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DETERMINATION OF OXIDATION STABILITY OF BIO

DIESEL ALONG WITH EFFECT OF TERT BUTYL


HYDROQUINONE(TBHQ) & PROPYL GALLATE(PG)
A PROJECT PHASE REPORT
Submitted by
JELIN.Y ( 190201011 )
LEOLIN R.B ( 190201016 )
NAVEEN PANDI.T ( 190201020 )

in the partial fulfilment for the award of the degree of

BACHELOR OF ENGINEERING
IN
AUTOMOBILE ENGINEERING

RAJALAKSHMI ENGINEERING COLLEGE

THANDALAM, CHENNAI-602105

ANNA UNIVERSITY
APRIL 2023
ANNA UNIVERSITY, CHENNAI

BONAFIDE CERTIFICATE

1
Certified that this report titled “DETERMINATION OF OXIDATION
STABILITY OF BIO DIESEL ALONG WITH EFFECT OF TERT
BUTYL HYDROQUINONE(TBHQ) & PROPYL GALLATE(PG)” is
the Bonafide work of “JELIN.Y (190201011), LEOLIN.R.B (190201016)
and NAVEEN PANDI.T (190201020)” who carried out the project work
under my supervision. Certified further that to the best of my knowledge the
work reported herein does not form part of any other thesis or dissertation
on the basis of which a degree or award was conferred on an earlier
occasionally on this or any other candidate.

Signature of the HOD Signature of the Supervisor


Dr. K. BHASKAR Mr. R. ANBALAGAN
Professor and Head, Associate Professor,
Dept. of Automobile Engineering Dept. of Automobile Engineering
Rajalakshmi Engineering College Rajalakshmi Engineering College
Thandalam, Chennai-602105. Thandalam, Chennai-602105.

submitted to Project and Viva-Voice Examination held on

Internal Examiner External Examiner

ACKNOWLEDGEMENT

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We thank Mr. S. MEGANATHAN, B.E., F.I.E., Founder &
Chairman, Dr. M. THANGAM MEGANATHAN, M.A., M.Phil., Ph.D.,
Chairperson and Mr. M. ABHAY SHANKAR, B.E., M.S., Vice Chairman
of Rajalakshmi
Institutions for Providing the pleasant environment.

It’s our pleasure to express my sincere gratitude to our respected


Principal Dr. S.N. MURUGESAN, Ph.D., for giving us an opportunity to do
project work.

We gratefully acknowledge and thank Dr.K.BHASKAR, Ph.D.,


Professor & Head, Department of Automobile Engineering for giving his
constant encouragement.

We thank our project co-ordinator, Mr. K. MOHANRAJ, M.E.,


Assistant Professor & Dr. MULLAISUDAROLI, Assistant professor of
Department of Automobile Engineering, for their timely support and
suggestion throughout this phase.

We thank our project guide, Mr. R. ANBALAGAN, M.E., Associate


Professor, Department of Automobile Engineering, for his valuable guidance
throughout this phase of project.

We also express our profound thanks to our family members and all
the faculty members and lab technicians of Automobile Engineering
Department who helped us to make this project successful.

3
ABSTRACT

Biodiesel, an eco-friendly and renewable fuel substitute for diesel has been
receiving the attention of researchers around the world. The hike and limitations
of fuel resources arose at the current situation and the strict emission norms put
forth by the environmental agencies forces us to look for an alternative which
introduces the concept of biodiesel. Transportation plays a significant part in
economic progress and globalisation, but air pollution has a negative impact on
all mediums. Bio diesel which refers to fatty acid alkyl esters, has attracted
considerable attention as an environmentally friendly alternative fuel for diesel
engines, and biodiesel has certain advantages as a renewable, biodegradable and
non-toxic fuel. Antioxidants reduce fuel aging, reduce deposit formation in fuel
injection equipment and filters. Additives like Propyl Gallate (PG) and Tert-
Butyl-Hydroquinone (TBHQ) were selected to evaluate their oxidation stability.
These experimental results carried out to evaluate the oxidation and storage
stabilities of biodiesel fuels with various additives with different proportion.

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TABLE OF CONTENT

CHAPTER TITLE
PAGE
NO NO
ABSTRACT 4

1 INTRODUCTION

1.1 GENERAL 8
1.2 MOTIVATION 9
1.3 OBJECTIVE 9
1.4 ABOUT BIO DIESEL 10
1.5 GLOBAL MARKET OF 11
BIO-DIESEL
1.6 COST BENEFITS OF 12
BIO-DIESEL
1.7 PROPERTY DETERMINATION 13
OF NEAT WASTE COOKING
OIL AND WCO SAMPLES

2 CONVERSION OF WASTE
COOKING OIL TO BIOBLEND

2.1 BIODIESEL PRODUCTION 14


2.2 TRANSESTERFICATION FOR

5
BIODIESEL CONVERSION 15
2.3 MAGNETIC STIRRING 16
2.4 ULTRASONIC CAVITATION 17
2.5 BIODIESEL REACTOR TANK 18
2.6 HYDRODYNAMIC CAVITATION 19

3 OXDIATION STABILITY TESTER

3.1 RAPIDOXY-100 20
2.2 FUEL SAMPLE 21
3.3 COMPONENTS OF RAPIDOXY-100 22
3.4 WORKING 23
3.5 PURGING 24
3.6 FILLING 25
3.7 CLEANING 25

