Faculty of Engineering

Chemistry Department

(Chem-101)

Production of Biodiesel

Student name ID
Nayera Hisham Elsaady 18100036
Radwa Mohamed Abdelaal 18100183
Shorouk Abdelfattah Alalem 18100433
Maryam Mohamed Elfdaly 18100215
Mohamed Masoud 18101478

Lecture/tutorial Group: Tutorial 4

Instructor: Dr. Mai Zohdy

Fall 2018
 Table of Contents

Abstract ............................................................................................................................................3
Introduction ......................................................................................................................................4
Research ...........................................................................................................................................5
Methods............................................................................................................................................8
Test plan .........................................................................................................................................13
Results ............................................................................................................................................14
Conclusion .....................................................................................................................................15
References ......................................................................................................................................16

I
 List of tables

Table (1): Comparison between emission levels of biodiesel (pure or mixed) and fossil fuel in
automotive engines .........................................................................................................................6
Table (2): Summary of the results according to each experiment ................................................14

List of figures

Figure (1): Egypt’s energy consumption ........................................................................................4

Figure (2): Production of major vegetable oils worldwide from 2012/13 to 2017/2018, by type
(in million metric tons) ...................................................................................................................6
Figure (3): Approximate oil yields for different crops ...................................................................7
Figure (4): Transesterification chemical process .............................................................................9
Figure (5): Biodiesel production process flow schematic ............................................................10
Figure (6): Continuous flow reactor design ..................................................................................10
Figure (7): Magnet stirring schematic ..........................................................................................12
Figure (8): Methanol production process ......................................................................................12
Figure (9): Third experiment sample .............................................................................................14
Figure (10): Fourth experiment sample ........................................................................................14

II
 ▪ Abstract

From the discovery of fire to that of the atom, the development of human societies has largely been
based on the consequent of energy. The world is experiencing one of its most serious energy crises
for decades, especially because energy has gradually become one of the key factors of social and
economic development. Energy problems have damaging impacts on many fields like health,
money and the limited resources of power. These problems include a large amount of wasted
energy due to the low efficiencies of the machine and lack of maintenance as there is about 5000
MW of wasted electricity because of the previous reasons (the ministry of electricity and
energy,2017). In addition, a harmful problem regarding sanitation has been badly caused by wasted
oils. Biomass energy plays an indispensable role in getting over both the continuous disquiet of
increasing energy consumption and the misuse of oils using cheap raw material. That’s why we
decided to work on using the cooking oil, or any wasted oil, to produce biodiesel fuel, which will
be used to generate electricity. As a prior solution, the researchers have used a mechanism for this
process with a duration of 10 to 11 hours. We have worked on developing this mechanism to take
no more than an hour. Another area of our interest was being eco-friendly, so we have produced
methanol to prevent greenhouse emission and pollution. To test the process, we have made a
testable prototype to meet the design requirements.

3
 ▪ Introduction

Over 1.1 billion people in the world have no access to electricity (international energy agency,
2018). This means that 1 out of 5 people are forced to live without something that a majority of
the world takes for granted every day. This is not the only crisis. Due to the world health
organization (2018), 3.8 million people die unnecessarily each year due to inhaling the indoor
smoke caused from burning coal, crop residue, wood, and even dung for heating and cooking
purposes. This led to an incredibly harmful phenomenon which is increasing global warming, that
has bad impacts on the climate and ecological balance. In addition, With the high rate of using oil,
gas, and coal these limited resources of energy will be consumed nearly in 2042, expanding the
ozone hole 3 times larger. Then, there will no longer have energy, in addition, the climate will not
be valid for life. Consequently, we have to rely on renewable resources to generate green cheap
energy.

