Biodiesel production

Biodiesel Production through Trans-esterification of vegetable oils

Project Report

Submitted By

Gautam parmar
(B. Sc. Biotechnology Semester VI)




Guided By


Mrs. Shweta Bhatt
Assistant Professor
Department of Biotechnology
Shree M. & N. Virani Science College,
Rajkot




" "
"Department of BIOTECHNOLOGY "
" "
"Shree M. & N. Virani Science College "
" "
"(Re-accredited at the "A" Level by NAAC & STAR College Department "
"status by MST-DBT) "
"(College with Potential for Excellence by UGC & Accredited at the "A" "
"Level by KCG) "
"Rajkot, Gujarat – 360005 "






Shree M. & N. Virani Science College

(Re-accredited at the "A" Level by NAAC & STAR College Department status by
MST-DBT)
(College with Potential for Excellence by UGC & Accredited at the "A" Level
by KCG)


Department of Biotechnology

Virani/Biotech/2014-15 Exam Seat No.



Date:

CERTIFICATE


This is to certify that the project entitled, "Biodiesel Production through
Trans-esterification of vegetable oils" was successfully carried out by
Gautam Parmar an under graduate student of Biotechnology Department, Shree
Manibhai Virani and Smt. Navalben Virani Science College affiliated to
Saurashtra University, Rajkot; for the degree of B.Sc. in Biotechnology
during academic year 2014-15.




"Dr. Shivani Patel "Mrs. Shweta Bhatt "
"Head, "(Guide) "
"Dept. of Biotechnology "Department of Biotechnology, "
"Shree M. & N. Virani Science "Shree M. & N. Virani Science "
"College, "College, "
"Rajkot - 360 005 "Rajkot -360005 "







DECLARATION


We hereby declare that this Project Report on, "Biodiesel Production
through Trans-esterification of vegetable oils", which is being submitted
as a part of the partial fulfillment for the degree of Bachelor of Science,
in Biotechnology, is the result of the work carried out by us, under the
guidance of Mrs. Shweta Bhatt, Faculty of Department of Biotechnology,
Shree M. & N. Virani Science College, and Rajkot.


"Name of Student " Gautam Parmar "


ACKNOWLEDGEMENTS


I wish to express my deep sense of gratitude to my Guide Mrs. Shweta Bhatt,
Faculty of Department of Biotechnology, Shree M. & N. Virani Science
College, for her able guidance and useful suggestions, which helped me in
completing the Undergraduate Research Project, in time.

I take immense pleasure in thanking (Dr.) Shivani Patel, Head Department of
Biotechnology for her kind permission to work in the department laboratory
& providing constant support & encouragement during the Project work.

I would also like to thank to my classmates, juniors, for their useful
suggestions during our Research Project and lastly I would also extend my
thanks to our pions kuldeep bhai ,Indrajeet bhai and lab assistant Kailash
mam.

Thanks to Bharat petroleum corp. and their staff members.

Finally, yet importantly, we would like to express our heartfelt thanks to
our beloved parents for their blessings.





























INDEX

"Chapter "Title "Page No. "
"No. " " "
" "List of Tables "24-25 "
" "List of Figures "12,14,18,20,21,"
" " "27 "
" "List of Abbreviations "10 "
"01 "Introduction "11-16 "
"02 "Review of literature "17 "
"03 "Materials and Method "18-21 "
"04 "Result & Discussion "24-29 "
"05 "Conclusion "30 "
"06 "References "31-32 "
" "Annexure – I "34 "
" " " "
" "Reagent Preparation " "
" "Annexure – II "34 "
" " " "
" "Instrument Used – Company " "












List of Table

"Table No. "Title "Page no. "
"1 "Transesterification process of different"24 "
" "oils.. " "
"2 "Comparison of properties of waste "25 "
" "cooking oil, biodiesel from waste " "
" "cooking oil and commercial diesel fuel. " "






































List of Figures



"Figure No. "Title "Page No."
"1 "Rudolf Diesel "12 "
"2 "Chemical process for methyl ester biodiesel. "14 "
"3 "Oil samples "18 "
"4 "Mixing of methoxide solution and oil "19 "
"5 "Transesterifcation process "20 "
"6 "Phase layer separation "20 "
"7 "Centrifugal separation of small particles "21 "
"8 "Two distinct layers "27 "






























List of Abbreviation

"Abbreviation "Full Form "
"KOH "Potassium hydroxide "
"NaOH "Sodium hydroxide "
" SVO "Straight vegetable oil "
"WVO "Waste vegetable oil "
"PPO "Pure plant oil "
"ASTM "American society for testing and "
" "materials "
"B100 "Biodiesel blend 100 "
"rpm "Rotation per minute "
"ULSD "Ultra low sulphur diesel "
"FFA "Free fatty acids "
"JTF "Jan Warnqvist test "




















