2.

CHAPTER

LITERATURE REVIEW

2.1 History and Production of Biodiesel

Sir Rudolf Diesel was the first to successfully run conventional diesel engines in the early

1900s without making any changes to the vegetable oil. Vegetable oil was used as diesel fuel

in the 1930s and 1940s especially in an emergency(Zahan & Kano, 2018). However,

additional research revealed that using vegetable and animal oils as diesel fuel is unfeasible

due to their huge molecular mass, low volatility, and high kinematic viscosity, which impair

engine performance and cause other issues such as oil thickening, gelling, and sticking.

Petroleum became the dominating energy source due to its low cost and simple availability,

and petroleum diesel was developed as the principal fuel for diesel engines. Nonetheless,

petroleum and its derivative fuels have been in limited supply on several occasions,

prompting the hunt for other energy sources(Arifin, 2009).

Biodiesel production is one possible solution to the difficulty of developing sustainable

energy and management of waste, particularly in the industrial and transportation

sectors(Silalahi et al., 2020). It's an alternative fuel made from renewable resources that burns

cleaner in diesel engines and emits less emissions. Biodiesel, like Petro-diesel, is made up of

hydrocarbon chains that are sulfur-free and do not contain aromatic components(Innocent et

al., 2013).

Biodiesel is a diesel fuel made from animal or vegetable oils that produces little soot, carbon

IV oxide, or particulate matter when burned. It is made from trans esterifying vegetable oil or

animal fat and consists of long chain mono-alkyl esters(Oliveira & Da Silva, 2013).

2.2 Advantages and Disadvantages of Biodiesel

The benefits of biodiesel use can be divided into three categories: environmental impact,

energy security, and economic impact. Based on environmental impact, it reduces

environmental effect of waste product as it is made from utilized cooking oils, when

compared to fossil fuel, biodiesel made from cooking oil emits 86% less greenhouse gases.

Biodiesel reduces particulate matter by 47 percent when compared to fossil fuel, which helps

to minimize dangerous exhaust emissions. Finally, because biodiesel is made from plants, it

is renewable, and what is used may be regrown(Ragel, 2018)

Concerning the energy security, it is critical to keep in mind that fossil oil is a finite resource.

Biomass, on the other hand, is a renewable resource that is abundant in many nations. The

creation of energy from locally available sources such as biomass reduces the country's

reliance on fossil oil(Go--, 2010).

In terms of employment, the bioenergy sector employed 2.8 million people worldwide in

2014. Local agriculture receives direct support, which is another way to show your support

for your farmer(Mizik & Gyarmati, 2021).

Although biodiesel has received a lot of scientific attention in recent years, it does have

significant drawbacks. When utilizing biodiesel, one of the issues that arise is an increase in

nitrogen oxide emissions, which can lead to smog and acid rain. Biodiesel, like Petro-diesel,

has a lower energy yield than Petro-diesel. More biodiesel is required to provide the same

quantity of energy as Petro-diesel(Negm et al., 2017). Furthermore, the utilization of valuable

cropland to cultivate biodiesel crops could raise food prices and lead to food scarcity(Viesturs

& Melece, 2014).

2.3 TRANSESTERIFICATION PROCESS

Triglycerides, which are big molecules made up of numerous organic acids coupled with

glycerol, an alcohol, are the oils found in wasted cooking oils. Esters are organic acids

coupled with other, lighter alcohols that make up the major components of vegetable oil.

Transesterification is the process of adding methanol or ethanol to vegetable oil to convert

it(Ullah et al., 2014).

Transesterification is defined as the separation of fatty acids from their glycerol backbone to

produce fatty acid esters (FAE) and free glycerol. Transesterification of triglycerides such as

animal fats can produce biodiesel in batches or constantly in the presence of a base or acid

catalyst, fat or vegetable oil with lower molecular weight alcohols. Monoglycerides and

diglycerides are intermediate products in this stepwise process(Marchetti, 2010).

Catalyst

Triglycerides + Methanol Glycerol + Methyl Ester

Figure 2.1- Transesterification reaction

The fatty acid mixture found in the parent vegetable oil or animal fat is reacted with an

alcohol (typically methanol) in the presence of a catalyst to give the corresponding alkyl

esters (thus, for methanol, the methyl esters) of the fatty acid mixture present in the parent

vegetable oil or animal fat. As demonstrated in Figure 2.2, the transesterification reaction

happens in steps(Zhang et al., 2003).