4 EXPERIMENTAL OUTPUTS

4.1 FOR 5ML BIO-DIESEL 27


4.2 FOR 5ML OF BIO-DIESEL 28
500PPM PG
4.3 FOR 5ML OF BIO-DIESEL 29
750PPM PG
4.4 FOR 5ML OF BIO-DIESEL 30
1000PPM PG

6
4.5 FOR 5ML OF BIO-DIESEL 31
500PPM TBHQ
4.6 FOR 5ML OF BIO-DIESEL 32
750PPM TBHQ
4.7 FOR 5ML OF BIO-DIESEL 33
1000PPM TBHQ
4.8 FOR 3.5ML OF DIESEL & 1.5ML 34
OF BIO-DIESEL
4.9 FOR 3.5ML OF DIESEL, 1.5ML 35
OF BIO-DIESEL & 500PPM TBHQ
4.10 FOR 4.6ML OF BIO-DIESEL, 0.4ML 36
OF DIETHYL ETHER & 1000PPM
TBHQ
4.11 FOR 4.6ML OF BIO-DIESEL, 0.4ML 37
OF DIETHYL ETHER & 2000PPM
TBHQ
4.12 FOR 4.6ML OF BIO-DIESEL, 0.4ML 48
OF DIETHYL ETHER & 2000PPM PG

5 CONCLUSION
39

6 REFERENCE
40

7
7 ACHIEVEMENT
41

CHAPTER 1
INTRODUCTION

1.1 GENERAL

Accessibility of energy sources and climate change are the two biggest
challenges that mankind facing in this century. The fast-growing population
and the increasing prosperity have led to rapid rise in the energy demand.
Human civilization predominantly depends on the utilization of energy, it
plays a big role in socioeconomic development by improving the standard of
living. Energy is vital for the economic development of every country. Every
sector of the economy such as agriculture, industry, transport, commercial and
domestic sectors require energy. Fossil fuel-based fuel sources such as
petroleum, coal and natural gas have been the predominant sources of energy
all over the world for a long time. The majority of the world energy needs,
about 81.1% is supplied through petrochemical sources such as coal, oil and
natural gas.

The high energy demand in the industrialized world as well as in the


domestic sector had caused environmental pollution problems due to their
widespread use of fossil fuels. Fossil fuel combustion has several public health
risks and environmental problems which extend to universal and potentially
irreversible consequences on global warming.

As a result, the concerns about environmental impacts have increased and


trigged the examination of alternative energy sources. Typical forms of

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renewable energy include wind power, hydropower, solar energy, biomass and
biofuels. The contribution of all these resources is important because of the
economic and environmental reasons, and biodiesel could be one of the
solutions.

1.2 MOTIVATION

Where India’s import of crude oil is likely to go up to 92% of total fuel


requirement by the year 2020 based on the current growth rate and available
new domestic sources. Because of this, India has started using biodiesel
partially in the automobile sector and railways. But the biodiesel is not
available uniformly and sufficiently throughout the country, since it is derived
from the plants and the particular plants are not available all over India. So,
biodiesel is used in limited quantity.

These factors make a thrust to find out a substitute fuel for diesel and
biodiesel production will definitely build the economy of the Nation.
Currently India utilizes 13% of world’s oil seed cultivated and produce
nearly about 18% of world’s oil seed with different types. Therefore, of
biodiesel will viable and it can be substituted for diesel fuel in the upcoming
years.

These background gives the idea to undertake the research study to


identify and to solve the fuel crisis, when the fossil fuels completely deplete in
nature. Further it is planned to develop biodiesel in the particular region, with
respect to the availability of biodiesel sources.

1.3. OBJECTIVE

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The objective of the review is to identify the non-fossil renewable fuels
which will performing better than conventional diesel engine in terms of
performance, emission and combustion characteristics without any
modification.

1.4. PREPARATION OF BIO DIESEL

Biodiesel is a substitute to diesel fuel derived from the triglycerides of


vegetable oils or animal fats. Biodiesel can be produced from various vegetable
oils such as palm oil, sunflower, soybean, rapeseed and castor oil using different
types of catalysts. In this article, the phrase “waste cooking oil” refers to edible
oil which has formerly been used for frying in restaurants and hotels, and no
longer be used for similar purpose. In most towns in developing countries
including in Ethiopia waste cooking oil simply dumping into the environment.
This causes serious environmental, social, economic and health problems to the
society. Improper or poor waste cooking oil disposal into water bodies rises the
level of organic pollutants in the water. This significantly lowers the water
quality and consequently affects the life of fish stocks, other aquatic living
things and the surrounding community.
Biodiesel production from WCO is environmentally friendly for it recycles
waste cooking oil and gives renewable energy with lower pollution. It
substitutes some amount of petrochemical oil import and also lowers the cost of
waste management. Biodiesel production from waste cooking oil has three
solutions those are economic, environmental and waste management.
Heterogeneous catalysts have attracted great attention in recent times for use in
the biodiesel production18. The need for development of heterogeneous

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catalysts has risen due to the fact that homogeneous catalysts used for biodiesel
production pose some limitations.
These drawbacks include; washing of products with water to remove
catalyst from the products which results in waste water generation and loss of
biodiesel as a result of washing, the use of intensive biodiesel separation
protocol, the corrosive nature of the catalysts and impossibility of catalyst reuse.
Heterogeneous catalysts have also the advantages of easy separation from the
product, reusability and eco-friendly. Calcium oxide nanoparticle has a higher
basicity, non-corrosive, can be synthesized with a lower price, lower solubility
and easier to handle than homogenous catalysts. In addition to these advantages,
its being safe to the ecosystem made it an interesting choice for a catalyst.
The main purpose of this research work is to enhance the production of
biodiesel from waste cooking oil feed stock. The use of waste oil biodiesel has
showed an increase of 4.75% in fuel density compared to pure diesel and also
there was a 13.43% decrease in calorific value of fuel and 7.24% for unused
oil biodiesel. The biodiesel showed improvement in the power, thermal
efficiency, torque and reduction in the specific fuel consumption. The study
on the usage of waste cooking oil from restaurants and found out that through
transesterification process pure biodiesel could be produced. Their study on
combustion characteristics with different blends and various compression
ratios shows that with increase in compression ratio the torque for all blends
increases and in contrary the BSFC decreases and with increased blends the
BSFC increases at all compression ratios.