INTRODUCTION

The term biofuel is used here to mean any liquid fuel made from plant
material that can be used as a substitute for petroleum-derived fuel.
Biodiesel is made from vegetable oil, recycled cooking oil and animal fats.
Chemically biodiesel is described as a mono alkyl ester. Through a process
called esterification, oil and fats are reacted with methanol and sodium
hydroxide catalyst to produce fatty acids along with the co-products:
glycerin. Biodiesel is biodegradable, nontoxic, and has significantly fewer
emissions than petroleum-based diesel when burned. The largest possible
source of suitable oil comes from oil crops such as soybean, rapeseed,
corn, and sunflower. At present, oil straight from the agricultural
industry represents the greatest potential source, but it is not being used
for commercial production of biodiesel simply because the raw oil is too
expensive. After the cost of converting it to biodiesel has been added,
the price is too high to compete with petroleum diesel. Waste vegetable
oil can often be obtained for free or already treated for a small price.
One disadvantage of using waste oil is it must be treated to remove
impurities like free fatty acids (FFA) before conversion to biodiesel is
possible. Biodiesel has a viscosity similar to petro diesel, the industrial
term for diesel produced from petroleum. It can be used as an additive in
formulations of diesel to increase the lubricity of pure Ultra-Low Sulfur
Diesel (ULSD) fuel, although care must be taken to ensure that the
biodiesel used does not increase the sulfur content of the mixture above 15
ppm. . Much of the world uses a system known as the "B" factor to state the
amount of biodiesel in any fuel mix, in contrast to the "BA" or "E" system
used for ethanol mixes. For example, fuel containing 20% biodiesel is
labeled as B20. Pure biodiesel is referred to as B100.B100 is generally not
suitable for use in low temperature condition. Transportation and storage
of B100 however require special management.B2 and B5are popular as a
lubricant due to biodiesel's high lubricity rating.. One of the major
reasons for the increased utilization of fatty acids for industrial use has
been the ability to tailor the products to specific needs. The concept of
using vegetable oil as an engine fuel likely dates to when Rudolf Diesel
(1858-1913) developed the first engine to run on peanut oil, as he
demonstrated at the World Exhibition in Paris in 1900.











Fig 1. Rudolf Diesel

Rudolf Diesel firmly believed the utilization of a biomass fuel to be the
real future of his engine. He wanted to provide farmers the opportunity to
produce their own fuel. In 1911, he said, "The diesel engine can be fed
with vegetable oils and would help considerably in the development of
agriculture of the countries which use it." "The use of vegetable oils for
engine fuels may seem insignificant today. But such oils may become, in the
course of time, as important as the petroleum and coal tar products of the
present time. "Rudolf Diesel, 1912 Unfortunately, Rudolf Diesel died in
1913 before his vision of a vegetable oil powered engine was fully
realized. At the time of Diesel's death, the petroleum industry was rapidly
developing and producing a cheap by-product called "diesel fuel" that would
power a modified "diesel engine". Thus, clean vegetable oil was forgotten
as a renewable source of power. Modern diesels are now designed to run on
a less viscous (easier flowing) fuel than straight vegetable oil, but, in
times of fuel shortages, cars and trucks were successfully run on preheated
peanut oil and animal fat.
















Availability

Waste vegetable oil
As of 2000, the United States was producing in excess of 11 billion liters
of waste vegetable oil annually, mainly from industrial deep fryers in
potato processing plants, snack food factories and fast food restaurants.
If all those 11 billion liters could be and used to replace the
energetically equivalent amount of petroleum, almost 1% of US oil
consumption could be offset.Use of waste vegetable oil as a fuel competes
with some other uses of the commodity, which has effects on its price as a
fuel and increases its cost as an input to the other uses as well.
Pure plant oil (Straight vegetable oil) Pure plant oil (PPO) (or Straight
Vegetable Oil (SVO)), in contrast to waste vegetable oil, is not a
byproduct of other industries, and thus its prospects for use as fuel are
not limited by the capacities of other industries. Production of vegetable
oils for use as fuels is theoretically limited only by the agricultural
capacity of a given economy. However, doing so detracts from the supply of
other uses of pure vegetable oil.




