Title: Bioprocess Group Assignment

Subject: UEMK 3233 Bioprocess Engineering

Course: Chemical Engineering - CL

Submission Date: 13 April 2018

Name of Lecturer: Dr. Woo Kwan Kit, Dr. Ong Ying Hui

Name Student ID Year/Semester

Lim Xue Heng 1402185 Y3/S3
Ng Boon Thai 1305649 Y4/S2
Ong Jun Jie 1402182 Y3/S3
Woon Zee Xian 1401368 Y4/S3
Table of Contents
Q1a) Process involve in Jetropha/Jatropha Oil production ........................................................................... 3
Q1b) Process involve in Palm Oil Methyl Ester Production....................................................................... 10
Q2) Advantages and Disadvantages of these 2 Biofuels ............................................................................ 14
Jetropha Oil ............................................................................................................................................. 14
Advantages:......................................................................................................................................... 14
Disadvantages: .................................................................................................................................... 15
Palm Oil Methyl Ester (POME) .............................................................................................................. 16
Advantages:......................................................................................................................................... 16
Disadvantages: .................................................................................................................................... 17
Q3) Select the best among the two options for biofuel production in terms of: ......................................... 18
(i) Biofuel yields....................................................................................................................................... 18
(ii) Engine performance .......................................................................................................................... 18
(iii) Exhaust emission .............................................................................................................................. 18
(iv) Suggestion for commercial production. ........................................................................................... 19
Conclusion: .................................................................................................................................................. 24
Reference: ................................................................................................................................................... 25
Q1a) Process involve in Jetropha/Jatropha Oil production
Jetropha curcas is a species of flowering plant which is native to the American tropics like Mexico.
It has been spread throughout the world in tropical, followed by naturalizing in many areas. The
plant could be grown in deserts as it is resistant to a high degree of aridity. Due to the presence of
phorbol esters, Jetropha curcas is toxic so it is not safe for human consumption. However, the plant
is cultivated in order to extract oil from its seed. According to analysis of Jetropha curcus seed,
the chemical compositions are 6.2% moisture, 18% protein, 38% fat, 17% carbohydrate, 15.5%
fiber and 5.3% ash. Generally, the oil content of the seed is 25-30% which contain 21% saturated
fatty acids and 79% unsaturated fatty acid. The oil can be synthesized as soap due to its high
content of saponification value. In addition, owing to high content of nitrogen and phosphorus, the
oil cake can be used as organic manure. The producing of biofuel from Jetropha Curcas seeds
divides into 2 major steps which are extraction of seed oil and conversion of seed oil to biodiesel.

Figure 1.1: Structure of Jetropha Plant and Seed.

Jetropha oil can be extracted from the seeds by three ways: mechanically, chemically and
enzymatically. Oil press method can be done by either powered or manually driven mechanical
device for the purpose of oil extraction. The most commonly used press is Bielenberg ram press
which can extract 60-65% of the oil among the different oil presses. Oil expeller is one of the
methods to extract oil. The Sayari oil expeller and the Komet Expeller are the conventional types
of oil expeller. The Sayari expeller is a device which operates using diesel while Komet expeller
is a single-screw oil expeller. In less developed area, the traditional method which is using simple
equipment by hand to extract the oil from the seeds is still employed. Other than that, hot oil
extraction that requires high pressure is introduced to extract oil from seeds. Then cold oil
extraction method is practiced to extract the oil from hot oil extraction because high viscosity
allows the oil flow easily.

Figure 1.2: Equipment design for Hexane Solvent Extraction and Recycle

In this modern era, aqueous enzymatic treatment is a chemical method to increase the
amount of Jetropha oil that can be extracted. Hexane is chosen as a chemical in the close system
which is batch-wise operation. Before hexane is add into the reactor, Jetropha seeds will be grinded
up to increase the surface area which will expose to hexane solvent. The seeds and solvent will be
allowed to contact for approximate 20 minutes. The wet seed cake which contains remaining
hexane will be sent to rotary dryer whereas miscella will be transported to stripper for hexane
recovery. The wet seed cake is dried by the steam produced from boiler, followed by sent to
incinerator. The vapour consists of hexane will be condensed and collected into a decanter.