1.5. GLOBAL MARKET OF BIO-DIESEL

A Diesel Engine is the most fuel-efficient combustion engine among the


available ones and the transport sector mainly uses diesel fuel due to its better
fuel economy and more effective power. Several countries such as USA,

11
Germany, France, Italy, Brazil, and Indonesia are using biodiesel blended with
diesel. In a country like India, biodiesel also can be used as alternative
automotive fuel & also in other sectors as CI engine fuels. Biodiesel is a fastest
growing alternative fuel. India has huge potential for biodiesel, but it is not yet
explored properly to replace at least some percentage of mineral diesels with
biodiesel.

1.6. COST BENEFITS OF BIODIESEL

The primary influences on the cost of manufacture of biodiesel are as follows:


• Capital and operating costs of the plant, including the processing
plant, services, catalyst, feedstock and product storage, and buildings.
• Feedstock used in the process: tallow, vegetable or waste oil, and
alcohol, most typically methanol.
• The glycerol by-product, which provides a secondary revenue
stream to the biodiesel produced or acts as an offset against the unit cost of
biodiesel production.
• The yields and quality of the biodiesel and glycerol produced
from the tallow/oil and methanol inputs.
• Although the price of conventional diesel fuel is not a direct
component of the cost of biodiesel production, it provides the baseline
against which the cost of biodiesel production must be compared. From the
perspective of the biodiesel producer, the price received for its biodiesel
output will most likely bear a close relationship, if not equivalence to the
price of diesel and therefore will be a direct influence on the profitability of
the producer’s operation. When reviewing the cost of biodiesel production, it
quickly becomes apparent that it is difficult to typify this cost as its

12
components, notably the principal feedstocks and the by-product glycerol, are
subject to considerable and unrelated market price fluctuations.

1.7 PROPETY DETERMINATION OF NEAT WASTE


COOKING OIL AND WCO SAMPLES

The iodine value, pH, density, congealing temperature, acid value,


viscosity, cetane index and an acid number of neat vegetable oil and clean
WCO samples were determined using the appropriate methods and equipment.

• PH: The pH of the WCO was determined with the aid of a pH meter.
• Congealing temperature: The congealing temperature of the samples
was determined by putting 20 ml of the sample of neat vegetable oil and
WCO in a 100-ml beaker, inserting the probe of a digital thermocouple
into the sample and putting it into deep freeze. The temperature of the
neat and WCO samples was monitored through a thermometer. The
congealing temperature is the mean of the temperatures at the
commencement and completion of gelation of the oil samples.
• Density and kinematic viscosity: The density and kinematic viscosity of
the neat vegetable oil and WCO samples were determined by a
viscometer at 20°C using a DMA™ 4100 M density meter.

Iodine value: The iodine value of the WCO samples was determined in
accordance with the AOCS Cd 1b-87 method.

13
CHAPTER 2

CONVERSION OF WASTE COOKING OIL INTO BIO BLEND

2.1 BIODIESEL PRODUCTION

For the commercialization of biodiesel as CI engine fuel throughout the


world, different production processes of it should be identified and made
available to the people working at grass root level. The raw materials needed
for its production may vary from country to country. Keeping this in mind
researchers are trying to find several ways to produce biodiesel from locally
available different feedstock such as vegetable oil – both edible and non-
edible, animal tallow, waste cooking oil and algae. As the viscosity of the oils
and fat derived from the above mentioned feedstock is much higher and
unsuitable for using in unmodified CI engines, the first step is to reduce its
viscosity. This is done through a chemical reaction called Transesterification.
In this process, the triglyceride present in the oil or fat reacts with
alcohol (methanol or ethanol) in the presence of a catalyst which is alkaline in
nature. A catalyst such as sodium or potassium hydroxide is required.
Glycerol (also called glycerine) is produced as a by product. The overall
reaction of the Transesterification process has been shown in Fig. 2.2.1
following Saka. Generally, methanol is used to produce biodiesel because of

14
its availability and lower reaction time, and the final product (biodiesel) is
called as methyl ester of the raw oil used. Sometimes, ethyl alcohol is also

used for the production of biodiesel, and it is called as the ethyl esters of the
corresponding oil. Ideally, Transesterification is potentially a less expensive
way of transforming the large, branched molecular structure of the biooils into
smaller, straight chain molecules of the type required in regular diesel
combustion engines.

2.2 TRANSESTERIFICATION FOR BIODIESEL


CONVERSION
Fig: 2.2.1 Overall Transesterification process

Transesterification is a chemical reaction used for the conversion of


triglycerides (fats) contained in oils, (Feedstocks) into usable biodiesel.
Biodiesel produced by the process of transesterification has a much lower
viscosity, making it capable of replacing petroleum diesel in diesel engines.

15
The biodiesel production method applied worldwide at industrial level is the
transesterification of triglycerides which are the main component of

vegetable oils and animal fats. The most common type of esters are methyl
esters, mainly because methanol is usually the cheapest alcohol. In Brazil,
however, the dominant esters produced are ethyl esters since ethanol is even
cheaper than alcohol. The reaction is catalysed by bases, acids and enzymes
and can take place either at low or high temperatures. The produced methyl
esters of fatty acids are characterized as biodiesel while glycerol is received
as a reaction by-product. The transesterification reaction of triglycerides
where R ‘, R”and R”’ are long chains containing carbon and hydrogen atoms
(chain fatty acids), shown in fig 2.2.2.