Figure (1), Egypt’s energy consumption

Since there is a problem that is very dangerous which is the erosion of sanitation as a result of
dumping the oil wastes in it. we decided to use these wastes instead of dumping it to help people
benefit from it. So, we have worked on producing clean fuel (biodiesel) that will be used in diesel
generators to produce electricity with a lower rate of gases emission than original diesel. These
emitted gases will be used to produce methanol by a combination of co2 and H2. Furthermore, the
biodiesel will be extracted within only 1 hour. Consequently, the developed project design will
save time and money, improve the efficiency of biodiesel, and decrease the air and sanitation
pollution.

4
 ▪ Research

Biodiesel is a liquid biofuel obtained by chemical processes from vegetable oils or animal fats and
alcohol that can be used alone or mixed with diesel oil in diesel engines. ASTM International
(originally known as the American Society for Testing and Materials) describes biodiesel as a
mixture of long-chain monoalkylic esters from fatty acids obtained from renewable resources, to
be used in diesel engines. Blends with diesel fuel are known as ‘‘Bx’’, where ‘‘x’’ is the percentage
of biodiesel in the blend. For instance, ‘‘B5’’ indicates a blend with 5% biodiesel and 95% diesel
fuel; in consequence, B100 indicates pure biodiesel.

- The biodiesel advantages are that it is:

• Renewable fuel obtained from animal fats or vegetable oils.

• Low toxicity, in comparison with diesel fuel.

• It degrades faster than diesel and minimizes the environmental impact of biofuel spills.

• Lower emissions of contaminants: carbon monoxide, particulate matter, polycyclic aromatic

hydrocarbons, aldehydes.

• Used cooking oils and fat residues from meat processing may be used as raw materials.

• It can be mixed in any proportion with diesel fuel; both fuels can be mixed during the vehicle
fuel supply.

• Excellent properties as a lubricant.

• It’s is the only alternative fuel that can be used without modifications in a conventional diesel
engine.

5
 Figure (2), Production of major vegetable oils worldwide from 2012/13 to 2017/2018
by type (in million metric tons)

Table (1) Comparison between emission levels of biodiesel and fossil fuel in automotive engines

EMISSION (KG/100 KM) BIODIESEL 100% BIODIESEL 30% DIESEL

CO 0.37 0.43 0.46
HYDROCARBONS 0.03 0.04 0.04
NOX 2.73 3.37 3.64
PARTICULATE MATTER 0.62 1.48 1.85
CO2 0.87 3.53 4.67
SO2 0 1.14 1.62

- Raw Materials for Biodiesel Production:

Biodiesel production raw materials’ are vegetable oils, animal fats, and short chain alcohols. The
oils most used for worldwide biodiesel production are rapeseed, soybean, palm, and sunflower,
although other oils are also used, including peanut, linseed, safflower, used vegetable oils, and
animal fats.

Although ethanol may also be used, methanol is the most commonly used alcohol. Because costs
are the main concern in the production and trade of biodiesel (mainly because of oil prices), the
use of non - edible vegetable oils have been studied for many years with good results. In addition
to its lower cost, another undeniable benefit for non-edible oils for biodiesel production lies in the
fact that no foodstuffs are spent to produce fuel. These and other reasons have led to medium- and
large-scale biodiesel production trials in several countries, using non-edible oils such as castor oil,
Tung, cotton, jojoba, and jatropha.

6
Animal fats are also an interesting option, especially in countries with plenty of livestock
resources, although preliminary treatment is necessary because they are solid; highly acidic fats
from cattle, pork, poultry, and fish are also available. Because of their very high oil yield,
microalgae appear to be a very important alternative to future biodiesel production; however, it
must be taken into account that only some species are useful for biofuel production. Although the
properties of oils and fats used as raw materials may differ, the properties of biodiesel must be the
same, complying with the requirements set by international standards. Figure (3) presents
approximate oil-yield values (in liters per hectare) for some of the mentioned crops.

Figure (3), Approximate oil yields for different crops

7
 ▪ Methods

Three types of processes for producing biodiesel from vegetable oils and waste cooking oils have
been investigated, namely: pyrolisis, emulsification, and transesterification.