To recover the hexane content from the miscella, stripper is used by allow two streams,
miscella and steam stream enter into stripper. Owing to different boiling point of hexane and seed
oil, the hexane is vapourise first before seed oil. The remaining product remained in the mixture
is seed oil that will be pumped to storage tank. The vapourised hexane will be condensed and
collected into the decanter where hexane and water will be separated base on difference in densities.
Water is excreted to sewer whereas hexane is recycled back to the process in order to save the cost.

The process of conversion of seed oil to biodiesel is transesterification. Generally most of

the plant oil composes of mono, di and tri-glycerides that can become biodiesel by going through
transesterification process. Biodiesel is a medium that has a combination of long chain esters which
possess good properties as a renewable fuel. As a biofuel, they must be stable at atmospheric
temperature, burned cleanly and least sulfur emitted compared to petroleum diesel. There are many
reasons choosing transesterification process for production of biofuel. One of the advantages is
ease of use as the chemical used in the process is general laboratory chemicals that can be
purchased through certain authorities.

Most of the industry prone to use a base catalyzed reaction with methanol and sodium
hydroxide (NaOH) for applications of transesterification. The reason choosing this reaction is
because acid catalyst mechanism involves high heat and time-consuming. Before adding the
mixture into the process, NaOH is dissolved in the methyl alcohol. NaOH not only could
deprotonate the alcohol before insertion into medium but simplifies the mixture of base catalyst
into the immiscible Jetropha oil. There are many chemical equation involved in the conversion of
biodiesel. The equation of alcohol mixture adding into the Jetropha oil involves:

𝑅𝑂𝐻 + 𝑁𝐴𝑂𝐻 → 𝑅𝑂 − + 𝐻2 𝑂 + 𝑁𝑎+

The equation of carbonyl group being attracted by a positive charge on the triglyceride is as shown
in Figure 1.3.
 Figure 1.3: Equation of carbonyl group with triglyceride.

After the reaction, the unstable tetrahedral intermediate breaks into an ester and a di-glycerol. The
equation proceeds as follows in Figure 1.4:

Figure 1.4: di-glycerol and ester

In the end, this process is repeated with two more carbonyl group to produce two additional esters
and a glycerol. The equation is shown in Figure 1.5:

Figure 1.5: Transesterification of a Triglyceride with Methanol

 The water content should be kept at less than 1% weight of Jetropha oil because the reaction
experiences emulsification which lead to incompletion if there is large amount of water exists in
the Jetropha oil. In Figure 1.7, the initial concentration of the water inside Jetropha seed is 0.2
which is considered low enough as the water content of Jetropha oil is said to be less than 1% mass
water. The saponification value is 190 which is within the range stated in Figure 1.8. The
formation of soap will be priority instead of biodiesel conversion if the value is out of
range.Another concern is the Free Fatty Acids (FFA) as it will foam soap by consuming the base
catalyst. The amount of FFA inside Jetropha plant is unavoidable as it depends on the age and the
location of growing. However, the problem can be eliminated by adding surplus catalyst and
methanol. The equation involved is as shown in Figure 1.6.