Fig2.2.2 Transesterification for Biodiesel Conversion

2.3 MAGNETIC STIRRING

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Fig 2.3 Magnetic stirring

The magnetic stirrer shown in fig 2.3 consists of two main parts: motor with
stirring mechanism and control electronics. Motor movement with a magnet on
top causes rotation of stir bars which mix liquids. Control electronics
supervises motor RPM, keyboard functions. Magnetic stirrers are designed for
mixing fluids of different viscosity with the help of a stir that spins very
quickly.
They are commonly used for sample preparation and analysis, in chemistry
Lab, biology lab, Pharmacy Lab and in such laboratory works as organic
synthesis, extraction, oil analysis, pH measurement, dialysis, soil suspending,
preparing buffer solutions where it is often needed to mix several types of
liquids to get homogeneous mixtures. Magnetic stirrers have different service
performance and technical parameters. The main difference is in the design
which means that mixing occurs by rotating or oscillating processes. When you
choose a magnetic stirrer, you should take into consideration the volume of the
liquid container, the speed of rotation, the oscillation intensity, and heating if
you need to raise the temperature of the mixture.
A magnetic stirrer is an electromechanical device that mixes with the help
of an external magnetic field that rotates a stir bar placed in the mixture. Stir
bar rotates at different speeds and can mix volumes up to one litter. Since only

17
a small magnet bar that can easily be cleaned and sterilized has to be put inside
the sample, the risk of contamination is minimized.
Magnetic stir bars work well in glass vessels. Glass is the material that
doesn’t affect a magnetic field. The stir bar has a limited size that is why it can
be used for relatively small experiments. They can have difficulties with
viscous liquids and thick suspensions. The plastic case of the device serves as
good isolation from spills. Magnetic stirrers have no moving parts and use a
magnetic field. The housing of the most magnetic stirrers is made of
polypropylene. The stir bar is made of ferrite enclosed in polypropylene.

2.4 ULTRASONIC CAVITATION

Ultrasonic Cavitation technique is used for biodiesel production.


Parametric optimization of biodiesel production using Taguchi method has been
done. Characterization of biodiesel shows that biodiesel can be good alternative
of petroleum-based fuel and it can be used in any compression ignition engine
without any modification.

2.5 BIO DIESEL REACTOR TANK

Fig 2.5 Biodiesel reactor tank

18
A Biodiesel Reactor tank shown in fig 2.5 is basically just a tank with a
heating element and a pump or a motor. The tanks are made from stainless steel
or even sometimes plastic. Some biodiesel reactors use a water heater to heat up
the mixture as the reaction takes place at around 122F (55C). For the reaction to
be complete the catalyst mixture must be added to the reactor, usually by a
motor with a propeller to stir it or a pump to mix it. A biodiesel reactor shortens
the amount of time and makes the process semi-automated or fully automated
so commercial amounts of biodiesel can be created. There are two main types of
biodiesel reactor units: shear and ultrasonic. Both work on biodiesel in different
ways, but both lead to the creation of large amounts of biodiesel with little work
on the part of the reactor operator.
An ultrasonic biodiesel reactor uses ultrasonic waves to make biodiesel
feedstock bubble. The bubbles are produced and collapse because of the
ultrasonic waves, causing a reaction from heat and pressure that makes the
feedstock transesterifications (the exchange of ester between an R group and an
Alcohol). An ultrasonic biodiesel reactor is normally used for large or
commercial needs, because these units have a hard time creating smaller
amounts of biodiesel. These units also tend to require less work from operators
and run at a more automatic pace than shear reactors. A shear biodiesel reactor
is used in laboratories that need small amounts of biodiesel for testing, can be
used in a home by a qualified person, and can also be ramped up for
commercial use. In biodiesel production, adequate mixing is required to create
sufficient contact between the vegetable oil/animal fat and alcohol, especially at
the beginning of the reaction. Ultrasonic waves cause intense mixing so that the
reaction can proceed at a much faster rate. Ultrasound transfers energy into fluid
and creates violent vibrations, which form cavitation bubbles. As the bubbles
burst, a sudden contraction of the fluid occurs, and the ingredients are mixed in
the area of the bubbles. Such a high energy action in liquid can considerably
increase the reactivity of the reactant mixture and shorten the reaction time

19
without involving elevated temperatures. In fact, this reaction can be achieved
at or slightly above ambient temperature. Because there is no need to heat the
mixture, energy may be saved.

2.6. HYDRODYNAMIC CAVITATION

HC is the process of pressure recovery by collapsing cavities or bubbles


and resulting in higher generation of energy in the form of shockwaves which
enhances rapid reaction rate. Transesterification of biodiesel, hence it is
presently a novel proposal in the biodiesel production field. Rubber seed oil
with high fatty acid content of about 72.36 mg KOH/g has been reduced to 2.64
mg KOH/g at a rapid reaction rate of about just 30 min by the application of HC
intensification technology, which is 6.5-fold higher energy efficiency, 4.9-fold
higher reaction rate and 5-fold shorter reaction duration when compared to
conventional mechanical stirring (MS).
CHAPTER 3
OXIDATION STABILITY TESTER
3.1 RAPIDOXY – 100