Pyrolisis in which the application of thermal energy in the presence of air or oxygen to produce a
chemical modification takes place. The thermal decomposition of triglycerides yields alkanes,
alkenes, alkadienes, aromatic compounds, and carboxylic acids. Due to the great differences of
reaction pathways, different reaction products are obtained. Despite the fact that products are
chemically similar to petroleum diesel, oxygen removal during thermal cracking reduces some of
the environmental benefits of these renewable oils

Microemulsions have been prepared with chemicals such as methanol, ethanol, and 1-butanol in
order to lower the viscosity of biodiesel. These microemulsions are isotropic, clear, and
thermodynamically stable dispersions of oil, water, and a surfactant; a cosurfactant is often
dispersed, using amphiphilic compounds. This process yields a fuel with lower viscosity, but its
injection in the engines is not so efficient, and a coarse deposition and incomplete combustion
happen.

The transesterification process, so-called alcoholysis, is the replacement of alcohol in the ester
molecule by another alcohol as in a hydrolysis reaction (using alcohol instead of water).

Transesterification of oils is the most efficient method, as it reduces the viscosity of triglycerides,
and also improves the physical properties of the final product (cetane number, injection efficiency),
resulting in a better fuel.

The transesterification process involves the reaction of alcohol in the presence of a catalyst (i.e.
potassium hydroxide). The reaction takes place in a specific temperature range starting from 55°C
within continuous stirred-tank reactors (CSTR). The resulting ester mixture has physio-chemical
properties similar to those of petroleum diesel. Suitable alcohols are methanol, ethanol, propanol,
butanol, and amyl alcohol. Methanol is the most commonly used, because of its low cost and good
physicochemical properties.

8
Vegetable oils (like animal fats) are triglycerides, composed of three chains of fatty acids bound
by a glycerin molecule. Triglycerides are esters. Esters are acids, like fatty acids, combined with
alcohol. Glycerin (= glycerol) is heavy alcohol. In the conversion process, triglyceride esters are
converted into alkyl esters (= biodiesel) using an alkaline catalyst (sodium or potassium
hydroxide), and an alcohol reagent, e.g. methanol, which yields methyl esters biodiesel. The
methanol replaces the glycerin.

Figure (4), transesterification chemical process

While alkali-catalysts are the most common, the reaction can also be accomplished with acidic
catalysts and enzymes.

Transesterification of triglycerides is catalyzed by inorganic acids, like sulphuric, phosphoric,

hydrochloric, and sulfonated organic acids. This catalytic process produces high conversions, at a
slow rate; and reaching full completion takes more than a day. An excess of alcohol improves the
conversion, but it makes glycerol recovery more complicated.

Enzymes have shown good tolerance for the level of free fatty acids in the feedstock, but the
enzymes are expensive and cannot provide the required degree of reaction completion to meet the
fuel requirements.

9
 Figure (5), Biodiesel production process flow schematic

In a reactor, alcohol, catalyst and oil are combined. Stoichiometrically, a TAG mole requires three
mol of alcohol in transesterification. Due to the reversible nature of the reaction, excess alcohol is
usually used in transesterification to shift the reaction to the products. Smaller plants often use
batch reactors, but most larger plants (N4 million liters/year) use continuous flow processes
involving continuous stirred-tank reactors (CSTR) as in figure (6) or plug flow reactors.

Figure (6) Continuous flow reactor design

10
The glycerin – the heaviest – will sink to the bottom. Biodiesel – the lightest – floats on the top
and they can be separated through a glycerol removal step (separator).

After separation from the glycerol, the methyl esters enter a neutralization step and then pass
through a methanol stripper, usually a vacuum flash process or a falling film evaporator, before
washing by water. Acid is added to the biodiesel to neutralize any residual catalyst and to split any
soap that may have formed during the reaction.

Neutralization before washing reduces the amount of required water and minimizes the potential
of emulsions formation when the wash water is added to the biodiesel. Soaps will react with the
acid to form water-soluble salts and free fatty acids. The salts will be removed during the washing
step, and the free fatty acids will be left in the biodiesel. The water washing step is intended to
remove any remaining catalyst, soap, salts, methanol, or free glycerol from the biodiesel.