Figure 1.6: Free Fatty Acid Treatment with Methanol

Figure 1.7: Properties of the Jetropha oil used for biodiesel production
 Figure 1.8: Standard specification of Jetropha oil

Figure 1.9: Production of Biodiesel using Transesterification Process

 By looking into Figure 1.9, Crude Jetropha Curcas Oil (JCO) is treated with acid-catalyzed
transesterification process that reduces the Free Fatty Acid (FFA) content of seed oil by converting
the free fatty acid into biodiesel intermediate in X-300 which is a batch reactor. By doing so can
increase the production rate of biodiesel. Sulphuric acid is used as a catalyst whereas methanol is
used to treat the crude JCO at pressure of 1 atm and a temperature of 60°C. The effluent will be
sent to V-310 where separation of two layers occurs. One of the layers consists of biodiesel, JCO,
sulphuric acid and FFA and second layer consists of water, glycerol, methanol and remaining
sulphuric acid. The first layer is sent to ventilation and second layer transported to X-301 where
convert the remaining crude JCO into biodiesel under base-catalyzed transesterification reaction.
The effluent of X-301 will be sent to V-311 where separation occurs. Then the biodiesel is obtained.
Q1b) Process involve in Palm Oil Methyl Ester Production
Palm Oil Methyl Ester (POME) has been hailed as the potential substitute to replace the fossil
fuel. Because the cetane number, energy content, viscosity and phase changes of POME are
similarity to fossil fuel after manufactured to petroleum-derived diesel fuel. Besides that, the
POME is also renewability, biodegradability, low sulphur content, low aromatic content and high
heat value (lower than diesel fuel). POME contain of 76.2% of carbon; 12.6% of hydrogen and
11.2% of oxygen, with the flash point of 135°C and it can produce 38.6 MJ of heat when 1kg of
POME been combusted. Table below show the properties of POME are within the biodiesel
America standards ASTM and European Standards EN.

Figure 1.10: Properties of POME are within the biodiesel America standards ASTM and
European Standards EN.

The POME can be produce by using trans-esterification. Trans-esterification is a chemical

reaction between triglyceride and alcohol in the presence of catalyst. The reaction process take
place in four steps. First step is to mix the alcohol for reaction with the catalyst (KOH or NaOH).
The alcohol-catalyst then react with the palm oil so that the trans-esterification reaction take
place.
Figure 1.11: Trans-esterification reaction of POME.

Catalyst for the reaction is prepared by mixing methanol and a strong alkaline such as sodium
hydroxide (NaOH) or potassium hydroxide (KOH). The OH ion of base abstracts the hydrogen
ion from the methanol to form water molecules and let the CH3O- available for the reaction. The
methanol must be as dry as possible in order to prevent side-reaction product which is unwanted.
Present of water will possibly make a side-reaction occurred that form soap. Following diagram
are the side-reaction of trans-esterification process.

Figure 1.12: Side-reaction of trans-esterification process.

After the catalyst is prepared, the reaction of palm oil molecule (triglyceride) will react with the
methanol. Excess methanol was used to ensure complete reaction due to it was the limiting
reagent. The 3 attached carbon with hydrogen react with OH- ions form glycerine and the CH3
group react with free palm oil molecule to form POME.
Figure 1.13: Quantity of chemical reactant needed for the trans-esterification process.

The diagram above shows the quantity of chemical reactant needed for the trans-esterification
process. Excess methanol (about 2times theoretical value) are required in order to achieve
complete reaction. Normally the reaction take place at temperature between 45-60°C and 1-4
hours for reaction time. The higher the reaction temperature will use shorter reaction time to
complete the reaction. Due to the methanol will evaporate at temperature above 65°C, if the
process wants to operating above the temperature a pressure vessel is required and instalment of
the vessel will also help to increase the methanol to oil molar ratio.

The following diagram shows the production of POME in industry scale. The glycerol formed
during reaction have to be removed from the production. Water is added into both glycerol and
POME to removed unwanted product which is glycerol and the water will evaporate and
removed from POME inside separator. To neutralized the unwanted product (glycerol), acid is
added in neutralizer for neutralisation process of the glycerol.
Figure 1.14: Process flow for neutralisation process of the glycerol.

The process by produce POME using supercritical methanol is known as Supercritical process.
The process is catalyst-free and use supercritical methanol at high temperature and pressure. In
supercritical state, the alcohol and oil are under single phase to make the reaction occurs rapidly.
This process method can tolerate water in the feedstock and no side-reaction occurred that form
unwanted product.

