Unlocking the future of sustainable energy: biodiesel synthesis from non-edible feedstocks powered by eco-friendly nano-magnetic catalysts

The present review primarily focuses on the perspectives and state-of-the-art of heterogeneous catalysts, nanocatalysts, biocatalysts, bifunctional catalysts, metal-organic frameworks (MOF), and covalent organic frameworks (COF) for biodiesel production. The environmental concern associated with nonrenewable fossil fuels has led to finding alternative energy sources that can be used to meet global energy demands. Biofuels such as biodiesel are one of the energy sources that could replace fossil fuels. The homogeneous acid and base catalysts are generally used for commercial biodiesel production. However, homogeneous catalysts have downsides such as toxicity, corrosion, soap formation, high wastewater output, and non-reusability. Consequently, heterogeneous acid and base catalysts have been introduced that are less sensitive to moisture and free fatty acids (FFAs), easily separated and recovered, and reusable. Recently, novel catalysts such as waste biomass-derived mesoporous heterogeneous catalysts, chemically synthesized heterogeneous catalysts, metal ion-doped heterogeneous catalysts, bifunctional acid-base catalysts, and carbonaceous char-supported hetero catalysts, nanocatalysts, MOF and COF catalysts have potential to replace homogeneous base catalysts, aid in sustainable and cost-effective biodiesel production. This review provides insights into the recent advancement of various catalysts, catalyst preparation and operations, type of catalysts and suitability, catalyst efficiency, life cycle assessment, catalyst-associated challenges, and prospects for sustainable biodiesel production.

Homogeneous base catalyst has wide acceptability in biodiesel production because of their fast reaction rates. However, postproduction costs incurred from aqueous quenching, wastewater and loss of catalysts led to the search for alternatives. Heterogeneous base catalyst is developed to cater these problems. The advantages of heterogeneous catalyst are their high basicity and non-toxicity. This work compared the production of biodiesel using two different kind of catalysts that is homogeneous catalyst (sodium hydroxide, NaOH and potassium hydroxide, KOH) and heterogeneous catalysts (calcium, oxide, CaO catalyst derived from chicken and ostrich eggshells). Transesterification of waste cooking oil (WCO) and methanol in the presence of heterogeneous base catalyst was conducted at an optimal reaction condition (calcination temperature for catalyst: 1000 °C; catalyst loading amount: 1.5 wt%; methanol/oil molar ratio: 10:1; reaction temperature: 65 °C; reaction time: 2 hours) with 97% biodiesel yield was obtained. While, the homogeneous base catalyst gave higher biodiesel yield of 98% at optimum operating condition (catalyst concentration: 0.75 wt%; methanol/oil molar ratio: 6:1; reaction temperature: 65 °C; reaction time: 1 hours). The slight difference in the biodiesel yield was due to the stronger basic strength in the homogeneous catalyst and were not statistically not different (p=0.05). However, despite these advances, the ultimate aim of producing biodiesel at affordable low cost and minimal-environmental-impact is yet to be realized.

Lactic acid (2-hydroxypropionic acid, CH3CHOHCOOH) is one of the platform chemicals derived from biomass. It is used in the food industry and in the manufacture of biodegradable plastics and useful chemicals. Recently, various examinations were carried out not only by fermentation but also by the chemical methods using heterogeneous and homogenous catalysts. This chapter focuses on the chemical processes with heterogeneous catalysts in lactic acid and lactate ester productions from sugars. Bronsted basic catalysts and Lewis acid catalysts gave lactic acid in high yields. In the lactic acid productions from triose, lactic acid ester is obtained with high yields of nearly 100 % in alcohols around 100 °C using Sn-β zeolite, Sn–carbon–silica, and H-USY catalysts. In the lactic acid production from hexose, lactic acid ester or a lactate salts was obtained from glucose, fructose, and sucrose with the comparatively high selectivity of about 50 % by several catalytic processes, that were in water around 50 °C using heterogeneous basic catalysts, such as activated hydrotalcite catalyst, in hydrothermal water around 300 °C using homogeneous basic catalysts, such as NaOH and ZnSO4, and in alcohols around 160 °C using heterogeneous Lewis acid catalysts, such as Sn-β zeolite.

A review of magnetic solid catalyst development for sustainable biodiesel production

A heterogeneous base catalyst transesterification process with a calcium oxide (CaO) catalyst was performed to produce high-purity methyl ester (ME) from pretreated sludge palm oil (PSPO) derived from sludge palm oil (SPO). Additionally, a comparative analysis was conducted with potassium hydroxide (KOH) as a homogeneous base catalyst to assess the distinctions between heterogeneous and homogeneous base catalysts. The response surface methodology (RSM) was utilized to determine the optimal and recommended conditions for both transesterification processes. For heterogeneous transesterification, a varying CaO catalyst loading (10–60 wt.%), methanol (25–65 wt.%), and reaction time (60–180 min) were essential parameters. Meanwhile, homogeneous transesterification involved investigating the KOH catalyst loading (1–3 wt.%), methanol (1.8–5.5 wt.%), and reaction time (20–60 min). For the heterogeneous-base-catalyzed reaction, the recommended conditions were as follows: a molar ratio of methanol to oil of 5.83:1 (41.61 wt.%), 31.3 wt.% CaO, and a reaction time of 119.0 min, which resulted in a ME purity of 96.51 wt.%. The optimal conditions for homogeneous transesterification were a molar ratio of methanol to oil of 0.49:1 (3.45 wt.%), a 40 min reaction time, and a 1.39 wt.% KOH concentration, which achieved 96.59 wt.% ME and met the standard.

