Assignment 4 Ekc 358

UNIVERSITI SAINS MALAYSIA
EKC358 OLEOCHEMICAL PROCESSING

SEMESTER 1, 2023/2024
INDIVIDUAL ASSIGNMENT
ASSIGNMENT 4
NAME: R. VIVEKA A/P RAMU
MATRICS NUMBER: 159293
SCHOOL: SCHOOL OF CHEMICAL ENGINEERING
LECTURER: ASSOCIATE PROFESSOR DR. VEL MURUGAN VADIVELU
SUBMISSION DATE: 19TH JANUARY 2024

a. Define supercritical transesterification of oleochemical and its role in biodiesel
production.
The process of supercritical transesterification uses alcohol under supercritical conditions to

convert oleochemicals into biodiesel. Biodiesel is an alternative, renewable fuel and can be
used in diesel engines. Transesterification is the chemical process employed to produce
biodiesel. These circumstances are above the mixture's critical point, which is the point at
which the separation between the liquid and gas phases vanishes. A variant of
transesterification is supercritical transesterification which uses supercritical methanol or
ethanol as the reaction medium.
The supercritical methanol exhibits unique properties that enhance its reactivity. It acts as
both the solvent and the reactant. It breaks down the triglycerides into fatty acid alkyl esters
and glycerol. The triglycerides (fats and oils) will react with the methanol (or ethanol) in the
process of transesterification at pressures between 100 and 300 bar and temperatures between
280 and 400 °C and will yield glycerol and fatty acid methyl ester (FAME) which is the
biodiesel.
Supercritical transesterification is a catalyst-free method. This eliminates the need for catalyst
separation and purification. This simplifies the whole transesterification process and reduces
the cost of the process. Nonetheless, the fuel quality is maintained while accounting for
environmental concerns. Triglycerides and alcohol are combined in a supercritical state
during the supercritical transesterification process, which can result in quicker reaction
kinetics and increased efficiency over traditional transesterification techniques.
It is commonly known that the high reaction rate of the supercritical methanol process
enables the reaction to be finished quickly. Because there is no catalyst in the system, the
process of separating and purifying its products is also simpler. High levels of free fatty acids
(FFA) and water in oils or fats do not affect the yield or conversion when using a supercritical
reaction. Instead, it was discovered that because the FFA were also converted to methyl
esters, they improved the methyl esters' formation. Therefore, waste cooking oil, which
typically has a high percentage of FFA, and water can be used in the supercritical fluid
transesterification process without the need for any prior preparation.
In the supercritical region, the hydrogen bonding between alcohol molecules drastically
reduces, enabling alcohol molecules to function as an acid catalyst. Alcohol monomer attacks
the carbonyl atom of the triglyceride directly at high pressure, imparting a positive charge.
After the intermediate dissociates and the methoxide is transferred, two molecules are
formed: a diglyceride and an alkyl ester of fatty acid. Until glycerol is the final product, this
process is repeated twice more.
b. Compare supercritical transesterification with traditional methods of biodiesel

production (such as base-catalyzed transesterification). Explain the advantages of
supercritical transesterification over conventional transesterification methods.
The process that is most frequently used to produce biodiesel is base-catalyzed

transesterification. This process uses a base catalyst to speed up the reaction between alcohol
and triglycerides. Typically, the catalyst is potassium or sodium hydroxide. At moderate
temperatures and atmospheric pressure, the reaction takes place. Although base-catalyzed
transesterification is a well-known and frequently used process, it has some disadvantages.
To attain high conversion rates, base-catalyzed transesterification frequently needs longer
reaction times. Energy consumption and production costs may rise as a result. When a base
catalyst is present, high concentrations of free fatty acids (FFAs) in the feedstock can cause
soap formation, which can interfere with saponification and make it more difficult to separate
biodiesel and glycerol. Usually, a large amount of alkaline catalysts are needed, which raises
expenses and produces waste by-products. Alkaline-catalyzed transesterification can result in
varying amounts of biodiesel, particularly when working with unclean raw materials or
different feedstocks.
Because supercritical transesterification doesn't require a catalyst, it makes the process of
producing biodiesel simpler and lowers the expenses and complexity involved in separating
or recovering the catalyst. Furthermore, no soap formation or wastewater generation occurs.
Although the yields can be higher, the reaction times are significantly shorter (minutes as
opposed to hours) than in the conventional alkali-catalyzed reaction. Unlike traditional
transesterification, the process is robust and unaffected by the presence of water or free fatty
acids in the reactants.
This eliminates the need for pre-treatment and enables the use of a much wider variety of
feedstocks, including lower quality and, consequently, lower cost feedstocks like spent oils
and animal fats. The supercritical environment is tolerant to impurities like water and free
fatty acids, allowing the use of waste cooking oils, animal fats, and other low-cost
feedstocks without extensive pre-treatment. Supercritical transesterification reactions
are faster and more efficient than conventional methods. Supercritical transesterification
utilizes a wider feedstock range including waste and low-cost materials. This process has no
harmful catalyst residues or wastewater generated.
One of the challenges of supercritical transesterification is high energy consumption. The

