ABSTRACT –

Diesel is a liquid fuel obtained by distillation of crude oil and is the most common fuel for
transportation of peoples and goods across the globe in today’s world. But as it is extracted
from crude oil, which is a non-renewable resource and hence cannot be generated easily
(once depleted, will be made after 1000’s of years). And if we continue to use the diesel as a
fuel then upto 2050 it will deplete and also the cost is continuously rising as its depleting.

Therefore we need an alternative fuel which can replace the non-renewable resource and will
be cheaper.

Waste to energy is the recent trend in the selection of alternate fuels. Use of TYRE
PYROLYSIS OIL (TPO) and PALM OIL in diesel fuel can act as a fuel for diesel engine
which would be cheaper than diesel fuel and would use waste tyres and oil as a raw material,
hence reusing the waste so as to reduce the problem of their disposal, As it’s not even safe to
dispose them directly to the environment.

TPO-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.

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 use of palm oil in the production of biodiesel has lead to concerns that the need of fuel is
being placed ahead of the need for food, leading to malnourishment in developing nations.
This is known as the food vs fuel debate. According to a 2008 report published in the
Renewable and sustainable energy reviews, palm oil was determined to be a sustainable
source of both food and biofuel. The production of palm oil biodiesel does not pose a threat
to edible palm oil supplies.
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.

INTRODUCTION-

Around the world, there are initiatives to replace gasoline and diesel fuel due to the impact of
fossil fuel crisis, hike in oil price and stringent emission norms. Millions of dollars are being
invested in the search for alternative fuels.
Therefore, it is important to find an alternative fuels to replace fossil fuels based on
renewable and natural sources like waste vegetable oil and fats or cooking oil.
This alternative will not only save environment but also cost.

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.

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.
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. 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.
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.
This project is aimed to develop a simple small plant to process the waste cooking oil to
biodiesel and use it in the factory.
A. Feedstock Waste Cooking Oil

Biodiesel can be produced from any material that contains fatty acids, be they linked to other
molecules or present as free fatty acids. Thus various vegetable fats and oils, animal fats, waste
greases, and edible oil processing wastes can be used as feed stocks for biodiesel production. The
choice of feedstock is based on such variables as local availability, cost, government support and
performance as a fuel. The primary feedstock is a vegetable oil or animal fat, biodiesel is
generally considered to be renewable. Since the carbon in the oil or fat originated mostly from
carbon dioxide in the air, biodiesel is considered to contribute much less to global warming than
fossil fuels. Diesel engines operated on biodiesel have lower emissions of carbon monoxide,
unburned hydrocarbons, particulate matter, and air toxics than when operated on petroleum-
based diesel fuel.

Importance-

Biodiesel from waste cooking oil (WCO) can reduce the cost of biodiesel production since the
feedstock costs constitutes approximately 70-95% of the overall cost of biodiesel production [6].
Although biodiesel cannot entirely replace petroleum-based diesel fuel, there are at least six
reasons that justify its development.
It provides a market for excess production of vegetable oils and animal fats.
It decreases, although will not eliminate, the country’s dependence on imported petroleum.
It helps dispose and reuse waste cooking oil and help reduse water pollution caused by disposing
WCO in sewage or other water bodies.
Biodiesel is renewable and does not contribute to global warming due to its closed carbon cycle.
A life cycle analysis of biodiesel showed that overall CO2 emissions were reduced by 78%
compared with petroleum-based diesel fuel [7].
The exhaust emissions of carbon monoxide, unburned hydrocarbons, and particulate emissions
from biodiesel are lower than with regular diesel fuel.
Unfortunately, most emissions tests have shown a slight increase in oxides of nitrogen (NOx).
When added to regular diesel fuel in an amount equal to 1–2%, it can convert fuel with poor
lubricating properties, such as modern ultra-low-sulfur diesel fuel, into an acceptable fuel.

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.
B. 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.

C. 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.

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.

2) 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 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.

D. 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.

3) 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.
E. 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.

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 –

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.”

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.

5) Water content –
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%.

RESULT AND DISCUSSION

A. 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

B. Transesterification Process –

 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

C. Washing & Distillation Process –

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.
D. 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.
  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.

E. 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.
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.

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
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 %).