R1R2R3ТG+CH3OH↔R2R3DG+МER1FA

R2R3DG+CH3OH↔R3МG+МER2FA

R3МG+CH3OH↔МER3FA+Glycerol

Figure 2.2- Transesterification reaction stepwise

R1, R2, and R3 are the alkyl groups of three distinct fatty acids, such as palmitic, oleic, and

linoleic acids, respectively.

TG = Triglyceride
DG = Diglyceride

MG = Monoglyceride

ME = Methyl Ester

FA = Fatty Acid

2.4 METHODS OF TRANSESTERIFICATION THAT HAVE BEEN USED TO

CONVERT USED COOKING OIL INTO BIODIESEL

Alkaline catalysed transesterification process

Base catalysts such as sodium methoxide, sodium hydroxide, potassium hydroxide, and

potassium methoxide are employed in the alkaline catalysed transesterification process. The

alkaline catalysed transesterification process converts triglycerides to esters most

effectively when the free fatty acid (FFA), any saturated or unsaturated monocarboxylic

acids found naturally in fats, oils, or greases, but not connected to glycerol backbones;

these might result in high acid fuels and require specific technologies to convert into

biodiesel level is less than 1%(Gebremariam & Marchetti, 2017)

Acid-catalyzed transesterification process

In the acid transesterification process, acidic catalysts, such as sulfuric acid, phosphoric

acid, hydrochloric acid and organic sulfonic acid, are used. In this process, a strong acid is

used as a catalyst for esterification of the FFAs and the transesterification of

triglycerides(Yacob et al., 1998)

Enzyme catalysed transesterification process

This method has a number of advantages over chemical-catalysed transesterification,

including the absence of by-products, ease of product removal, use of moderate process

conditions (temperature, 35–45 °C), and catalyst recycling. Enzymatic reactions can

successfully be employed for the transesterification of spent cooking oil since enzymatic

activities are indifferent to the presence of free fatty acids and the feedstock's water

content(Vela et al., 2020)

Non-catalysed supercritical transesterification process

A new approach dubbed non-catalysed supercritical methanol transesterification has been

developed to circumvent the constraints of base and acid catalysed transesterification.

Under supercritical circumstances (temperature 350–400 °C and pressure greater than 80

bar), the transesterification process can be completed in a very short time (just 4 minutes)

(Karki et al., 2017). This process It obviates the need for filtration in the latter stages.

Heterogeneous catalyst transesterification process

For heterogeneous catalysed processes, extensive study has been conducted to develop

acceptable solid acid or solid base catalysts. Soap cannot be made with a heterogeneous

catalyst. As solid catalysts, solid metal oxides such as tin, magnesium, and zinc are utilized.

They do, however, become metal soap or metal glycerates. The use of a comprehensive

heterogeneous catalyst can solve this problem(Faruque et al., 2020). The use of a

comprehensive heterogeneous catalyst can solve this problem. It is made up of a zinc and

aluminium oxide mixture that aids in the transesterification process without causing catalyst

loss. Alkali or alkaline oxides covered over a vast surface area make up the majority of

solid catalysts(Arumugam, 2010).

Figure 2.3: Diagram of the biodiesel production process

Reference

Arifin, S. F. (2009). Production of Biodiesel From Waste Cooking Oil and Rbd. May.

Arumugam, S. (2010). Development of heterogeneous base catayst for transesterification

reaction.

Faruque, M. O., Razzak, S. A., & Hossain, M. M. (2020). Application of heterogeneous

 catalysts for biodiesel production from microalgal oil—a review. Catalysts, 10(9), 1–25.

https://doi.org/10.3390/catal10091025

Gebremariam, S. N., & Marchetti, J. M. (2017). Biodiesel production technologies: Review.

In AIMS Energy (Vol. 5, Issue 3). https://doi.org/10.3934/energy.2017.3.425

Go--, D. O. E. (2010). Biodiesel handling and use guide. In Biodiesel Handling and Use

Guide (Issue November).

