energies Review An Overview of Biodiesel Production via Calcium Oxide Based Catalysts: Current State and Perspective Hoora Mazaheri 1, Hwai Chyuan Ong 2,*, Zeynab Amini 3, Haji Hassan Masjuki 4, M. Mofijur 2,5 , Chia Hung Su 6, Irfan Anjum Badruddin 7,8 and T.M. Yunus Khan 8 1 Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur 50603, Malaysia; [email protected] 2 Centre for Green Technology, Faculty of Engineering and Information Technology, University of Technology Sydney, Sydney, NSW 2007, Australia; MdMofi[email protected] 3 Centre for Agriculture and the Bioeconomy, Queensland University of Technology, 2 George Street, Brisbane, QLD 4000, Australia; [email protected] 4 Department of Mechanical Engineering, Faculty of Engineering, International Islamic University Malaysia (IIUM), Kuala Lumpur 50728, Malaysia; [email protected] 5 Mechanical Engineering Department, Prince Mohammad Bin Fahd University, Al Khobar 31952, Saudi Arabia 6 Department of Chemical Engineering, Ming Chi University of Technology, New Taipei City 24301, Taiwan; [email protected] 7 Research Center for Advanced Materials Science (RCAMS), King Khalid University, P.O. Box 9004, Abha 61413, Saudi Arabia; [email protected] 8 Mechanical Engineering Department, College of Engineering, King Khalid University, P.O. Box 394, Abha 61421, Saudi Arabia; [email protected] * Correspondence: [email protected] Citation: Mazaheri, H.; Ong, H.C.; Abstract: Biodiesel is a clean, renewable, liquid fuel that can be used in existing diesel engines without Amini, Z.; Masjuki, H.H.; Mofijur, M.; modification as pure or blend. Transesterification (the primary process for biodiesel generation) Su, C.H.; Anjum Badruddin, I.; Khan, via heterogeneous catalysis using low-cost waste feedstocks for catalyst synthesis improves the T.M.Y. An Overview of Biodiesel economics of biodiesel production. Heterogeneous catalysts are preferred for the industrial generation Production via Calcium Oxide Based of biodiesel due to their robustness and low costs due to the easy separation and relatively higher Catalysts: Current State and reusability. Calcium oxides found in abundance in nature, e.g., in seashells and eggshells, are Perspective. Energies 2021, 14, 3950. promising candidates for the synthesis of heterogeneous catalysts. However, process improvements https://doi.org/10.3390/en14133950 are required to design productive calcium oxide-based catalysts at an industrial scale. The current work presents an overview of the biodiesel production advancements using calcium oxide-based Academic Editor: João Fernando Pereira Gomes catalysts (e.g., pure, supported, and mixed with metal oxides). The review discusses different factors involved in the synthesis of calcium oxide-based catalysts, and the effect of reaction parameters on Received: 11 May 2021 the biodiesel yield of calcium oxide-based catalysis are studied. Further, the common reactor designs Accepted: 18 June 2021 used for the heterogeneous catalysis using calcium oxide-based catalysts are explained. Moreover, Published: 1 July 2021 the catalytic activity mechanism, challenges and prospects of the application of calcium oxide-based catalysts in biodiesel generation are discussed. The study of calcium oxide-based catalyst should Publisher’s Note: MDPI stays neutral continue to be evaluated for the potential of their application in the commercial sector as they remain with regard to jurisdictional claims in the pivotal goal of these studies. published maps and institutional affil- iations. Keywords: biodiesel production; heterogeneous catalyst; alternative fuel; renewable energy; alkaline metal oxides Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. 1. Introduction This article is an open access article The rapid depletion of fossil fuel supplies affects energy security and increases green- distributed under the terms and house gas emissions and carbon dioxide (CO2) concentration in the atmosphere, and these conditions of the Creative Commons key drivers necessitate the search for alternative sources of energy [1–3]. Energy supplies Attribution (CC BY) license (https:// have transitioned from fossil fuels since the early twentieth century to renewable sources creativecommons.org/licenses/by/ (at a much slower rate, though) [4,5], and some of the most remarkable alternative energy 4.0/). Energies 2021, 14, 3950. https://doi.org/10.3390/en14133950 https://www.mdpi.com/journal/energies Energies 2021, 14, 3950 2 of 23 sources that can stand in for fossil fuels are wind, solar, water, and biofuel. Solar, wind, and hydro energy are the chief sources of electricity and heat generation used globally. In the United States, 20% of total electricity was produced from renewable sources in 