Isabel de Marco Rodriguez et al., (2001) studied the behavior and chemical analysis of Tyre
pyrolysis oil.
In this work it is reported that Tyre Oils are a complex mixture of organic compounds of 5-20
carbons and with a higher proportion of aromatics. In this work, the percentage of
aromatics,aliphatic, nitrogenated, benzothiazol was also determined in the Tyre pyrolysis oil at
various operating temperatures of the pyrolysis process. Aromatics were found to be about 34.7
% to 75.6 % when the operating temperature varied between 300 oC and 700oC, while Aliphatics
were about 19.8 % to 59.2 %. In the same work, an automatic distillation test was carried out at
500oC to analyse the potential use of Tyre pyrolysis oil as petroleum fuels. It was observed that
more than 30 % of the Tyre pyrolysis oil was easily distillable fraction with boiling points
between 70oC and 210oC, which is the boiling point range specified for commercial petrol. On
the other hand, 75 % of the pyrolytic oil has a boiling point under 370oC, which is the upper limit
specified for 95 % of distilled product of diesel oil. It was mentioned that distillation carried out
between 150oC and 370oC has a higher proportion of the lighter and heavier products and a lower
proportion of the middle range of products than commercial diesel oil. The chemical
composition of Tyre pyrolysis oil derived at 500oC.
Care: Carbon (85.6±0.5 %), Hydrogen (10.1±0.1%), Nitrogen (0.4±0.03 %), Sulphur (1.4±0.2
%), Ash (not available) and Oxygen by difference (2.5±0.5 %).

Used tires were thermally decomposed at 500°C and at a total pressure of 20 kPa in a process
development unit consisting of a horizontal reactor vessel 3 m long and 0.6 m in diameter
(Chaala and Roy, 1996). The chemical compositions of the Tyre pyrolysis oil are: Carbon
(86.51%), Hydrogen (10.10 %), Nitrogen (1.2 %), Sulphur (0.8 %), and Oxygen by difference
(1.39%). Suat Ucar et al, (2005) compared two pyrolytic oils derived from passenger car tyres
and truck tyres from a fixed bed reactor. An optimum temperature at 650 oC, the chemical
compositions of Tyre pyrolysis oil derived from truck tyres are: Carbon (86.47%), Hydrogen
(11.73 %), Nitrogen (<1 %), Sulphur (0.83%), Ash (<1 %) and Oxygen by difference (not
available).
The chemical composition of Tyre pyrolysis oil derived from waste automobile tyres from bomb
reactors are: Carbon (86.11 %), Hydrogen (10.92), Nitrogen (0.41 %), Sulphur (0.83 %), Ash
(not available) and Oxygen by difference (1.73 %).

Studies have been carried out on wood pyrolysis oil as an alternate fuel in internal combustion
engines. Reliable operation was recorded with wood pyrolysis oil-diglyme blends without any
modification in the engine.

In the present study, TPO-Diesel blends were used as a fuel in a single cylinder air cooled DI
diesel engine.
The performance, emission and combustion characteristics of the engine were analysed and
compared with diesel fuel operation.

PYROLYSIS OF WASTE AUTOMOBILE TYRES-

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 and high volatile fractions of
hydrocarbons [10]. 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.