20
Fig 3.1 Rapidoxy 100

RapidOxy 100 Fuel consists of a high-grade gold plated aluminium test


chamber in which the sample is tested applying pure oxygen, heat and pressure.
The evaluation of the test result focuses on the time until a specified pressure
drop is measured due to oxygen uptake of the sample. RapidOxy 100 Fuel
allows accelerated oxidation stability tests on raw materials and finished
products directly on the whole sample. The oxidation stability of spark ignition
fuels and all kinds of diesel fuels ranging from pure diesel (B0) and diesel with
FAME/ blends (B1 - B99) to pure biodiesel (B100) is the typical application for
the RapidOxy 100 Fuel. Both the RapidOxy 100 and RapidOxy 100 Fuel
measure the induction period of a sample under accelerated oxidation
conditions. A typical test is conducted with a small sample volume of 5 mL or 4
g. The sample is filled or placed into a test chamber that is charged with oxygen
to 500 kPa or 700 kPa at a starting temperature of 15 °C to 25 °C. The
measurement begins by heating the test chamber to the defined target

21
temperature and lasts until the break point is reached, which is a pressure drop
of a defined percentage (e.g. 10 %) below the maximum pressure of the test run.

3.2 FUEL SAMPLE

Fig 3.2 Testing Fuel

Reproducibility / Repeatability of up to 99%

 Rapid Small-Scale Oxidation Test (RSSOT)


 Compliance with ASTM D8206, ASTM D7545, ASTM D7525, EN
16091
 Excellent reproducibility / repeatability
 Small sample amounts: only 5 mL / 4 g
 Broad range of measurable samples – from liquids to solids

22
3.3 COMPONENTS OF RAPIDOXY 100

23
Fig 3.3 Components of Rapdioxy 100

# Description

1 Screw Cap

2 Touchscreen

3 Test Chamber

4 Locking pins of the cover

5 Cover

6 Over Handle

7 USB Socket

3.4 WORKING OF RAPIDOXY 100

The unique oxidation stability tester accelerates the oxidation process by using
increased temperature and an excess of pure oxygen. RapidOxy 100 is highly
suitable for oxidation stability determination of vegetable oils and animal fats.
Fast and unique measuring method. Excellent reproducibility and repeatability.
Measuring range of up to 180 °C. Short test time with results in a fraction of the
time compared to other accelerated aging methods. Small sample volume,
usually only 5 mL or 4g• No sample preparation necessary. Optional magnetic
stirrer available. Fast and easy cleaning of the test chamber and the inserted
glass dish with soft paper tissue and ethanol. Commercially available extra-dry
oxygen of not less than 99.6 % purity is required for the operation of the
RapidOxy 100. If you use a filling pressure of 700 kPa (7 bar), a 10 L oxygen
bottle will last for approximately 180 measurements. The inlet pressure must

24
not exceed 800 kPa (8 bar). RapidOxy 100 consists of a highest-quality stainless
steel test chamber in which the sample is tested applying pure oxygen, heat and
pressure. The evaluation of the test result focuses on the time until a specified
pressure drop is measured due to oxygen uptake of the sample. RapidOxy 100
allows accelerated oxidation stability tests on raw materials and finished
products directly on the whole sample. The oxidation stability of natural oils
and fats, cosmetics, flavours & fragrances, or products containing any of these
is the typical application for the RapidOxy 100.

Precautions for highly inflammable samples and cleaning agents:


• Observe and adhere to your national safety regulations for handling the
measured samples (e.g., use of safety goggles, gloves, respiratory protection
etc.). • Only store the minimum required amount of sample, cleaning agents and
other inflammable materials near the RapidOxy 100.
• Do not spill samples/cleaning agents or leave their containers uncovered.
Immediately remove spilled samples/cleaning agents.
• Make sure that the setup location is sufficiently ventilated. The environment of
the RapidOxy 100 must be kept free of inflammable gases and vapours.
• Connect the RapidOxy 100 to the mains via a safety switch at a safe distance
from the instrument. In an emergency, turn off the power using this switch
instead of the power switch on RapidOxy 100. Do not obstruct this switch!
• Supply a fire extinguisher.
• Ensure the sufficient supervision of the RapidOxy 100 during operation.

Typical samples to be measured:


• fuels
• gasoline
• diesel
• FAME

25
• diesel/FAME blends Unknown samples for unknown or potentially hazardous
samples, the device should be placed under a suitable exhaust outlet Sample
loading With RapidOxy 100 Fuel only liquid samples are tested.

3.5 PURGING

The purging feature flushes oxygen through the ducts and/or the test chamber of
the RapidOxy 100 instrument. This flushing feature removes any sample traces
in the instrument and guarantees that all ducts and the pressure line are actually
filled with oxygen. To manually start the purging feature, select "Purging 1" or
"Purging 2" from the "Manual Functions" menu.

• Purging 1 Oxygen is conducted into the oxygen inlet and out of the oxygen
outlet. No oxygen is conducted into the test chamber, the respective valve is
closed. This ensures that the ducts and pressure line are actually filled with
oxygen.
• Purging 2 Oxygen is conducted through the pressure inlet of the test chamber.
For cleaning purposes, the screw cap and the cover are kept open during
"Purging 2".

3.6 FILLING

The filling feature loads the test chamber with oxygen and a defined filling
pressure. This feature can be used to test the filling functionality itself and also
for leak testing.

• Insert a new O-ring, close the screw cap of the test chamber and the lid.

• Tap to open the "Manual Functions" menu.

26
• Tap "Fill Pressure [kPa]" and enter the desired filling pressure. The value
range is between 0 kPa and 1000 kPa.

• Tap "Fill Pressure". The RapidOxy 100 fills the test chamber with oxygen. A
screen shows the build-up of pressure. When the pressure is reached, the
"Manual Functions" menu is displayed again. The test chamber is pressurized.

3.7 CLEANING

In order to ensure proper and safe functioning of the RapidOxy 100 instrument,
perform maintenance and cleaning routines regularly during standard operation.
Make sure that all equipment used is completely clean and undamaged.