Figure 1.15: Process flow for Supercritical process.

Another production method called using high-shear and batch reactor for POME production.
This method allows production of POME continuously, semi-continuous or also batch. It reduces
the production time and increase the productivity of POME. The reaction take place in the high-
energetic shear zone of the Ultra- and High Shear mixer to reduce the droplet size of reactant to
form a large surface area to faster the catalyst reacts.

Q2) Advantages and Disadvantages of these 2 Biofuels

Jetropha Oil
Advantages:
1) Easy cultivation

Jetropha plant can grow on most of the climatic condition especially in Malaysia with constant
weather changes, relatively stable of humidity and temperature. The plant is drought resistant
which means it can withstand a period of time without water. It also has the ability to grow on
poor and infertile soil.

2) Low costing

The price of the jetropha seed is cheaper compare with another biofuel plant. No special step to
be taken during the cultivation of seed.

3) High yield percentage

The jetropha seed have high oil content which means it can produce more amount of oil per seed
with the sufficient supplied of nutrient. Besides, it grows quickly which means it can be harvest a
few times a year than harvest annually.

4) Long life sustainability

The plant can sustain for 50 years to be harvest which can maximize the profit tremendously
compare with the initial seed investment.
Disadvantages:
1) Host for disease

The rust on the leaf and root on the jetropha plant is found to be the suitable as the host of
disease such as African cassava mosaic virus(ACMV), anthracnose (Colletotrichum
gloeosporioides) and so on. This disease will infect other plant as well and causing the massive
changes on the botanical ecology.

2) Poisonous by-products

Jetropha plant has poisonous fruit and seeds which has no future processing value after
extracting the oil. It is not suitable to ingest by organisms as it can cause diarrhea and nauses.

3) Large planting space

Plantation of Jetropha plant required larger space compare with other plant because of the size of
the plant is reaching 6m or more.

4) High water consumption

Although it is the plant that can withstand drought, but to make sure the stability of the oil
content, the water supplied must be enough to ensure the oil produce by the plant is maximize.

5) High cost for processing

The factory or plant require higher investment than the plantation site because the process of
extracting the oil is very complicated and also the further process of detoxification of the
remaining seeds.

6) Food vs fuel

There is always the argument between plants for food or fuel. For examples, if originally the
corn is served as food sources all over the world, but now due to the production of bioethanol,
the large amount of corn are now used as fuel sources. The food prices will increase and the
hunger and malnutrition issues will become more serious.
Palm Oil Methyl Ester (POME)
Advantages:
1) Renewable resources

Unlike petroleum products that will vanish in years, biodiesel is a renewable energy which can
be produced from animal and vegetable fat.

2) Less greenhouse gas emissions

Significantly reduced the GHGs (CO2, CO) up to 78% compare to petroleum diesel. Reduction
of GHGs also protect the environment from global warming.

3) Environmental friendly

Biodiesel is the only biofuel has successfully meet the emissions testing accordance with the
Clean Air Act. It is biodegradable which means the spillage of biodiesel is less harmful to the
environment and clean up job is easier.

4) Safer

Biodiesel is about ten times less toxic than table salt through the research found. It has a higher
flash point than conventional diesel. Thus, the storage and transportation is easer and safer.

5) Ready to use by current diesel engine

Little or no modifications is required for the current diesel engine in order to use biodiesel.
Biodiesel can be either used with B100 (100% biodiesel) or blended with petroleum diesel.

6) Extent the working life of engines

Biodiesel has the properties of high fuel lubricity. It improve the engine lubrication and prolongs
the working life of the engines.

7) Decrease the dependence on petroleum

As the natural resources of crude oil are going to deplete in the near future, the development of
biodiesel is reducing the dependence on petroleum diesel.
Disadvantages:
1) Gelling effect in low temperature

The gel point of biodiesel is relatively low. This means biodiesel would not be likely used in the
cold climates countries. The fuel tank need heating to use the biodiesel in cold climates.