 Fixed bed reactors -

Aydın and Ilkılıc (2012) investigated the pyrolysis of waste tyres, with steel and fabric removed, in a 1.15
l capacity fixed bed reactor in nitrogen over the temperature range of 400–700 _C. They found that the oil
yield increased from 31 wt.% at 400 _C, increasing to 40 wt.% at 500 _C, with little change in yield at
higher temperatures. There was a consequent increase in gas yield. They also investigated the influence of
nitrogen flow rate on product yield and found only negligible differences in yield. Williams et al. (1990)
used a small scale, fixed bed, batch reactor to investigate the influence of pyrolysis temperature from 300
to 720 _C and heating rate from 5 to 80 _C min_1 on product yield from the pyrolysis of _50 g of tyre. At
the low temperature of 300 _C there was little thermal degradation of the tyres. To maximise oil yields of
between 54 and 58.8 wt.%, pyrolysis temperatures of 600–720 _C were required. It should be noted that
raising the temperature in a fixed bed reactor system beyond where the rubber has been thermally
degraded only marginally increases the yield of oil and gases. These oils and gases are most probably
produced from the volatilisation of some of the solid, very higher molecular hydrocarbon content of the
char (Dodds et al., 1983).
Using a larger fixed bed reactor with a feedstock loading of 1.5 kg and a pyrolysis temperature of 475 _C
and heating rate of 5 _C min_1 Cunliffe and Williams (1998a) obtained yields of oil, char and gas at 58.2
wt.% oil, 37.3 wt.% char and 4.5 wt.% gas. Islamet al. (2011) using a fixed bed reactor pyrolysed 750 g
batches of waste tyre and also found a high oil yield of 55 wt.% at 475 _C pyrolysis temperature with a
corresponding char and gas yield of 36 wt.% and 9 wt.% respectively. Kar (2011) pyrolysed 10 g batches
of waste tyres in a fixed bed, nitrogen purged reactor at 10 _C min_1 heating rate. The influence of
pyrolysis temperature from 375 to 500 _C was investigated and it was reported that the maximum oil
yield of 60.0 wt.% oil was obtained at 425 _C. At the higher temperature of pyrolysis, of 500 _C, the oil
yield decreasedto 54.12 wt.%. The gas yield increased from 2.99 to 20.22 wt.% and char yield decreased
from 50.67 to 26.41 wt.% as the temperature of pyrolysis was increased from 375 to 500 _C. However,
for similar pyrolysis conditions, Banar et al. (2012) reported that for pyrolysis of tyre derived fuel (steel
removed) the maximum oil yield was only 38.8 wt.%, with char yield at 34 wt.% and a high gas yield of
27.2 wt.% for a heating rate of 5 _C min_1 at a pyrolysis temperature of 400 _C. A similar oil yield of
38.0 wt.% at the pyrolysis temperature of 500 _C and 15 _C min_1 heating rate was obtained by
Laresgoiti et al. (2004) and de Marco et al. (2001). Rada et al. (2012) also obtained an oil yield of 40 wt.
% and gas yield of 20 wt.% and char yield of 40 wt.% for the fixed bed batch pyrolysis of tyres.
Differences in heating rates and in particular pyrolysis gas residence times can significantly impact the
relative yields of oil and gas, where higher temperatures of pyrolysis and long gas residence times in the
hot zone of the reactor can crack the oil to gas.
Williams et al. (1990) reported that increasing the heating rate showed an increase in gas yield, being 6.6
wt.% at 5 _C min_1 heating rate which increased to 14.8 wt.% gas at 80 _C min_1 heating rate, where
both experiments were undertaken at 720 _C pyrolysis temperature. Banar et al. (2012) reported a
significant influence of heating rate, where oil yield decreased to 35.1 wt.% and gas yield increased to
33.8 wt.% as the heating rate was increased from 5 to 35 _C min_1 at the pyrolysis temperature of 400
_C. The influence of very fast heating rates of 1200 _C min_1 have been investigated over a temperature
range of 500–1000 _C (Leung et al., 2002). It was shown that under such high heating rate conditions, the
gas yield increased from 5.0 wt.% at 500 _C to 23 wt.% at 900 _C. Large batch reactor systems
processing around 1 tonne of whole and shredded waste tyres have reported lower yields of oil for
example, 20.9 wt.% oil (24.0 wt.% oil, corrected for steel) and 23.9 wt.% gas for a pyrolysis temperature
of 950 _C (Williams et al., 1998).For such large batch reactors, there is a major drawback related to the
transfer of heat to the large volume of tyres contained within the reactor. For example, the reported 950
_C pyrolysis temperature represented the maximum attained temperature over an 8 h 40 min heating
period. The reactor design would produce pyrolysis at the outer edge of the reactor and for tyres located
in the inner part of the reactor and pyrolysed later in the heating cycle, the evolved gases would be subject
to significant secondary cracking reactions resulting in oil decomposition and cracking to produce
increased gas For example, Williams and Taylor (1993) examined the influence of tyre pyrolysis gas
residence time at high temperature by passing pyrolysis gases produced at 450 _C through a secondary
reactor at temperatures from 500 to 720 _C and a gas residence time of _30. The gas and oil yields
showed a marked change with secondary reactor temperature; the gas yield increased from 10 to 20 wt.%
and the oil yield decreases from 51.5 to 41.5 wt.% as the secondary reactor temperature was increased
from 500 to 720 _C.