Following the wash process, any remaining water is removed from the biodiesel by a vacuum flash
process, and pure biodiesel is produced at the end of the process. The glycerol stream leaves the
separator containing most of the methanol and soaps formed. It goes through some processes that
end with extracting glycerol (85% pure) and methanol that can be re-used in the reaction.

- Prototype:

A small-scale prototype has been made to simulate the large-scale project.

1. Firstly, an oil container was connected by using pipes with another big container that will
include oil also. After that, we inserted a burette inside a small jar that will include methanol
then put it into the small oil container.
2. Secondly, we connected temperature sensor with Arduino to give an alert that the temperature
had reached 60°, so a valve at the end of the methanol container will open to insert the methanol
into the mixture.
3. Thirdly, a timer has been put that will give a noise when half an hour had passed while the
temperature is constant between 60° and 65° not increase or decrease. Then we connected a
pipe to the water path (in which the oil container is put) and oil container that will be opened
to make the glycerol and biodiesel pass through it going to the separating funnel that will
separate biodiesel from glycerol. A color sensor has been put to distinguish between biodiesel
and glycerol.

11
4. Fourthly, we connected a container with the diesel generator to take CO2 coming from it and
connected the container with another one using pipes that we will make electrolysis for water
inside it, then it passes the H2 to the first container and we will add catalyst RU and will heat
this container for 15 minutes at 125°. Methanol will be formed in the container.
5. Fifthly, a burette has been connected to the container in which KOH will be put, after receiving
an alert that 15 (the time of formation of methanol) minute had a path. Consequently, this
container will include KOH And methanol
6. Finally, we connected this container with the first methanol container to support it when the
quantity in it finish.
7. The stirring System:

It will consist of a magnet in the shape of a ring (see figure 7). Inside it, there are four sticks made
of wood and at the end of each one will be a magnet, the wood is added to prevent the cutting of
the magnetic field so the repulsion force between the small magnets and the big one will make it
rotate. Also, the magnet will decrease the amount of methanol that we need to its half. We will
insulate the wires to prevent it from melting.

Figure (7), Magnet stirring schematic Figure (8), Methanol production process

This great motion of the magnet will be used for generating electricity with the generator that is
connected with the magnet. This electricity will be used in an electrolysis process of water in
another container to separate the water components. The hydrogen separated will later be used in
another container that will hold the gather CO2 emissions produced for the system to produce
methanol (see figure 8). The purpose of this process is to make the system closed and independent.

12
 ▪ Test Plan
Three major design requirements have been chosen to be tested on the prototype:

I. High efficiency:

It is symbolized in getting the largest amount of biodiesel in the smallest time and with the accurate
viscosity. That is why many experiments have been made to reach this efficiency.

- Experiments:
1. First experiment: a solution of sodium hydroxide has been made, then 1 gm of it was put on
10ml of water then put it on 250 ml of oil and 40ml of methanol and there was no stirring.
2. Second Experiment: It was decided to increase the amount of methanol to exceed the amount
of oil put so we put 60 ml of methanol on 20 ml of oil and 1 gm of KOH (This time we used
it because we find its efficiency is more than NaOH) and left it for 7 hours on a temperature
60°
3. Third Experiment: this time 100 ml of oil + 20 ml of methanol +1gm of KOH have been put.
The mixture was stirred manually from time to time and left it for 4 hours.
4. Fourth Experiment: This time we put 80 ml of oil + 8ml of methanol + 0.4gm of KOH and
left it for 30 minutes on the heater with stirring using a ring-shaped magnet.

Note that each of these steps and experiments has been done twice as two types of oils were used;
lard oil and canola oil, to monitor their yield percentages.

II. Cost:
- The machine has been constructed as a closed system that produces its own electricity.
- The time was made lesser than any other way – from 11:20 hours to half an hour.
- The CO2 that produced from the diesel is used to make methanol.
- The magnet in the tank will produce electricity that will turn on the 2 heaters and help in mixing
the oil.