2020; wind (8.4%), hydropower (7.3%), solar (2.3%), biomass (1.4%), and geothermal (0.5%) [6]. Biomass is a renewable organic material and bioenergy utilizes biomass, in order to produce heat, electricity, and biofuel, such as biogas and liquid fuels. The predominant types of renewable energy from biomass (i.e., biofuel) are biochar (solid), biodiesel and bioethanol (liquid), and bio-hydrogen, biogas, and biosynthetic gas (gaseous) [7,8]. Although energy sources other than biomass are preferred for electricity and heat generation, biofuels as liquid fuels serve as energy-dense fuels that can be blended with petroleum-based fuels, i.e., gasoline and diesel [9]. Petroleum diesel (petrodiesel) fuel exhausts emissions, such as particulate matter, nitrogen oxide (NOx), and aerosols that can cause various health issues, such as respiratory diseases, allergy, cancer, and vascular diseases [10]. Unlike petrodiesel, biodiesel does not contain any metals, residues, or sulphur aromatics, and releases minimal amounts of glasshouse gases [11,12]. In this way, biodiesel can be used in combination with petrodiesel, as they have similar characteristics [13]. Biodiesel can also be used as an alternative to fossil fuel in diesel engine with no modification [14]. However, biodiesel might not be viewed as a petrodiesel substitute; rather, it can be considered as an essential component of a secure and diverse energy supply. Transesterification is the general process for biodiesel production, in which alcohol (chiefely methanol) and oil react, and the reaction is usually catalyzed by the utilization of a homogeneous or heterogeneous catalyst [15,16]. There is some technological difficulty (corrosion and emulsification) when acid or base homogeneous catalysts are applied in the reaction [17]. On the contrary, compared to homogeneous catalysts, such as potassium hydroxide (KOH), that dissolve in the reactant [18], heterogeneous catalysts are advan- tageous for their easy separation, possibility of high-quality glycerol with high levels of purity (≥98%) from the product, and possible reusability of the catalyst for several cycles. Therefore, transesterification via heterogeneous catalysis as a green process can value add to the process. Calcium oxide (CaO)-based catalysts are heterogeneous, low-cost, available material in abundance in nature that can be produced from waste feedstocks, such as seashells and eggshells [19]. Cao-based catalysts have relatively high activity, and their leaching problem can be overcome by supporting it on different carriers or mixing with other oxides [20]. This review focuses on biodiesel generation via transesterification reactions from a catalytic standpoint. In this regard, this review firstly discussed the heterogeneous and homogeneous catalysts, as well as their advantages and disadvantages; and secondly, evaluated CaO- (in the different forms of pure, supported and mixed with other oxides) catalyzed transesterification. Additionally, CaO catalysts derived from natural resources were reviewed and the effect of various parameters on the transesterification, including catalyst reusability, catalyst-loading amount, water content, total primary sites, calcination time and temperature, and reaction time were studied in brief. Moreover, the reactors in use for heterogeneous catalysts were discussed. Finally, the future perspective of the CaO-derived catalysts was reviewed to assess their capacity in biodiesel production. 2. Biodiesel Biodiesel is a sustainable liquid fuel for transportation [21] and it has improved characteristics compared to petrodiesel, such as lower density and viscosity. The density of the fuel affects the engine’s fuel injection system and the lower dense and viscous fuel leads to better atomization and mixing properties [22]. The properties of the developed biodiesel for further use as a pure compound or a blend should be tested, and the properties must be commensurate with international standards for testing biodiesel, such as EN 14,214 and ASTM D6751, according to the European Committee for Standardization and Energies 2021, 14, 3950 3 of 23 American Standards for Testing and Materials. The biodiesel properties were compared with petrodiesel and listed in Table1. Table 1. Pure biodiesel properties versus petrodiesel [23–27]. Biodiesel Petrodiesel Exhaust emissions Low High Renewable supply Renewable Non-renewable Biodegradability Good Poor Toxicity Non-toxic Toxic Brake thermal efficiency Low High Lubricity Good Poor Combustion Complete Incomplete Carbon monoxide emissions Low High Sulphur dioxide: ~500 ppm Sulphur and aromatic content 0.0% Aromatics: 20–40% Explosively Non-explosive Explosive Flashpoint (K) 423 337 Cetane number 45–70 40–52 Chemical