator speed
were used to mix the solvents until they became murky. This was then heated to about 60° C for 2
hours. A higher temperature or a faster stirring rate may push the acidic esterification equation to
convert free fatty acid to methyl ester.

1) Separation 1 –

Separation needed 3hour to get the top methanol and bottom oil layers of the biodiesel. Two layers
could clearly be seen in the successful basic esterification biodiesel. The top layer was mainly

16
methanol. The bottom layer was mainly triglyceride product esterification after remove the water.
These processes to reduce free fatty acid until below 2%. The density of the methanol is less than
the bottom triglyceride.

2.b.4 Transesterification –
Transesterification process work as to reduce viscosity in biodiesel. This process can be directly if
FFA less than 2% show in fig. 1. Sodium hydroxide was used as catalyst in this process. The
amount of catalyst had an impact in the conversion of esters during the transesterification process.
The reaction was carried out using 1% of catalyst concentration. Before tranesterification process
Sodium hydroxide was first mixed with methanol together in one container before adding to the
waste cooking oil. After adding the methanol / sodium hydroxide and waste cooking oil the agitator
speed were used to mix the solvents until they became murky. This was then heated to about 60° C
for 2 hours.

2) Separation 2 –
Transesterification process and any methanol evaporation the resultant biodiesels were left to lie for
at least 8 hours. Separations were used to separate the top (methyl ester) and bottom (glycerol)
layers of the biodiesel samples. Two layers could clearly be seen in the successful basic
transesterification biodiesel samples. The top layer was mainly composed of free fatty acid methyl
esters. The bottom deposit was mostly made up of glycerol, salts, soap, other impurities and excess
methanol as it is a very polar compound i.e. it partitions more with polar glycerol as opposed to the
non-polar methyl esters.

2.b.5 Washing –
The top methyl ester layer was separated and removed from every production sample. The water
washing process was then used on some of the biodiesel batches. Once separated from the glycerin
the biodiesel is sometimes purified by washing gently with warm water to remove residual catalyst
or soaps, dried, and sent to storage. In some processes this step is unnecessary. This is normally the
end of the production process resulting in a clear amber-yellow liquid with a viscosity similar to
petrodiesel. In some systems the biodiesel is distilled in an additional step to remove small amounts
of color bodies to produce a colorless biodiesel.

17
18
 CHAPTER 2(c):
PHYSICAL PROPERTIES

19
 2.c PHYSICAL PROPERTIES

Properties are one of method to determine the standard of biodiesel. Biodiesel can check using
density, viscosity, flash point, acid value and water content.

1 Density –

Fig. 7 shows how to measure density using pycnometer. The density of biodiesel at 15⁰C was found
to be 87 g/cm3 that density is a function of temperature and decreased linearly for canola methyl
esters, soy methyl esters, and fish oil ethyl esters by 1.23 kg/m3 ⁰C for temperatures between 20–
300⁰C.

2 Kinematic viscosity –

20
Fig. 8 is equipment for testing kinematic viscosity and Standard method for kinematic viscosity is
ASTM D 445 – Kinematic viscosity, 40 º C, requirement: 1.9 – 6.0 mm2/s. Kinematic viscosity:
“the resistance to flow of a fluid under gravity”. The kinematic viscosity is equal to the dynamic
viscosity/density the kinematic viscosity is a basic design specification for the fuel injectors used in
diesel engines. Too high a viscosity and the injectors do not perform properly. Dynamic viscosity –
‘ratio between applied shear stress and rate of shear of a liquid.” Density – “the mass per unit
volume of a substance at a given temperature.” The viscosity of biodiesel can be predicted ± 15 %
using the esters composition determined using ASTM D 6584. The viscosity apparatus to run D 445
is not critical to the QC laboratory, but it is valuable as a quick assay method for estimating the
degree of completion for a reaction batch.

3 Flash point –

Fig. 9 show the equipment for testing combustion in biodiesel using method ASTM D93- Flash
point, closed cup, requirement 130 ºC min. The flash point is defined as the “lowest temperature
corrected to a barometric pressure of 101.3kPa (760 mm Hg), at which application of an ignition
source causes the vapors of a specimen to ignite under specified conditions of test.”

21
 4 Acid number –

Fig. 10 is testing for acid value using method ASTM D 664 – Acid number, requirement 0.80 mg
KOH/g. The acid number is “The quantity of base, expressed as milligrams of potassium hydroxide
per gram of sample, required to titrate a sample to a specified end point.” The acid number is a
direct measure of free fatty acids in B100. The free fatty acids can lead to corrosion and may be a
symptom of water in the fuel. Usually, for a base catalyzed process, the acid value after production
will be low since the base catalyst will strip the available free fatty acids. However, the acid value
may increase with time as the fuel degrades due to contact with air or water. This test should be
performed regularly as a part of the producer QC program.