Innocent, D. S., ’donnell, O., Sylvester, P., Yahaya, M. F., & Isiomanwadike, L. N. O.

(2013). Comparative Analysis of Biodiesel and Petroleum Diesel. International Journal

of Education and Research, 1(8), 1–8.

Karki, S., Sanjel, N., Poudel, J., Choi, J. H., & Oh, S. C. (2017). Supercritical

transesterification of waste vegetable oil: Characteristic comparison of ethanol and

methanol as solvents. Applied Sciences (Switzerland), 7(6).

https://doi.org/10.3390/app7060632

Marchetti, J. M. (2010). Biodiesel production technologies. Biodiesel Production

Technologies, July, 1–166.

Mizik, T., & Gyarmati, G. (2021). Economic and Sustainability of Biodiesel Production—A

Systematic Literature Review. Clean Technologies, 3(1), 19–36.

https://doi.org/10.3390/cleantechnol3010002

Negm, N. A., Abou Kana, M. T. H., Youssif, M. A., & Mohamed, M. Y. (2017). Biofuels

from vegetable oils as alternative fuels: Advantages and disadvantages. Surfactants in

Tribology, Volume 5, 289–368. https://doi.org/10.1201/b20780

Oliveira, L. E., & Da Silva, M. L. C. P. (2013). Comparative study of calorific value of

rapeseed, soybean, jatropha curcas and crambe biodiesel. Renewable Energy and Power
 Quality Journal, 1(11), 679–682. https://doi.org/10.24084/repqj11.411

Ragel, K. B. (2018). Enzymatic synthesis of biodiesel from high free fatty acid feedstock

using a recombinant Rhizopus oryzae lipase. Tdx.Cat, 195.

https://www.tdx.cat/handle/10803/650368

Silalahi, F. T. R., Simatupang, T. M., & Siallagan, M. P. (2020). Biodiesel produced from

palm oil in Indonesia: Current status and opportunities. AIMS Energy, 8(1), 81–101.

https://doi.org/10.3934/energy.2020.1.81

Ullah, Z., Bustam, M. A., & Man, Z. (2014). Characterization of Waste Palm Cooking Oil for

Biodiesel Production. International Journal of Chemical Engineering and Applications,

5(2), 134–137. https://doi.org/10.7763/ijcea.2014.v5.366

Vela, M. A. F., Acevedo-Páez, J. C., Urbina-Suárez, N., Basto, Y. A. R., & González-

Delgado, Á. D. (2020). Enzymatic transesterification ofwaste frying oil from local

restaurants in east colombia using a combined lipase system. Applied Sciences

(Switzerland), 10(10). https://doi.org/10.3390/app10103566

Viesturs, D., & Melece, L. (2014). Advantages and disadvantages of biofuels: Observations

in Latvia. Engineering for Rural Development, 13(January 2014), 210–215.

Yacob, M. R., Kabir, I., Radam, A., Abed, K. A., El Morsi, A. K., Sayed, M. M., Shaib, A. A.

E., Gad, M. S., Carlo, A. ., Carolina, L. ., Ejikeme, P. M., Anyaogu, I. D., Ejikeme, C.

L., Nwafor, N. P., Egbuonu, C. A. C., Ukogu, K., Ibemesi, J. A., Chemistry, I.,

Polytechnic, F., … Matheus, R. (1998). Catalysis in Biodiesel Production by

Tranesterification Process-An Insight. Egyptian Journal of Petroleum, 9(1), 332–337.

http://www.scielo.br/scielo.php?pid=S0103-

50531998000300002&script=sci_arttext&tlng=en

%0Ahttps://doi.org/10.1016/j.ejpe.2018.02.008%0Ahttp://linkinghub.elsevier.com/retrie
 ve/pii/S1878029615006532

Zahan, K. A., & Kano, M. (2018). Biodiesel production from palm oil, its by-products, and

mill effluent: A review. Energies, 11(8), 1–25. https://doi.org/10.3390/en11082132

Zhang, Y., Dubé, M. A., McLean, D. D., & Kates, M. (2003). Biodiesel production from

waste cooking oil: 1. Process design and technological assessment. Bioresource

Technology, 89(1), 1–16. https://doi.org/10.1016/S0960-8524(03)00040-3