2) Food vs fuel

The biodiesel can be made from the animal or vegetable oil. It will affect the food oil supply in
the market if all the farmers plant the crops for biodiesel manufacturing. The oil prices will rise
up due to the supply shortage for food usage.

3) Excess use of fertilizers

To produce more biodiesel, the more crops are needed to plant to meet the demand. There will be
more fertilizer used and lead to soil erosion and even land pollution or underground water
pollution.

4) Low fuel efficiency

From the researches, it was found that B20 mixtures can reduce the fuel efficiency by 1 to 2 %
which equal to 10 % reduction in power. It would need 1.1 gallons of biodiesel to equal 1 gallon
of standard diesel.

5) More expensive

As the increment of the price of the feedstock and the production problems cost, the biodiesel is
more expensive than the petroleum diesel.
Q3) Select the best among the two options for biofuel production in terms of:

(i) Biofuel yields

From the comparison of Jetropha oil and palm oil in the difference reaction time and
different molar ratio, we have enable the yield of biodiesel from Jetropha oil at optimal
potassium hydroxide catalyst with the reaction time of 5 hours and molar ratio of ethanol to oil at
8:1 was 90% while the palm oil is only having a reaction time of 1 hour and molar ratio of
methanol to oil of 10:1 was 93.6%. From the observation of reaction above we are able to
conclude the palm oil is having a better yield compare to Jetropha oil.

(ii) Engine performance

As from the graph 3.1 attached, we observe the magnitude and engine performance using
the types of fuel after endurance test are quite difference from that before endurance test. The
data from graph shows the using of Jetropha oil (PJO) gives the highest BSFC among other PPO
before the endurance test even though its own energy content is not the lowest. After endurance
test, all oil’s BSFC decreased with the largest reduction is of PJO, followed by PPaO (Palm Oil)
and PCO (coconut Oil). This degradation happens not because a better combustion but less
friction loss occurred as shown in the component.
As from the data, we can observe Jetropha oil is having a better thermal efficiency when
compare to Palm Oil, furthermore the unburn hydrocarbon of Palm Oil is far higher than the
Jetropha oil. Form the data we can conclude that Jetropha oil is better than Palm oil in terms of
engine performance. The figure 1 also clearly show that Jetropha Oil leaves lesser deposit on
injector than Palm Oil. Although the figure 2 shows that Jetropha Oil leaves more residue in
impingement point, in overall, Jetropha oil is better than Palm oil.

(iii) Exhaust emission

Perfect combustion produces lower both carbon monoxide and oxygen and higher carbon
dioxide emission. By comparing the graph 3.2, 3.3, 3.4, 3.5, 3.6, and 3.7, it can be concluded that
pure plant oil (PPO) produce more incomplete combustion. Oxygen content in PPO gives higher
result that diesel fuel but it does not indicate that diesel fuel combustion more perfect than PPO
because oxygen content can be obtained from PPO itself.
As the unburn hydrocarbon in palm oil is higher than the jetropha oil, this phenomenon
caused by poor atomization of palm oil and consequently poor fuel vaporization and combustion.
(iv) Suggestion for commercial production.
As for Jetropha oil and palm oil, they are considered biodiesel and poorer compare to
diesel as they having the following limitation: High Viscosity, Poor Atomization, Polymerization
in combustion chamber leading to deposits, Injection fouling by deposits, causing fuel line and
filter clogging, and etc. These limitations have cause the production of Jetropha less
commercially than the diesel as the production cost are not effective. In order to encourage
production of plant-based diesel, the better economic possibility like, incentives from the
government, guaranteed marker of their produce by processors and availability of the credit to
support production.