6 Water content –

22
Fig. 11 shows the testing of water content. This testing is very important in biodiesel. Before
biodiesel are use in the engine water content must be follow the standard to avoid damage. The
standard ASTM method D2709 is max 0.005%.

23
 CHAPTER 2(d):
RESULTS & DISCUSSIONS

24
 2.d RESULTS AND DISCUSSION

d.1 Esterification Process -

 Fig. 2 shows the separation between methanol and triglycerin.

 At the top will be presence methanol and at the bottom show triglycerin.
 Involves the reaction of alcohol (such as methanol) with fatty acids as catalyzed
 to reduce the levels of FFA in the low-cost feedstocks to an acceptable range
 Reaction between acids and alcohols in the presence of strong acid catalyst
 Produce ester and water
 free fatty acid of material must be less than 2%
It needs to use methanol and Sodium Hydroxide as catalyst

d.2 Transesterification Process –

25
 Fig. 3 show two layer separation between glycerol and FAME
 At the top will be presence FAME and the at bottom is glycerol
 Reduce the high viscosity of triglyceride ( TG )
 methanol and catalyst produce methyl ester and glycerol
 involves the reaction of alcohol (methanol) with oil.

A. Washing & Distillation Process –

26
Fig. 4 shows separation between water and FAME.
 to remove small amounts of colour bodies to produce a colourless biodiesel it need washing
many time
 To obtain pure methyl esters (Biodiesel/ FAME)
 To remove soap, catalyst, methanol and other pollutants of biodiesel, using water
 If the washing is not complete, it will be repeated by esterification and transesterification or
washing.

B. Biodiesel –

 Biodiesel can be shown in fig. 5 which left is raw material and right is biodiesel.
 The percentage of biodiesel around 68-70% can be produce.
 Increase in the molar ratio the conversion of WCO to FAME decrease.

27
  At the same time, the waste can be converted to useable energy, pollution due to waste
cooking oil can be avoided, and energy can be continuously saved and renewed.

C. Drying -

After washing water still have inside biodiesel. Fig. 6 show oven for drying biodiesel. Then the
water must be removed from the biodiesel using drying at 120⁰c for 24 hours.

28
CHAPTER 3
TYRE PYROLYSIS OIL

29
 Tyre Pyrolysis Oil
Approximately 1.5 billion tyres are produced each year which will eventually enter the waste
stream representing a major potential waste and environmental problem. However, there is growing
interest in pyrolysis as a technology to treat tyres to produce valuable oil, char and gas products.

Waste to energy is the recent trend in the selection of alternate fuels. Fuels like alcohol, biodiesel,
liquid fuel from plastics, etc. are some of the alternative fuels for the internal combustion engines.In
order to prevent waste rubber and in particular discarded automobile tyres from damaging the
environment, it is highly desirable to recycle this material in a useful manner. However, the total
quantity of tyres currently recycled in a given year (excluding reuse, retreading, or combustion) is
less than 7% of the annual tyre generation rate in the world.

Pyrolysis oil is a synthetic fuel under investigation as substitute for petroleum. It is extracted

by biomass to liquid technology of destructive distillation from dried biomass in a reactor at
temperature of about 500 °C with subsequent cooling. Pyrolysis oil (or bio-oil) is a kind of tar and
normally contains too high levels of oxygen to be a hydrocarbon .Which results in non-volatility,
corrosiveness, being immiscible with fossil fuels, thermal instability and a tendency to polymerize
with exposure to air. As such it is distinctly different from similar petroleum products.

3.A.2 LITERATURE REVIEW:

Pyrolysis is the process of thermally degrading a substance into smaller, less complex molecules.
Pyrolysis produces three principal products: such as pyrolytic oil, gas and char. The quality and
quantity of these products depend upon the reactor temperature and design. A range of different
reactors, such as fixed-bed (batch), screw kiln, rotary kiln, vacuum and fluidised-bed have been
used for pyrolysis of waste tyres.
In the Pyrolysis process, larger hydrocarbon chains break down at certain temperatures in the
absence of oxygen that gives end products usually containing solids, liquids and gases. If the
temperature is maintained at 550 ºC, the main product is a liquid, which could be a mixture of
various hydrocarbons depending on the initial composition of the waste material.
At temperatures above 700 ºC, the gas becomes the primary product due to further cracking of
liquids. The gas is basically composed of CH4, with C2H6, C2H4, C2H2, and other gaseous

30
hydrocarbons however in lesser quantities. The quality and quantity of these products depend upon
the reactor temperature and design. In the present work pyrolysis oil from waste tyres by vaccum
pyrolysis is obtained. Though solid carbon black and pyrolysis gas are also obtained, the pyrolysis
process will be much more prominent to produce liquid.