III. Eco-friendly:

It is achieved by emitting the smallest amount of CO2 and not allow this CO2 to escape to the
environment.

13
 ▪ Results

Every project throughout history had to be tested to know whether it was successful or not. Our
project has been tested in many ways to know if we have achieved the design requirements or not.

I. Efficiency:
- In the first experiment: the time taken was 12 hours because of the amount methanol and NaOH
and there was no stirring. The viscosity was 3.8.
- In the second experiment: the time taken was 7 hours because we increased the amount of
methanol above the amount of oil so the viscosity became 2.5 but it didn’t form biodiesel.
- In the third experiment: the quantitities of components was more accurate and also the time
was reduced because of using the stirring and the viscosity was 4.3. The result was that 86%
of oil changed into biodiesel. As shown in the fig. (9)
- In the fourth experiment: The magnet was used to the frequency was more than that of the
manual steering and the components were more accurate. Consequently, the viscosity was 4.6
and the amount of biodiesel produced was 90% of the oil. as shown in fig. (10)

Figure (9) Figure (10)

- According to the European standard, “the viscosity of the biodiesel should be between 3.5 and
5 mPa s” That is why the last experiment is the one which we determined to use as it is the
most accurate one.

Experiments 1ST Exp. 2nd Exp. 3rd Exp. 4th Exp.

Viscosity (MPA.S) 3.8 2.5 4.3 4.6
No. of hours 12 7 4 0.5
Table (2), Summary of the results according to each experiment

14
II. Eco-friendly:

As increasing viscosity, the amount of CO2 decrease, thus achieving the eco-friendly design
requirement.

III. Cost:

As reducing the time like in third and fourth experiment (using stirring) the cost reduced because
less electricity and less amount of methanol and KOH were used.

▪ Conclusion

Bio-diesel is a very efficient solution for diesel engines. It's better than petroleum-based fuel and
has excellent solvent properties such as the amount of octane that affects the viscosity degree of it
and make it, decreasing the resistance between the engine parts hugely. It results in a massive
reduction in the carbon dioxide emissions than petroleum.

The burning of biodiesel fuel also effectively eliminates sulfur oxide and sulfate emissions, which
are major contributors to acid rain. That’s because unlike petroleum-based diesel fuel, bio-diesel
is free of sulfur impurities.

The usage of the magnet stirring decreased the time needed for the reaction than most conventional
reactors would take. Having an independent closed system is very advantageous as the efficiency
and the production of the system will increase. The system proved to be efficient, sustainable, eco-
friendly and cost-effective, achieving all the requirements for a better solution than using fossil
fuels.

15
▪ References
1. Gerpen, J. (2005). Biodiesel processing and production. Available at:
https://www.sciencedirect.com/science/article/pii/S0378382004001924 [Accessed 1 Dec.
2018].
2. Issariyakul, T. and Dalai, A. (2014). Biodiesel from vegetable oils. [online] Available at:
https://www.sciencedirect.com/science/article/pii/S0378382004001924 [Accessed 1 Dec.
2018].
3. Luque, S., Prados, J. and Cervero J. (2008). Production of biodiesel from vegetable oils.
Available at:
https://www.researchgate.net/publication/26524146_Production_of_biodiesel_from_vege
table_oils [Accessed 1 Dec. 2018].
4. Romano, Silvia and Sorichetti, Patricio (2011). “Introduction to Biodiesel Production’’
Dielectric Spectroscopy in Biodiesel Production and Characterization, London: Springer
pp.7 - 27. Available at: https://www.canr.msu.edu/uploads/files/biodiesel_production.pdf
[Accessed 3 Dec. 2018].
5. Statista. (2018). Worldwide production major vegetable oils, 2012-2018 | Statistic. [online]
Available at: https://www.statista.com/statistics/263933/production-of-vegetable-oils-

16