Transesterification

Transesterification of natural glycerides with methanol to methyl esters is
a technically important reaction that has been used extensively in the soap
and detergent manufacturing industry worldwide for many years. Almost all
biodiesel is produced in a similar chemical process using base catalyzed
trans esterification as it is the most economical process, requiring only
low temperatures and pressures while producing a 98% conversion yield.
During the esterification process, the triglyceride is reacted with alcohol
in the presence of a catalyst, usually a strong alkaline like sodium
hydroxide. The alcohol reacts with the fatty acids to form the mono-alkyl
ester, or biodiesel, and crude glycerol. In most production, methanol or
ethanol is the alcohol used (methanol produces methyl esters, ethanol
produces ethyl esters) and is base catalyzed by either potassium or sodium
hydroxide. Potassium hydroxide has been found more suitable for the ethyl
ester biodiesel production, but either base can be used for methyl ester
production.



Fig 2. Chemical process for methyl ester biodiesel.

The reaction between the fat or oil and the alcohol is a reversible
reaction, so the alcohol must be added in excess to drive the reaction
towards the right and ensure complete conversion. The products of the
reaction are the biodiesel itself and glycerol.

A successful Trans esterification reaction is signified by the separation
of the methyl ester (biodiesel) and glycerol layers after the reaction
time. The heavier co-product, glycerol, settles out and may be sold as is
or purified for use in other industries, e.g. pharmaceutical, cosmetics,
and detergents. After the Trans esterification reaction and the separation
of the crude heavy glycerin phase, the producer is left with a crude light
biodiesel phase. This crude biodiesel requires some purification prior to
use. Biodiesel's commercial fuel quality is measured by the ASTM standard
designated D 6751. The standards ensure that biodiesel is pure and the
following important factors in the fuel production process are satisfied:
Complete reaction, Removal of glycerin, Removal of catalyst, Removal of
alcohol, Absence of free fatty acids, Low sulfur content.









Characteristics of Alcohols Used in Biodiesel Production

Alcohols that can be used in biodiesel production are those with short
chains, including methanol, ethanol, butanol, and amylic alcohol. The most
widely used alcohols are methanol (CH3OH) and ethanol (C2H5OH) because of
their low cost and properties. Methanol is often preferred to ethanol in
spite of its high toxicity because its use in biodiesel production requires
simpler technology; excess alcohol may be recovered at a low cost and
higher reaction speeds are reached.

Methanol-Most widely used, in spite of its toxicity. It is a substance of
petrochemical origin. Ethanol-Less used, requires more complex production
technology and the reaction speeds are lower. It can be produced from
biomass.

Catalyst used

The catalysts used for the transesterification of triglycerides may be
classified as basic, acid or enzymatic. Basic catalysts include sodium
hydroxide (NaOH), potassium hydroxide (KOH), carbonates and their
corresponding alcoxides (for instance, sodium methoxide or ethoxide). There
are many references on basic catalysts in the scientific literature.NaOH is
generally preferred over KOH because it takes lesser time to speed up the
reaction of conversion of fatty acids into biodiesel. The reaction time
varies according to the amount of catalyst used. For 500 ml 3.5 gm of NaOH
is sufficient to enhance the reaction of trans esterification.

Advantages of Biodiesel Production

1. Biodiesel is bio renewable. Feed stocks can be renewed one or more
times in a generation.

2. Biodiesel is carbon neutral. Plants use the same amount of CO2 to make
the oil that is released when the fuel is burned.

3. Biodiesel is rapidly biodegradable and completely nontoxic, meaning
spillages represent far less risk than petroleum diesel spillages.

4. Biodiesel has a higher flash point than petroleum diesel, making it
safer in the event of a crash.

5. Blends of 20% biodiesel with 80% petroleum diesel can be used in
unmodified diesel engines. Biodiesel can be used in its pure form but may
require certain engine modifications to avoid maintenance and performance
problems.

6. Biodiesel can be made from recycled vegetable and animal oils or fats.

7. Biodiesel is nontoxic and biodegradable. It reduces the emission of
harmful pollutants, mainly particulates, from diesel engines (80% less CO2
emissions, 100% less sulfur dioxide). But emissions of nitrogen oxide, the
precursor of ozone, are increased.

8. Biodiesel has a high cetane number of above 100, compared to only 40 for
petroleum diesel fuel. The cetane number is a measure of a fuel's ignition
quality. The high cetane numbers of biodiesel contribute to easy cold
starting and low idle noise. The use of biodiesel can extend the life of
diesel engines because it is more lubricating and, furthermore, power
output is relatively unaffected by biodiesel.

9. Biodiesel replaces the exhaust odor of petroleum diesel with a more
pleasant smell of popcorn or French fries.

Objective
1. To produce biodiesel through Trans esterification of vegetable oils.
2. To perform confirmatory tests of biodiesel produced.