Adrian M. Cunliffe and Paul T. Williams (1998), studied the composition of oils derived from the
batch pyrolysis of tyres in a nitrogen purged static-bed batch reactor, used to pyrolyse 3 kg of
shredded scrap tyres at temperatures between 450°C and 600°C. It was reported that pyrolysis of
scrap tyres produced oil similar in properties to a light fuel oil, with similar calorific value, sulphur
and nitrogen contents. The oil was found to contain 1.4 % sulphur and 0.45 % nitrogen on mass
basis and have similar fuel properties to those of diesel fuel. The oils contained significant
concentration of polycyclic aromatic hydrocarbons some of which have been shown to be either
carcinogenic and or mutagenic. A single oil droplet combustion study was carried out and also the
oil was analysed in detail for its content of polycyclic aromatic hydrocarbons (PAH).

The derived oil was combusted in an 18.3 kW ceramic-lined, oil-fired, spray burner furnace, 1.6 m
in length and 0.5 m internal diameter. The emissions of NOx, SO2, particulate and total unburned
hydrocarbons were determined in relation to excess oxygen levels. Throughout the combustion
tests, comparison of the emissions was made with the combustion of diesel. The concentration of
PAH increased from 1.5 to 3.4 wt. % of oil as the pyrolysis temperature increased from 450 to
600°C. The formation of PAH was attributed to a Diels–Alder type mechanism involving
cyclisation of alkenes and dehydrogenation to form aromatic hydrocarbons. A range of potentially
high value volatile hydrocarbons was identified in significant concentrations in the oils. It was
found that tyres pyrolysed at 475 o C found to be optimum pyrolysis temperature and the Tyre
pyrolysis temperature at this temperature has the chemical composition by % wt are: Carbon (84.6
%), Hydrogen (11.2), Nitrogen (0.5 %), Sulphur (1.4 %), Ash (0.002 %) and Oxygen by difference
(2.2 %).

31
CHAPTER 3(B)
METHODOLOGY

32
 METHODLOGY

In the present work, an automobile tyre was cut into a number of pieces and the bead, steel wires
and fabrics were removed. Thick rubber at the periphery of the tyre was alone made into small
chips. The tyre chips were washed, dried and fed in to a mild steel pyrolysis reactor unit. The
pyrolysis reactor used was a full insulated cylindrical chamber of inner diameter 110 mm and outer
diameter 115 mm and height 300 mm. Vaccum was created in the pyrolysis reactor and then
externally heated by means of 1.5 kW heater. A temperature controller controlled the temperature
of the reactor. The process was carried out between 450oC and 650oC in the reactor for 2 hours and
30 minutes. The products of pyrolysis in the form of vapour were sent to a water cooled condenser
and the condensed liquid was collected as a fuel. The schematic diagram of the pyrolysis process of
waste automobile tyres is shown in Figure 1.

The non-condensable gases were let out to atmosphere. The TPO collected was crude in nature. For
an output of 1 kg of TPO about 2.09 kg of waste tyres feedstock was required. The product yields
from the process are: Tyre Pyrolysis Oil (50 %), Pyro gas (40 %) and char (10 %). The heat energy
required to convert the waste tyres into the products was around 7.8 MJ/kg. The residence time of
the pyrolysis process was 90 minutes. The elemental composition of TPO is given in Table 1. The
composition of TPO reconfirms and comparable with the values available in the early research
works. Since the oil collected for this study was untreated, the TPO contains impurities, dust, low

33
and high volatile fractions of hydrocarbons. TPO was filtered by fabric filter and again filtered by
micron filter. The efficiency of the filtration is 99 %.

PYROLYSIS REACTORS AND PRODUCT YIELD-

The pyrolysis reactor is designed for pyrolysis of waste materials like biomass, agricultural wastes,
scrap tyres etc.

Types of reactors –
 Fixed bed
 Batch reactor
 Screw kiln and rotary kiln reactors
 Fluidised bed reactors

Fixed bed, batch reactors have been widely used to investigate pyrolysis of waste tyres. The reactor
is typically heated externally by an electric furnace and nitrogen or another inert gas is used as a
carrier gas. The thermally degradation of the tyre starts at around 350 _C and therefore pyrolysis
experiments are usually in the range of 450–700 _C. The derived gas products are carried by the
carrier gas and condensed downstream and the non-condensable gases are collected and analysed.
The residual char and any steel are collected after experimentation. Although there are some
commercial fixed bed batch reactors for processing tyres, the desire for a continuous process has led
to investigations of rotary kilns, moving bed screw reactors and fluidised beds. In such systems the
waste tyre is fed directly to the hot reactor.