The effective transesterification process to produce fatty acid methyl esters (FAME) requires the use of low-cost, less corrosive, environmentally friendly and effective catalysts. Currently, worldwide biodiesel production revolves around the use of alkaline and acidic catalysts employed in heterogeneous and homogeneous phases. Homogeneous catalysts (soluble catalysts) for FAME production have been widespread for a while, but solid catalysts (heterogeneous catalysts) are a newer development for FAME production. The rate of reaction is much increased when homogeneous basic catalysts are used, but the main drawback is the cost of the process which arises due to the separation of catalysts from the reaction media after product formation. A promising field for catalytic biodiesel production is the use of heteropoly acids (HPAs) and polyoxometalate compounds. The flexibility of their structures and super acidic properties can be enhanced by incorporation of polyoxometalate anions into the complex proton acids. This pseudo liquid phase makes it possible for nearly all mobile protons to take part in the catalysis process. Carbonaceous materials which are obtained after sulfonation show promising catalytic activity towards the transesterification process. Another promising heterogeneous acid catalyst used for FAME production is vanadium phosphate. Furthermore, biocatalysts are receiving attention for large-scale FAME production in which lipase is the most common one used successfully This review critically describes the most important homogeneous and heterogeneous catalysts used in the current FAME production, with future directions for their use.

The relevance of heterogeneous catalysis in biodiesel production cannot be overemphasized, as heterogeneous catalysts have eliminated the demerits associated with a homogeneous catalysts. Some heterogeneous catalysts experience drawbacks such as partial recoverability and reusability, energy and waste conservation issues during biodiesel processing and leaching of active catalyst sites. This paper highlights and summarizes several heterogeneous catalysts used in biodiesel production. The catalyst preparation, reaction conditions, feedstock, and biodiesel yield for the heterogeneous base and acid catalysts were emphasized. The inability of heterogeneous base catalysts to trans-esterify low-grade oil with high free fatty acid (FFA) is a primary concern; the cost of processing low-grade oil with high FFA using heterogeneous acid catalysts is also a big issue. Nano-doped heterogeneous catalysts with unique properties were recommended because they can process oil with high FFA transesterification, improve reaction efficiency, simplify production, reduce the leaching of active sites, enable better biodiesel yield by minimizing energy and waste, and increase catalyst recoverability, activity, selectivity and durability.

Waste cooking oil from restaurants and hotels is expected to be thrown away. As a result, waste cooking oils (WCO) which have no pre-treatment will unfavourably pollute the earth. One of the approaches to treat and use the waste cooking oil is by its conversion into biodiesel. This paper illustrates the study on the active reaction of waste cooking oil transesterification into biodiesel and identifies the best set of input parameters for the most economical yield of biodiesel. The sample of WCO for the present study was collected from the restaurants. Methanol was used as a reactant along with two homogeneous base catalysts(KOH, NaOH) and one heterogeneous base catalyst(CaO). The input parameters selected for the study were methanol-to-oil molar ratio, catalyst type, reaction temperature and reaction time. The orthogonal experimental array L9 was selected for the present study with four parameters and three levels. The optimum set of input parameters for the transesterification process is; 8:1 methanol-to-oil molar ratio, KOH as a catalyst, 55 °C reaction temperature and 120 min of reaction time. The optimum yield of FAME was 92.5% with 1.0% catalyst concentration by weight.