When to perform:

• After each test run

Required tools:

• Soft tissues

• Ethanol

Remove any remaining sample and the O-ring from the test chamber. Discard
the O-ring - never use O-rings twice. Wipe the chamber and the screw cap with
a dry soft tissue first. Soak a clean tissue with ethanol and wipe the chamber and
the screw cap. Do not rinse or immerse the screw cap into any liquid. Let all
parts dry completely.

27
Fig 3.7 Cleaning

28
CHAPTER 4
EXPERIMENTAL OUTPUT
4.1 FOR 5ML BIO-DIESEL
Program:
Program name B0 - B100 Pressure
12
Program type Present program
10
Start temperature 25.0 °C
Filling pressure 7.000 bar 8

Preesure bar
Target temperature 140.0 °C 6

Purging Standard 1x 4
Stop criterion 2
Pressure drop 10.00% 0
Cooling temperature 35.0 °C 0 90 180 270 360 450 540 630 720 810 900 9901080

Result Time in 's'


Status OK
Pressure drop result 10.0 % at 18.97 min Pressure bar
Test duration result OK
Condition -
Fig 4.1.1
Emergency -
Total runtime 18.97 min
The pressure starts at 6.995 bar and ends
Average temperature 140.1 °C
at 9.521 bar. The maximum pressure is
Max. temperature 140.3 °C
10.581 bar and the pressure difference
Pressure at start 6.995 bar
Max. pressure 10.581 bar Is 1.059 bar, the time period is 18 min.
Pressure at stop 9.521 bar
Pressure difference 1.059 bar

Fig 4.1.2 Fig 4.1.3

29
4.2 FOR 5ML OF BIO-DIESEL 500PPM PG
Program:
Pressure
Program name B0 - B100
12
Program type Present program
10
Start temperature 25.0 °C 8

Pressure bar
Filling pressure 7.000 bar 6

Target temperature 140.0 °C 4

2
Purging Standard 1x
0
Stop criterion 2 303 604 905 1206150718082109241027113012
Time in 's'
Pressure drop 10.00%

Result Pressure bar

Status OK Fig 4.2.1


Pressure drop result 10.0 % at 54.78 min The pressure starts at 6.999 bar and ends
Test duration result OK at 9.564 bar. The maximum pressure is
10.631 bar and the pressure difference is
Condition - 1.067 bar, the time period is 54.78 min.
Emergency -

Total runtime 54.78 min

Average temperature 140.0 °C

Max. temperature 140.3 °C

Pressure at start 6.999 bar

Max. pressure 10.631 bar

Pressure at stop 9.564 bar

Pressure difference 1.067 bar

30
Fig 4.2.2 Fig 4.2.3
4.3 FOR 5ML OF BIO-DIESEL 750PPM OF PG

Program name B0 - B100


Program type Present program
Pressure
12
Start temperature 25.0 °C
10
Filling pressure 7.000 bar
8
Pressure bar

Target temperature 140.0 °C


6
Purging Standard 1x
4
Stop criterion
2
Pressure drop 10.00%
0
Cooling temperature 35.0 °C 4 499 994 14891984247929743469396444594954
Result Time in 's'
Status OK
10.0 % at 90.57
Pressure drop result min Pressure bar

Test duration result OK Fig 4.3.1


Condition -
The pressure starts at 6.999 bar and ends
Emergency - at 9.511 bar. The maximum pressure is
Total runtime 90.57 min 10.570 bar and the pressure difference is
Average temperature 140.0 °C 1.059 bar, the time period is 90.57 min.
Max. temperature 140.3 °C
Pressure at start 6.999 bar
Max. pressure 10.570 bar
Pressure at stop 9.511 bar
Pressure difference 1.059 bar

31
Fig 4.3.2 Fig 4.3.3

4.4 FOR 5ML OF BIO-DIESEL 1000PPM OF PG

Program:
Pressure Bar
Program name B0 - B100
Program type Present program 12
Start temperature 25.0 °C 10
Filling pressure 7.000 bar
8
Pressure bar

Target temperature 140.0 °C


6
Purging Standard 1x
Stop criterion 4
Pressure drop 10.00% 2
Cooling temperature 35.0 °C 0
Result 11 1236 2461 3686 4911 6136 7361 8586 9811 11036
Status OK Time in 's'
10.0 % at 202.32
Pressure drop result min Pressure bar
Test duration result OK
Condition -
Fig 4.4.1
Emergency -
Total runtime 202.32 min The pressure starts at 7.009 bar and ends
Average temperature 140.0 °C at 9.491 bar. The maximum pressure is
Max. temperature 140.4 °C 10.550 bar and the pressure difference is
Pressure at start 7.009 bar 1.059 bar, the time period is 202.32 min.
Max. pressure 10.550 bar
Pressure at stop 9.491 bar
Pressure difference 1.059 bar

32
Fig 4.4.2 Fig 4.4.3
4.5 FOR 5ML OF BIO-DIESEL 500PPM OF TBHQ

Program:
Program name B0 - B100
Pressure
12
Program type Present program 10
Pressure bar

8
Start temperature 25.0 °C
6
Filling pressure 7.000 bar 4
Target temperature 140.0 °C 2
0
Purging Standard 1x 1 211 421 631 841 105112611471168118912101
Stop criterion Time in 's'
Pressure drop 10.00%
Cooling temperature 35.0 °C
Pressure bar
Result
Status OK Fig 4.5.1
10.0 % at 38.27
Pressure drop result min The pressure starts at 6.999 bar and ends
Test duration result OK at 9.445 bar. The maximum pressure is
10.449 bar and the pressure difference is
Condition -
1.054 bar, the time period is 38.27 min.
Emergency -
Total runtime 38.27 min
Average temperature 140.0 °C
Max. temperature 140.3 °C
Pressure at start 6.999 bar
Max. pressure 10.499 bar
Pressure at stop 9.445 bar
Pressure difference 1.054 bar