REVIEW OF LITERATURE

The first record of the use of vegetable oils as liquid fuels in internal
combustion engines is from 1900 when Rudolf Diesel used peanut oil (Shay,
1993). However because of its low cost and easy availability, Petroleum
became dominant energy source and petroleum diesel was then developed as
the primary fuel for diesel engines. Nonetheless, petroleum and its
derivatives fuels have periodically been through short supply and
consequently, the search for alternative energy sources has emerged (Zanin
et al, 2000). At that time the pyrolysis of different triglycerides was
also used for liquid fuel supply in different countries. For example,
hydrocarbons were produced in Chinaby a tung oil pyrolysis batch system
used as liquid fuels (Chang and Wan, 1947). Another approach proposed at
this time was the use of fatty acids ethyl or methyl esters, obtained by
transesterification or alcoholysis of vegetable oils or esterification of
fatty acids combined with transesterification of triglycerides (Keim,
1945). Biodiesel production is a very modern and technological area for
researchers due to the relevance that it is winning everyday because of the
increase in the petroleum price and the environmental advantages (Marchetti
et al, 2005). It is an alternatives fuel for diesel engines that is
produced by chemical reaction of a vegetable oils or animal fats with an
alcohol such as methanol. The product is called as methyl ester or
biodiesel, which is receiving high attention as an alternative, nontoxic,
biodegradable and renewable diesel fuels (Ma and Hanna, 1999). When
biodiesel displaces petroleum diesel, it reduces global warming gas
emission such as carbon dioxide. Biodiesel has no aromatics, almost no
sulfur and contains 11% oxygen by weight. These characteristics of
biodiesel reduces the emissions of carbon monoxide, hydrocarbon and
particulate matter in the exhaust gas compare petroleum-based diesel fuels
(Peterson and Hustrulid, 1998).
Vegetable oils are widely available from various sources, and the
glycerides present in the oils can be considered as a viable alternative
for diesel fuel. Biodiesel, which is synthesized from bio-oil, is a
realistic alternative of diesel fuel because it provides a fuel from
renewable resources and has lower emissions than petroleum diesel. It is
biodegradable and contributes a minimal amount of net greenhouse gases or
sulfur to the atmosphere. More specifically, biodiesel cuts down on the
amount of carbon dioxide, hydrocarbons, and particulate matter released
into the environment (Dalai et. al., 2003). There are several sources that
can be use as raw material for biodiesel production, such as non-edible
oil, animal fats and vegetable oil.
MATERIALS AND METHOD
Objective

1. To produce biodiesel through Trans esterification of vegetable oils.
2. To perform confirmatory tests of biodiesel produced.
1. Collection of sample- Seven Different oil samples was collected from
shop vendors, restaurants, industries, and houses of friends. The oil
samples collected were Soybean oil, castor oil, sunflower oil, rice bran
oil, groundnut oil, corn oil, cotton oil.





Fig-3 Oil samples

2. Pre-treatment of oil samples- All the samples of oil were subjected to
filtration through filter paper to remove the chunks and debris present in
it. This makes oil sample free from large fragments of contaminants and
helps in maintain the homogenous composition of the oil.
3. Warm up oil- Pour about 500 ml of oil into the flask and turn the
electric heater to low. We need to warm up the oil for a couple of reasons.
First, the heating will make the oil less viscous so it will stir more
easily. Second, the heat helps the conversion to biodiesel go faster
4. Methoxide solution- Take 2 gm of NaOH in 70ml of methanol for castor
oil. Take 2.5 gm of NaOH in 80 ml of methanol for sunflower oil. Take 3 gm
of NaOH in 90 ml o methanol for corn oil. Take 3.5 gm of NaOH in 100ml
methanol for soybean oil. Take 1 gm of KOH in 50 ml of methanol for cotton
oil. Take 1.5 gm 0f KOH in 60 ml of methanol for groundnut oil. Take 0.5 gm
of KOH in 40 ml of methanol for rice bran oil. Mix each of the contents in
the flask and keep it in orbital shaker for 2 hrs for proper mixing and
care must be taken because this solution is exothermic solution and
carcinogenic.
5. Pour Methoxide solution into different oils samples- Now cool down oil
at room temperature and pour the methoxide solution into the oil from the
side walls and mix it properly for the conversion of triglycerides into
biodiesel. Turn on the magnetic stirrer to mix the methoxide, oil and
methanol. The stirrer should not be too fast, the meagnetic bar may get
unstable. Stirring time is normally listed as 2hrs. To get maximum yield of
biodiesel, 2hrs is recommended.