 Screw kiln and rotary kiln reactors –

Continuous operating reactors have been developed for the pyrolysis if waste tyres. For example, Aylon
et al. (2008, 2010) used a moving bed reactor and investigated the influence of various parameters,
including pyrolysis temperature, between 600 and
800 _C and mass flow rate of tyres through the reactor on product yield and composition. The reactor was
a continuous screw kiln reactor, externally heated by electrical furnaces. The reactor was fed by a screw
feeder from the hopper containing shredded tyres with throughputs from 3.5 to 8.0 kg h_1. Pyrolysis oils
were condensed in a shell-and-tube condenser and non-condensable gases were combusted. The solid
char was recovered at the end of the screw kiln reactor outlet. The reported maximum oil yield of 48.4 wt.
% was obtained at a pyrolysis temperature of 600 _C and a tyre mass flow rate of 8 kg h_1. The research
group report that experiments on a small scale fixed bed reactor produced oil yields of 56.4 wt.%, the
difference compared to the moving bed screw reactor were attributed to the differences in heating rate and
gas residence times between the two reactors (Aylon et al., 2008). Diez et al. (2005) also used a screw
kiln reactor, externally heated by an electrical furnace to investigate the pyrolysis of shredded tyre at a
pyrolysis temperature of 500/600 _C. The plant was designed to produce gas and very little oil, so had a
long gas residence time and fast heating rate. The reported product yields were _33.5 wt.% char and _66.5
wt.% gas.
Galvagno et al. (2002) (reactor details in, Fortuna et al. (1997)) used a pilot scale rotary kiln reactor to
investigate the influence of temperature on the product yield from pyrolysis of waste tyres.
The rotary reactor was 0.4 m diameter and rotated at 3 r.p.m. and externally heated by electrical furnaces
with a throughput of 4.8 kg h_1. A condensation system allowed condensed fractions of heavy and light
pyrolysis oil and the non-condensable gases were scrubbed to remove acid gases and then combusted in a
flare. The solid residue of pyrolysis (char) was continuously discharged in a water cooled tank. A
maximum yield of product oil of 38.12 wt.% was obtained at 550 _C and maximum gas yield of 10.75 wt.
% at 680 _C. Li et al. (2004) also used a rotary kiln reactor to investigate
tyre pyrolysis at different pyrolysis temperatures. The rotary kiln consisted of a 0.3 m diameter, 3 m long
reactor rotating at between 0.45 and 0.9 r.p.m., externally heated by electrical furnaces corresponding to
an effective heated length of 1.8 m. The highest oil yield of 45.1 wt.% was obtained at 500 _C pyrolysis
temperature ith a gas yield of 13.6 wt.%. Maximum gas yield was 18.3 wt.% at 650 _C due to the
secondary cracking reactions of the oil vapour at higher temperatures and the long residence time of gases
in the hot zone of the rotary kiln reactor.

 Fluidised bed reactors -

Fluidised bed pyrolysis of tyres has been extensively researched by Kaminsky and co-workers (Kaminsky
and Sinn, 1980; Kaminsky, 1985; Kaminsky and Mennerich, 2001; Kaminsky et al., 2004, 2009).
Fluidised bed reactors have been investigated at laboratory scale with 1 kg h_1 throughput, technical
scale with 30 kg h_1 throughput to pilot scale with 200 kg h_1 throughput.