process requires high temperatures and pressures, increasing energy input. The reactor design
and material selection are also another disadvantage of this process. Special equipment is
needed to withstand supercritical conditions because very high temperatures and pressures in
used in this process. Since the technology is still under development and has not been widely
adopted on a large scale yet, there is limited commercialization of this process.
Overall, supercritical transesterification holds significant promise for the future of biodiesel
production. Its efficient and sustainable approach can contribute to a cleaner and more secure
energy future.
c. Assess the current status and prospects of supercritical transesterification for large-
scale biodiesel production.
Supercritical transesterification is still in the early stages, and research is being done to
optimize efficiency and refine operational parameters for a range of feedstocks. Although
there are pilot plants, there is little commercial application on a large scale.
Apart from that, it takes a lot of energy to achieve and maintain supercritical conditions,
which makes it difficult to be sustainable and cost-effective. To allay this worry, process
optimization and the integration of renewable energy are essential. Compared to conventional
techniques, supercritical transesterification requires specialized equipment and high-pressure
reactors, which raises the initial investment costs. Over time, advances in technology and
novel materials may result in lower costs. Although supercritical transesterification has the
advantage of flexible feedstock and possibly higher yields, large-scale economic viability
depends on striking a balance between energy consumption and capital costs as well as the
dynamics of the current market.
By utilizing waste oils, animal fats, and algae oils, supercritical transesterification can make
use of a large and sustainable pool of feedstock, which lessens the need for edible oils and
encourages resource conservation. To maximize yield and reduce energy consumption for
feedstocks, ongoing research focuses on optimizing reaction parameters, such as pressure,
temperature, and type of alcohol. Compared to conventional techniques, the removal of
catalyst use simplifies supercritical transesterification, lowers waste production, and has
positive environmental effects.
Larger-scale supercritical transesterification plants are becoming possible due to
advancements in reactor design and materials, which makes the production of biodiesel for
commercial use more and more viable.
Translating laboratory-scale success to large-scale production poses challenges, including the

need for robust and cost-effective supercritical fluid reactors. Integrating supercritical
transesterification into existing biodiesel production infrastructure may require significant
modifications and investments. For widespread adoption, supercritical transesterification
must be seamlessly integrated with the current logistical and biodiesel production
infrastructure. Financial incentives and governmental policies that support the use of
sustainable fuels and renewable energy sources can be extremely helpful in facilitating the
widespread adoption of supercritical transesterification. Increased demand for sustainable
biodiesel can be a result of increasing public awareness of the advantages and potential of
supercritical transesterification, which will accelerate market adoption.
REFERENCES
1. Marulanda, V.F. (2012). Biodiesel production by supercritical methanol
transesterification: process simulation and potential environmental impact
assessment. Journal of Cleaner Production, 33, pp.109–116. doi:
https://doi.org/10.1016/j.jclepro.2012.04.022.
2. Deshpande, S.R., Sunol, A.K. and Philippidis, G. (2017). Status and prospects of
supercritical alcohol transesterification for biodiesel production. Wiley
Interdisciplinary Reviews: Energy and Environment, 6(5), p.e252. doi:
https://doi.org/10.1002/wene.252.
3. Zahan, K. and Kano, M. (2018). Biodiesel Production from Palm Oil, Its By-Products,
and Mill Effluent: A Review. Energies, 11(8), p.2132. doi:
https://doi.org/10.3390/en11082132.
4. Dhaval, N. and Modi (2010). Scholars’ Mine Scholars’ Mine Masters Theses Student
Theses and Dissertations Biodiesel production using supercritical methanol Biodiesel
production using supercritical methanol. [online] Available at:
https://core.ac.uk/download/pdf/229285238.pdf.
5. Demirbas, A. (2009). Biodiesel from waste cooking oil via base-catalytic and
supercritical methanol transesterification. Energy Conversion and Management,
50(4), pp.923–927. doi: https://doi.org/10.1016/j.enconman.2008.12.023.
6. Demirbas, A. (2009). Biodiesel from waste cooking oil via base-catalytic and
supercritical methanol transesterification. Energy Conversion and Management,
50(4), pp.923–927. doi: https://doi.org/10.1016/j.enconman.2008.12.023.
7. Ang, G.T., Tan, K.T. and Lee, K.T. (2014). Recent development and economic
analysis of glycerol-free processes via supercritical fluid transesterification for
biodiesel production. Renewable and Sustainable Energy Reviews, 31, pp.61–70. doi:
https://doi.org/10.1016/j.rser.2013.11.004.
8. Saka, S. and Kusdiana, D. (2001). Biodiesel fuel from rapeseed oil as prepared in
supercritical methanol. Fuel, 80(2), pp.225–231. doi: https://doi.org/10.1016/s0016-
2361(00)00083-1.
9. Hoang, D., Bensaid, S. and Saracco, G. (2013). Supercritical fluid technology in

biodiesel production. Green Processing and Synthesis, 2(5). doi:
https://doi.org/10.1515/gps-2013-0046.

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UNIVERSITI SAINS MALAYSIA

EKC358 OLEOCHEMICAL PROCESSING

NAME: R. VIVEKA A/P RAMU

MATRICS NUMBER: 159293

SCHOOL: SCHOOL OF CHEMICAL ENGINEERING

LECTURER: ASSOCIATE PROFESSOR DR. VEL MURUGAN VADIVELU

SUBMISSION DATE: 19TH JANUARY 2024

The process of supercritical transesterification uses alcohol under supercritical conditions to

b. Compare supercritical transesterification with traditional methods of biodiesel

The process that is most frequently used to produce biodiesel is base-catalyzed

One of the challenges of supercritical transesterification is high energy consumption. The

Translating laboratory-scale success to large-scale production poses challenges, including the

9. Hoang, D., Bensaid, S. and Saracco, G. (2013). Supercritical fluid technology in

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