33
Fig 4.5.2 Fig 4.5.3

34
4.6 FOR 5ML OF BIO-DIESEL 750PPM OF TBHQ

Program: Fig 4.6.1


Program name B0 - B100
Program type Present program The pressure starts at 7.006 bar and ends
Start temperature 25.0 °C at 9.521 bar. The maximum pressure is
Filling pressure 7.000 bar 10.581 bar and the pressure difference is
Target temperature 140.0 °C
Purging Standard 1x Pressure
Stop criterion 12
Pressure drop 10.00% 10
Cooling temperature 35.0 °C 8

Pressure bar
Result
6
Status OK
10.0 % at 99.62 4
Pressure drop result min 2
Test duration result OK 0
5 521 1037155320692585310136174133464951655681
Condition -
Emergency - Time in 's'
Total runtime 99.62 min
Average Pressure bar
temperature 140.0 °C
1.059 bar, the time period is 99.62 min.
Max. temperature 140.3 °C
Pressure at start 7.006 bar
Max. pressure 10.581 bar
Pressure at stop 9.521 bar
Pressure difference 1.059 bar

Fig 4.6.2 Fig 4.6.3

35
4.7 FOR 5ML OF BIO-DIESEL 1000PPM OF TBHQ

Program: Fig 4.7.1


Program name B0 - B100
Program type Present program The pressure starts at 6.989 bar and ends
Start temperature 25.0 °C at 9.597 bar. The maximum pressure is
Filling pressure 7.000 bar
Target temperature 140.0 °C
Purging Standard 1x Pressure
Stop criterion 12
Pressure drop 10.00% 10
Cooling temperature 35.0 °C
8

Pressure bar
Result
Status OK 6
10.0 % at 129.32 4
Pressure drop result min
2
Test duration result OK
Condition - 0
7 663 1319197526313287394345995255591165677223
Emergency -
Time in 's'
Total runtime 129.32 min
Average temperature 140.0 °C
Max. temperature 140.4 °C Pressure bar
Pressure at start 6.989 bar 10.668 bar and the pressure difference is
Max. pressure 10.668 bar 1.071 bar, the time period is 129.32 min.
Pressure at stop 9.597 bar
Pressure difference 1.071 bar

Fig 4.7.2 Fig 4.7.3

36
4.8 FOR 3.5ML OF DIESEL & 1.5ML OF BIO-DIESEL
Sample Name B30 3.5diesel 1.5biod Fig 4.8.1
Date and time 3/22/2023 8:46:09 AM
The pressure starts at 6.999 bar and ends
User Administrator
at 10.792 bar. The maximum pressure is
Program:
11.994 bar and the pressure difference is
Program name B0 - B100
Program type Present program
Pressure
Start temperature 25.0 °C
Filling pressure 7.000 bar 14

Target temperature 140.0 °C 12


Purging Standard 1x
10
Stop criterion
Pressure drop 10.00%
Pressure bar
8
Cooling temperature 35.0 °C
6
Result
Status OK 4
Pressure drop result 10.0 % at 45.55 min
2
Test duration result OK
Condition - 0
2 254 506 758 1010126215141766201822702522
Emergency -
Total runtime 45.55 min Time in 's'
Average
temperature 140.0 °C
1.201 bar, the time period is 45.55 min.
Max. temperature 140.3 °C
Pressure at start 6.999 bar
Max. pressure 11.994 bar
Pressure at stop 10.792 bar
Pressure difference 1.201 bar

37
Fig 4.8.2 Fig 4.8.3
4.9 FOR 3.5ML OF DIESEL, 1.5ML OF BIO-DIESEL &
500PPM TBHQ
B30 3.5diesel 1.5biod Fig 4.9.1
Sample Name 500 tbhq
User Administrator The pressure starts at 6.999 bar and ends
Program:
Program name B0 - B100 Pressure
Program type Present program
14
Start temperature 25.0 °C
12
Filling pressure 7.000 bar
10
Target temperature 140.0 °C

Pressure bar
8
Purging Standard 1x
6
Stop criterion
4
Pressure drop 10.00%
2
Cooling
temperature 35.0 °C 0
7 679 1351202326953367403947115383605567277399
Result Time in 's'
Status OK
Pressure drop
result 10.0 % at 128.35 min
Pressure bar
Test duration result OK
Condition - at 10.308 bar. The maximum pressure is
Emergency - 11.458 bar and the pressure difference is
Total runtime 128.35 min 1.150 bar, the time period is 128.35 min.
Average
temperature 140.0 °C
Max. temperature 140.4 °C
Pressure at start 6.999 bar
Max. pressure 11.458 bar
Pressure at stop 10.308 bar
Pressure difference 1.150 bar

38
Pressure
14
Fig 4.9.2
12

4.10 FOR 4.6ML OF BIO- 10

Pressure bar
DIESEL, 0.4ML OF 8
6
DIETHYL ETHER &
4
1000PPM TBHQ 2
0
1 157 313 469 625 781 937 109312491405156117171873
Time in 's'

Pressure bar

39
Program: Fig 4.10.1
Program name B0 - B100 The pressure starts at 6.999 bar and ends
Program type Present program at 10.312 bar. The maximum pressure is
Start temperature 25.0 °C 11.458 bar and the pressure difference is
Filling pressure 7.000 bar 1.146 bar, the time period is 32.58 min.
Target temperature 140.0 °C
Purging Standard 1x
Stop criterion
Pressure
Pressure drop 10.00%
12
Cooling temperature 35.0 °C
10
Result
Status OK 8