Large scale pilot plant studies were able to process whole tyres.
The fluidised bed is heated indirectly to typical temperatures of between
500 and 780 _C via radiant heat tubes within the bed of quartz sand, in which the product pyrolysis gas is
combusted to provide heat. The fluidising gas is also the product gas and is preheated to 400 _C. Any ash
build up in the fluidised bed is removed by a screw extractor. The product gases pass through a cyclone to
remove particulate material and the oils condensed and distilled to produce two oil fractions, heavy and
light oils. The gases undergo further removal of oil droplets in an electrostatic precipitator before storage.
Kaminsky et al. (2009) reported that for the laboratory scale 1 kg h_1 fluidised bed reactor oil yields at
740 _C pyrolysis temperature were 30.2 wt.% and for the 200 kg h_1 pilot scale reactor processing whole
tyres at 700 _C, oil yield was 26.8 wt.%, but on a steel free basis was similar to the laboratory reactor oil
yield at
30.9 wt.%.
A laboratory scale fluidised bed reactor was used by Williams and Brindle (2003a) to pyrolyse tyre crumb
(size 1.0–1.4 mm) over the temperature range of 450–600 _C. The reactor was 7.5 cm diameter and 100
cm high with quartz sand as the reactor bed and a throughput of _220 g h_1 of tyre. The incoming fluid
isingair was nitrogen and was pre-heated to 400 _C by an external electrical furnace. Condensation was
via a series of water cooled and dry ice/acetone cooled condensers. The maximum oil yield of
55 wt.% was found at 450 _C pyrolysis temperature which was reduced to 43.5 wt.% at 600 _C, with a
consequent increase in gas yield from 2.5 to 14.0 wt.%.
A laboratory scale circulating fluidised bed reactor was developed by Dai et al. (2001) to investigate the
influence of tyre particle size (0.32 mm and 0.8 mm), temperature of pyrolysis (360–810 _C) and gas
residence time (1–5 s) on product yield and composition.
The circulating fluidised bed was 10 cm diameter and 290 cm high.
The tyre was fed to the bed via a screw feeder and quartz sand is circulated at high fluidising velocity
through the reactor. Sand and char escaping the bed are trapped in two cyclones and recirculated back to
the reactor bed. Oils are condensed in a water cooled condenser and product pyrolysis gases are preheated
and used as the fluidising gas. Dai et al. (2001) report a maximum oil yield of _52 wt.% at 450 _C which
decreased markedly to 30 wt.% at 810 _C with a consequent increase in gas yield from _15 to _40 wt.%.
The influence of particle size was reported as higher yields of oil (_50 wt.%) for the smaller (0.32 mm)
particles compared to the larger particles of tyre (0.8 mm) which produced an oil yield of 41 wt.% at the
same pyrolysis temperature of 500 _C.
Longer residence times of the pyrolysis gases in the hot zone of the circulating fluidised bed reduced the
oil yield from _51 wt.% at 1 s residence time to _48 wt.% at 5 s residence time for a pyrolysis
temperature of 500 _C.

FUEL COMPOSITION AND 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.
Murugan et al. (2008a, 2008b, 2008c, 2008d) have extensively investigated the use of tyre pyrolysis oil
blended with petroleum diesel fuel in a direct injection diesel engine.

For blended tyre pyrolysis oil-diesel fuel blends, Murugan et al. (2008a) reported that the brake thermal
efficiency (overall efficiency) of the engine was only marginally influenced by the use of the tyre
pyrolysis oil-diesel fuel blends compared to using diesel fuel alone at blends of 10%,30% and 50% of tyre
pyrolysis oil. In some cases, there was a marginal increase in brake thermal efficiency with the blended
fuel.
They also reported that there was no seizing of the engine or injector nozzle blocking with the use of the
blended tyre oil and diesel fuel. In terms of emissions, it was reported that hydrocarbon emissions were
significantly increased by 15% and 21% when tyre oil diesel fuel blends of 30% and 50% respectively
were used under peak load conditions compared to diesel fuel. This was attributed to the higher
concentration of PAH in tyre oil compared to diesel fuel. In addition, nitrogen oxides (NOx) emissions
were found to be 4.5% and 10% higher for the 30% and 50% tyre oil blends respectively compared to
diesel fuel under peak load conditions. The emission of smoke (particulate material) was increased by 7%
compared to diesel fuel when the 50% blend of tyre oil and diesel was used at peak load.

Higher ratios of tyre pyrolysis oil-diesel fuel with up to 90% addition to diesel fuel were also investigated
by Murugan et al. (2008b, 2008d). At higher blend ratios the tyre oil was modified by sulphur reduction,
moisture removal and distillation prior to blending. It was reported that the direct injection diesel engine
could not operate satisfactorily on 100% modified tyre pyrolysis oil, but could at 90% tyre oil with 10%
diesel fuel. A small (2%) reduction in engine efficiency and an 11% increase in hydrocarbon emissions
was observed but an 18% decrease in NOx was reported at peak load using the 90% tyre oil blend. There
was however a marked increase in the emission of smoke.

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.