[EN] In this work is presented the production of high added value chemicals and biofuels from platform molecules derived from biomass such as 5-hydroxymethylfurfural using heterogeneous catalysts.
\nFirstly, it has been carried out the synthesis of precursors molecules of surfactant by acetalization of HMF with fatty alcohols. Optimization of the catalyst showed that the zeolite Beta modified with sodium through the ion exchange route was the best catalyst for carrying out both direct acetalization of HMF with fatty alcohols and transacetalisation of dimethyl acetal HMF with fatty alcohols, the latter giving excellent yields and selectivities. 
\nIn a second part, a new class of anionic surfactants with the structure of the 5-alkoxymethylfuroate have been obtained by the etherification of HMF with fatty alcohols (C8, C12, C16, C18) using zeolite Beta as acid catalysts. The subsequent oxidation of the aldehyde group with Au/CeO2 allowed the synthesis of the 5-alkoxymethylfuranoics acid derivatives with high selectivity. It has been shown that the sodium salts of these acids exhibit surfactant properties very similar to conventional surfactants.
\nThe synthesis of furan chalcones with pharmacological properties was performed through the Claisen-Schmidt condensation reaction between HMF and acetophenones in the presence of different heterogeneous basic catalysts. It has been shown that the control of polarity of the reaction medium is critical to reach both excellent yields and selectivities towards furanochalcones. The most active and selective catalyst was an Al/Mg mixed oxide working in ethanol-water as a solvent, exhibiting better catalytic properties than conventional homogeneous basic catalysts.
\nFinally, biofuels of second generation have been synthesized from HMF and aromatic hydrocarbons in a two-step process. Firstly it has been carried out the alkylation of aromatic hydrocarbons with HMF in the presence of different heterogeneous acid catalysts. In a second step, the alkylated compounds were transformed into hydrocarbon biofuels through a hydrodeoxygenation process. ITQ-2 and USY zeolites were the most suitable catalysts for the alkylation of aromatic hydrocarbons with HMF catalysts. The 5-benzylfurfural derivatives thus obtained were submitted to a hydrodeoxygenation process using a mixture of Pt/C and Pt/TiO2 as catalyst, resulting in a mixture of alkyl cycloalkanes. It has been shown that this alkylation-hydrodeoxygenation process gives a mixture of hydrocarbons in the range of diesel and kerosene which may be used as high quality additives for these fuels.

Chapter 3 - Applications of heteropoly acids as heterogeneous catalysts

Several techniques, in which different homogenous catalysts and procedures, that are in use for transesterification of a vegetable oil or an animal fat have been successful in synthesizing biodiesel, although with some certain limitations. For such a purpose, among the catalysts employed are acidic as well as basic catalysts. It has been found that acidic catalysts can be tolerant with a high content of free fatty acids found in those low value feedstock oils/fats to be transesterified, although some sort of pretreatment by means of esterification might be required in order to synthesize biodiesel. Moreover, with employing homogenous acidic catalysts, it seems that biodiesel purification procedures are simplified; thus, reducing synthesis cost. In fact, these features of homogenous acidic catalysts render them advantageous over basic ones. With basic homogenous catalysts this; however, has not been possible due to the development of saponification reaction. To effectively perform, such catalysts require that the content of free fatty acids in the feedstock oil/fat is minimal. This requirement is also applicable to the moisture level in the feedstock. In terms of corrosive effects; nevertheless, acidic catalysts are disadvantageous compared to basic ones.

With the rapid development of industry and the increasing demand for transportation, traditional sources of energy have been excessively consumed. Biodiesel as an alternative energy source has become a research focus. The most common method for biodiesel production is transesterification, in which lipid and low carbon alcohol are commonly used as raw materials, in the presence of a catalyst. In the process of transesterification, the performance of the catalyst is the key factor of the biodiesel yield. This paper reviews the recent research progress on homogeneous and heterogeneous catalysts in biodiesel production. The advantages and disadvantages of current homogeneous acid catalysts and homogeneous base catalysts are discussed, and heteropolyacid heterogeneous catalysts and biomass-derived base catalysts are described. The applications of the homogeneous and heterogeneous catalyst derivatives ionic liquids/deep eutectic solvents and nanocatalysts/magnetic catalysts in biodiesel production are reviewed. The mechanism and economic cost of current homogeneous acid catalysts and homogeneous base catalysts are also analyzed. The unique advantages of each type of catalyst are compared to better understand the microscopic details behind biodiesel. Finally, some challenges of current biodiesel catalysts are summarized, and future research directions are presented. This review will provide general and in-depth knowledge on the achievements, directions, and research priorities in developing novel homogeneous/heterogeneous catalysts for the green and cost-effective production of biodiesel.

Use of CaO and Na3PO4 Catalysts in the Synthesis of Biodiesel and Investigation of Fuel Properties

 One of the prospective alternative sources of energy is biodiesel, which is obtained from conventional and substandard sources via various methods. One of them is transesterification in the presence of a catalyst. The catalyst may be either harmonized or varied. This chapter will give detailed information about the various catalysts used in biodiesel synthesis. The chapter focuses on the efficiency, limitations, and advantages of all kinds of catalysts and their properties, and appropriateness in the transesterification method. An extensive study has been carried out on the usage of homogeneous and heterogeneous catalysts for biodiesel production. The data reviewed reflects that those homogeneous catalysts are proficient in converting oil with low FFA and feedstock that contains water. On the other hand, heterogeneous catalyst gives a range of selectivity on high FFA content and water adaptability. It is known that the numbers of acidic or basic sites control the properties of heterogeneous catalysts. Zirconia and Zeolites-based catalysts by some modifications, can be used as both basic and acidic catalysts. Heterogeneous catalysts derived from waste have received an important role in biodiesel production. Lately, high catalytic activities under optimum operating conditions have been recognized of Nanocatalysts. This review article gives elaborated information on various materials used as catalysts.<br>

Liquid fuel synthesis via CO2 hydrogenation by coupling homogeneous and heterogeneous catalysis