Fig-4. Mixing of methoxide solution and oil

6. Transfer the solution into separating funnel- After 2hrs of stirring,
the obtained product is poured into the separating funnel. And the reaction
mixture is kept overnight for phase separation of two distinctive layer. If
triglycerides present in oil are converted into esters then it will form
two distinctive layers. One obtained at upper side is lighter golden and
other is denser at bottom.










Fig 5. Transesterification process




Fig 6. Phase layer separation



7. Drain off glycerin- Turn the stopcock so the glycerin drains out.
Glycerin can be saved to be used for other purposes. This glycerin has some
contamination with NaOH/KOH and methanol, but the NaOH/KOH is neutralized
and the methanol will evaporate. The NaOH/KOH can be neutralized with a
little lemon juice to get it around a pH of 6 or 7.
8. Drain off biodiesel- The biodiesel is collected in a beaker. The
biodiesel is obtained in a Liquid gold colour. The biodiesel is dried, to
remove the traces of water. It is kept in sunlight for sedimentation of
particulate matter and other impurities present in it and for removal of
excess methanol present



9. Centrifugation of biodiesel produced- For the removal of small
particulate impurities centrifugation of produced biodiesel from different
samples is done. Biodiesel is centrifuged at 8000 rpm for 15 minutes.
Observe for pellet formation, if present discard the pellet and take out
the supernatant biodiesel in fresh tube with the help of micropipette and
store at room temperature.










Fig 7 Centrifugal separation of small particles

















Properties studied for Confirmatory test of Biodiesel Produced

1. Density (g/cm³) - Is the weight per unit volume. Oils that are denser
contain more energy. For example, petrol and diesel fuels give
comparable energy by weight, but diesel is denser and hence gives more
energy per liter (0.87-0.89)

2. Viscosity (mm/³s) - Viscosity refers to the thickness of the oil, and
is determined by measuring the amount of time taken for a given
measure of oil to pass through an orifice of a specified size.
Viscosity affects injector lubrication and fuel atomization. Fuels
with low viscosity may not provide sufficient lubrication for the
precision fit of fuel injection pumps, resulting in leakage or
increased wear. Fuel atomization is also affected by fuel viscosity.
Diesel fuels with high viscosity tend to form larger droplets on
injection which can cause poor combustion, increased exhaust smoke and
emissions.

3. Cloud point (C°) - The temperature at which an oil starts to solidify
is known as the cloud point. While operating an engine at temperatures
below oil's cloud point, heating will be necessary in order to avoid
waxing of the fuel (3-15 C°).

4. Temperature (C°)- It is the optimum temperature at which conversion of
fatty acid into biodiesel takes place.(35-40 C°)

5. Sulphur content (%)- The percentage by weight, of sulfur in the fuel
Sulfur content is limited by law to very small percentages for diesel
fuel used in on-road applications

6. Flash point (C°) - The flash point temperature of a fuel is the
minimum temperature at which the fuel will ignite (flash) on
application of an ignition source. Flash point varies inversely with
the fuel's volatility. Minimum flash point temperatures are required
for proper safety and handling of diesel fuel (110-130 C°)

7. pH- Normal PH of petro diesel should be between 6-7.

8. Water content (%) -it is the amount of water present in petro diesel.
It should be minimum between (0.02-0.05).

9. Color- This is a visual inspection of the finished biodiesel. Water
free biodiesel will be clear and will be of golden yellow color

10. Pour point (C°) - Melt or pour point refers to the temperature at
which the oil in solid form starts to melt or pour. In cases where the
temperatures fall below the melt point, the entire fuel system
including all fuel lines and fuel tank will need to be heated.(-3to
-8).

11. Clarity Testing Finished Biodiesel for Water- This is a visual
inspection of the finished biodiesel. Water free biodiesel will be
clear. The common method of testing is to put a sample in a jar and if
you can read a newspaper through the biodiesel then it passes the
test. For larger batches, the ability to see the bottom of a drum of
biodiesel clearly is often used. This is a good test however it does
not detect water that is dissolved in the biodiesel.







































Result and Discussion

Objective-

1. To produce biodiesel through Trans esterification of vegetable oils.

2. To perform confirmatory tests of biodiesel produced.



Table 1. Transesterification process of different oils..

"Oil sample "Amount of oil (ml) "
"Balance "CYBER LAB "
"Autoclave "EQUITRON "
"Incubator "Yorko "
"Orbital shaker "ASIND "
"Centrifuge "REMI "
"Spectrophotometer "LAB INDIA "
"Refrigerator "LG "
"pH meter " "
"Microwave oven "Samsung "
"Hot air oven "Yorko "