Pressure bar
10.0 % at 32.58 6
Pressure drop result min
4
Test duration result OK
2
Condition -
Emergency - 0
1 191 381 571 761 951 114113311521171119012091
Total runtime 32.58 min Time in 's'
Average temperature 140.0 °C
Max. temperature 140.3 °C Pressure bar

Pressure at start 6.999 bar


Max. pressure 11.458 bar
Pressure at stop 10.312 bar
Pressure difference 1.146 bar

Fig 4.10.2 Fig 4.10.3


4.11 FOR 4.6ML OF BIO-DIESEL, 0.4ML OF DIETHYL
ETHER & 2000PPM TBHQ

40
Program: Fig 4.11.1
Program name B0 - B100 The pressure starts at 6.999 bar and ends
Program type Present program at 10.281 bar. The maximum pressure is
Start temperature 25.0 °C 11.428 bar and the pressure difference is
Filling pressure 7.000 bar 1.147 bar, the time period is 37.42 min.
Target temperature 140.0 °C
Purging Standard 1x
Stop criterion
Pressure drop 10.00%
Cooling temperature 35.0 °C
Result
Status OK
Pressure drop result 10.0 % at 37.42 min
Test duration result OK
Condition -
Emergency -
Total runtime 37.42 min
Average
temperature 140.0 °C
Max. temperature 140.3 °C
Pressure at start 6.999 bar
Max. pressure 11.428 bar
Pressure at stop 10.281 bar
Pressure difference 1.147 bar

Fig 4.11.2 Fig 4.11.3


4.12 FOR 4.6ML OF BIO-DIESEL, 0.4ML OF DIETHYL
ETHER & 2000PPM PG

41
Program: Fig 4.12.1
Program name B0 - B100
The pressure starts at 6.993 bar and ends
Program type Present program
at 10.708 bar. The maximum pressure is
Start temperature 25.0 °C
11.902 bar and the pressure difference is
Filling pressure 7.000 bar
1.194 bar, the time period is 157.52 min.
Target temperature 140.0 °C
Purging Standard 1x
Stop criterion
Pressure drop 10.00%
Cooling temperature 35.0 °C Pressure
Result 14
Status OK 12
Pressure drop result 10.0 % at 157.52 min 10

Pressure bar
Test duration result OK 8

Condition - 6

Emergency - 4

Total runtime 157.52 min 2

Average temperature 140.0 °C 0


8 806 1604240232003998479655946392719079888786
Max. temperature 140.3 °C
Time in 's'
Pressure at start 6.993 bar
Max. pressure 11.902 bar
Pressure bar
Pressure at stop 10.708 bar
Pressure difference 1.194 bar

Fig 4.12.2 Fig 4.12.3

42
CHAPTER 5
CONCLUSION

 Antioxidants reduces fuel aging.


 In this study Oxidation Stability of Bio-Diesel along with effect of Tert-
Butyl Hydroquinone (TBHQ) & Propyl Gallate (PG) is analysed and
studied.
 The unsaturated fatty acid percentages and the longer chain double bonded
hydrocarbon in the biodiesel have the great influence on the stability of the
biodiesel, as these are higher, the quality of the fuel would be poor as well as
the properties would be degraded faster with increasing storage time.
 These experimental results were carried out and evaluation of the oxidation
and storage stabilities of biodiesel fuels with various additives with
different proportion is noted.
 It can also be predicted from the trends of the figures that fuel quality would
be deteriorated with increasing storage time. Since the oxidation of fuels are
largely dependent on the storage conditions. Further study is required to
investigate the stabilities of the biodiesel applying various conditions which
would help to improve fuel quality by improving the oxidation, thermal and
storage stabilities.

43
CHAPTER 6
REFERENCE

1. Dunn RO, Knothe G. Oxidative stability of biodiesel in blends with jet


fuel by analysis of oil stability index. J Am Oil Chem Soc
2003;80:1047–8.
2. Karavalakis G, Stournas S. Impact of antioxidant additives on the
oxidation stability of diesel/biodiesel blends. Energy Fuels
2010;24:3682–6.
3. Sarin A, Arora R, Singh NP, Sarin R, Malhotra RK. Blends of
biodiesels synthesized from non-edible and edible oils: influence on
the OS (oxidation stability). Energy 2010;35:3449–53.
4. Sarin R, Sharma M, Sinharay S, Malhotra RK. Jatropha–palm
biodiesel blends: an optimum mix for Asia. Fuel 2007;86(10–
11):1365–71.
5. Dunn RO. Effect of oxidation under accelerated conditions on fuel
properties of methyl soyate. J Am Oil Chem Soc 2002;79:915–20.
6. Dunn RO. Effect of antioxidants on oxidative stability of methyl
soyate. Fuel Process Technol 2005;86:1071–85.
7. Knothe G, Dunn RO. Dependance of oil stability index of fatty
compounds on their structure and concentration and presence of
metals. J Am Oil Chem Soc 2003;80:1021–6.
8. Ferrari RA, Oliveira VD, Scabio A. Oxidative stability of biodiesel
from soyabean oil fatty acid ethyl esters. Sci Agric 2005;62:291–5.
9. Park JY, Kim DK, Lee JP, Park SC, Kim YJ, Lee JS. Blending effects
of biodiesel on oxidation stability and low temperature flow
properties. Bioresource Technol 2008;99:1196–203.

44
CHAPTER 7
ACHIEVEMENT

45
46
47
48

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