The pilot run of these demonstrations must include the small and marginal farmers and
cultivators as these will act as a business enterprise that oversees soil, water, and other natural
resource system as well as crop management and business enterprise cluster creation. This
approach will allow the energy farm enterprise to explore different technology alternatives and
identify the best cultivation methods for Jetropha plantation management. Such demonstration
can also promote plant-based diesel farming and serve the energy needs of agricultural
communities, as well as provide rural employment and alternative income.

There is a lot of opportunity for this diesel fuel to be substitute the diesel like what is
taken place during WWII as the lack of production of diesel forces scientist to produce diesel
fuel substitute from seeds oil. But there is also some thread facing for plant based fuel especially
to Jetropha oil as the by product is toxic in nature and not suitable to make them as animal food.
Moreover, to substitute a country’s energy with biodiesel will be very high in the first few years
as the percentage of the country’s fuel supply will be not too high.

Unlike Jetropha oil, palm oil is facing the different challenging. Among them is the wide
uses of palm oil, this situation caused the choice of palm oil as an alternative for diesel more
challenging. Palm oil is now widely use as cooking oil and some food manufacturing. The
sudden increase in need on the need of palm oil will be a big impact on the palm oil industry and
causing the increase in palm oil pricing which might affect the whole economic as it is consider
one of the main in food source.

In order to commercialise the biodiesel, there are a few advices to be given in a nutshell.
First, there are still much work to be done in order to increase the efficiency of the extraction and
production of the biodiesel, and the process of treating the waster production. Besides, the
substitution of the diesel to biodiesel should be implement phrase by phrase to prevent the
sudden impact on the society. Moreover, the variety of possibility energy source of biodiesel
should be study and making the biodiesel of these variety to be as universal as possible. This
conversion will make the possibility of producing cheapest oil in different location with different
plant. Last but not least, the government and industries should look more closely in the situation
of biodiesel fuel and provide the necessary help in terms of money and skill.

Graph 3.1. BSFC at 1500rpm

Graph 3.2. Thermal Efficiency at 1500rpm

 Graph 3.3. Oxygen Emission at 1500rpm.

Graph 3.4. Carbon Dioxide Emission at 1500rpm

 Graph 3.5. Carbon Monoxide Emission at 1500rpm.

Graph 3.6. Unburn hydrocarbon Emission at 1500rpm.

Graph3.7. Opacity Emission at 1500rpm

Figure 3.1. Injector condition after test compare to new condition

Figure 3.2. Piston condition after test compare to new condition.

Conclusion:
To sum it up, Jetropha Oil should be the better oil substitution compare with Palm Oil Methyl
Ester. However, the only institute that invest R & D on Jetropha Oil is Malaysian Rubber Board
(Lembaga Getah Malaysia). The report shows that the current bottle neck is the desire volume of
yield is unachieveable because of the current cultivation method is not suitable for Malaysia soil.
There is currently a total area of 50 hectare of Jetropha Oil plantation had established in
Malaysia. To fulfil the market requirement, the effort on looking for new cultivation method is
urgent so that the production rate of dry seed can be increased.

For the Palm Oil Methyl Ester, there are currently 3 government body that make regulations and
make improvisation on the technology which is Malaysian Palm Oil Board (MPOB), Malaysian
Palm Oil Council (MPOC) and Palm Oil Research Institute of Malaysia (PORIM). Besides,
Federal Land Development Authority (FELDA, Lembaga Kemajuan Tanah Persekutuan) also
works with some companies included Sime Darby, Genting Plantations, IOI that own palm oil
plantation to increase the Palm Oil production in Malaysia. With the alliance of these body and
company, the price of palm oil is relatively stable throughout the years and increasing gradually.

From here, we can know that the management regards the palm oil in Malaysia is more complete
than Jetropha Oil. To transform our country from palm oil based to both oil share the biodiesel
market together, the are a lot of effort need to be done either in assist from government, standard
of the oil grade and so on. So that the Jetropha oil can meet the consumer or industrial required
standard and able to monetize and export to other country in the world.
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