34
 CHAPTER 3(C)
PHYSICAL PROPERTIES

35
 PHYSICAL PROPERTIES

TPO-Diesel Fuel blend gives different values of physiochemical properties, like heating value, viscosity,
flash point, pour point etc. compared to Diesel Fuel. These properties may affect the spray characteristics,
performance, combustion and emissions of the engine.
Some basic properties of TPO are-
 The viscosity of TPO is higher by about 1.5 times than diesel.
 The flash point and fire point of the TPO are closer to diesel.
 Sulphur and carbon content are also higher for TPO than Diesel Fuel.
TPO blended with Diesel Fuel is indicated as TPO xx. For example, 10 % TPO blended with 90 % Diesel
Fuel is denoted as TPO 10.

36
CHAPTER 4:
CONCLUSION

37
 5 CONCLUSION
Palm biodiesel-
An initiative to replace gasoline and diesel fuel due to the impact of fossil fuel crisis, hike in oil
price,etc. is using biodieselfuel.
The biodiesel is prepared from waste cooking oil sample collected from local factories. The
biodiesel was characterized for its physical and fuel properties using ASTM standard methods for
biodiesel fuel quality assurance The composition of final biodiesel was determined by physical
properties such as density, viscosity, flash point, water content and acid value. Out of 5 properties
tested, all of them met the ASTM criteria for fuel standard.
Production of biodiesel from waste cooking oils for diesel substitute is particularly important
because the increasing cost of oil extracted from petroleum source and also it is good for
enviroment. Waste cooking oil can be an important source for biodiesel production in the coming
years.
Tyre pyrolysis oil -
A review of the literature related to the pyrolysis of waste tyres has shown that most research has
been carried out using a range of reactors, such as fixed-bed (batch), screw kiln, rotary kiln, vacuum
and fluidised-bed.
The yield and composition of the products produced from pyrolysis, in particular the oils and
gases, are largely determined by the type of reactor used and the temperature and heating rate.
It is found that higher temperatures of pyrolysis and long gas residence times in the hot zone of the
reactor can crack the oil to gas.
The oil produced from pyrolysis of tyres is chemically very complex containing aliphatic, aromatic,
hetero-atom and polar fractions. The main aliphatic compounds are alkanes, with straight chain
hydrocarbons from C6–C37 and lower concentrations of alkenes.
Determination of the fuel properties of tyre pyrolysis oils shows that they are similar to a gas oil
(Diesel fuel) or light fuel oil and have been successfully combusted in test furnaces or blended with
Diesel fuel and used in Diesel engines.

38
 REFERENCES
A.K. Agarwal, 2007 , Biofuels (alcohols and biodiesel) applications as fuels for internal
combustion engines, Progress in Energy and Combustion Science 33 (2007) 233–271

A.K. Agarwal, Dhar A, 2013. Experimental investigations of performance, emission and

combustion characteristics of Karanja oil blends fuelled DICI engine, Renewable Energy 52,
283-291.
D. Agarwal, L. Kumar, A.K. Agarwal, 2008, Performance evaluation of a vegetable oil fuelled
compression ignition engine, Renewable Energy, 33 (2008), pp. 1147–1156
B. Deepanraj, C. Dhanesh, R. Senthil, 2011, Use of palm oil biodiesel blends as a fuel for
compression ignition engine, American Journal of Applied Science., 8 (2011), pp. 1154–1158
F.K. Forson, E.K. Oduro, E. Hammond-Donkoh, 2004, Performance of jatropha oil blends in a
diesel engine, Renewable Energy, 29 (2004), pp. 1135–1145

A.E. Ghaly, D. Dave, M. Brooks, 2010., Production of biodiesel by enzymatic

transesterification: review, American Journal of Biochemistry and Biotechnology., 6 (2010),
pp. 54–76

"Wikipedia," [Online]. Available: http://en.wikipedia.org/wiki/EPA

M. Murena, E. Garufi, R. B. Smith and F. Gioia, "Hydrogenative Pyrolysis of Waste Tires,"
Journal of Hazardous Material, vol. 50, pp. 79-98, 1996
P. T. williams, B. P. Bottrill and A. M. Cunliffe, "Combustion of Tyre Pyrolysis Oil," Institution
of Chemical Engineers, vol. 76, pp. 957-963, 1998.

39