The delay in the energy transition, focused in the replacement of fossil diesel with biodiesel, is mainly caused by the need of reducing the costs associated to the transesterification reaction of vegetable oils with methanol. This reaction, on an industrial scale, presents several problems associated with the glycerol generated during the process. The costs to eliminate this glycerol have to be added to the implicit cost of using seed oil as raw material. Recently, several alternative methods to convert vegetable oils into high quality diesel fuels, which avoid the glycerol generation, are being under development, such as Gliperol, DMC-Biod, or Ecodiesel. Besides, there are renewable diesel fuels known as “green diesel”, obtained by several catalytic processes (cracking or pyrolysis, hydrodeoxygenation and hydrotreating) of vegetable oils and which exhibit a lot of similarities with fossil fuels. Likewise, it has also been addressed as a novel strategy, the use of straight vegetable oils in blends with various plant-based sources such as alcohols, vegetable oils, and several organic compounds that are renewable and biodegradable. These plant-based sources are capable of achieving the effective reduction of the viscosity of the blends, allowing their use in combustion ignition engines. The aim of this review is to evaluate the real possibilities that conventional biodiesel has in order to success as the main biofuel for the energy transition, as well as the use of alternative biofuels that can take part in the energy transition in a successful way.

Many countries are immersed in several strategies to reduce the carbon dioxide (CO₂) emissions of internal combustion engines. One option is the substitution of these engines by electric and/or hydrogen engines. However, apart from the strategic and logistical difficulties associated with this change, the application of electric or hydrogen engines in heavy transport, e.g., trucks, shipping, and aircrafts, also presents technological difficulties in the short-medium term. In addition, the replacement of the current car fleet will take decades. This is why the use of biofuels is presented as the only viable alternative to diminishing CO₂ emissions in the very near future. Nowadays, it is assumed that vegetable oils will be the main raw material for replacing fossil fuels in diesel engines. In this context, it has also been assumed that the reduction in the viscosity of straight vegetable oils (SVO) must be performed through a transesterification reaction with methanol in order to obtain the mixture of fatty acid methyl esters (FAMEs) that constitute biodiesel. Nevertheless, the complexity in the industrial production of this biofuel, mainly due to the costs of eliminating the glycerol produced, has caused a significant delay in the energy transition. For this reason, several advanced biofuels that avoid the glycerol production and exhibit similar properties to fossil diesel have been developed. In this way, “green diesels” have emerged as products of different processes, such as the cracking or pyrolysis of vegetable oil, as well as catalytic (hydro)cracking. In addition, some biodiesel-like biofuels, such as Gliperol (DMC-Biod) or Ecodiesel, as well as straight vegetable oils, in blends with plant-based sources with low viscosity have been described as renewable biofuels capable of performing in combustion ignition engines. After evaluating the research carried out in the last decades, it can be concluded that green diesel and biodiesel-like biofuels could constitute the main alternative to addressing the energy transition, although green diesel will be the principal option in aviation fuel.

The aim of this work is to analyze the effect of using diethyl ether (DEE) as an oxygenated additive of straight vegetable oils (SVOs) in triple blends with fossil diesel, to be used in current compression ignition (C.I.) engines, in order to implement the current process of replacing fossil fuels with others of a renewable nature. The use of DEE is considered taking into account the favorable properties for blending with SVO and fossil diesel, such as its very low kinematic viscosity, high oxygen content, low autoignition temperature, broad flammability limits (it works as a cold start aid for engines), and very low values of cloud and pour point. Therefore, DEE can be used as a solvent of vegetable oils to reduce the viscosity of the blends and to improve cold flow properties. Besides, DEE is considered renewable, since it can be easily obtained from bioethanol, which is produced from biomass through a dehydration process. The vegetable oils evaluated in the mixtures with DEE were castor oil, which is inedible, and sunflower oil, used as a standard reference for waste cooking oil. In order to meet European petrodiesel standard EN 590, a study of the more relevant rheological properties of biofuels obtained from the DEE/vegetable oil double blends has been performed. The incorporation of fossil diesel to these double blends gives rise to diesel/DEE/vegetable oil triple blends, which exhibited suitable rheological properties to be able to operate in conventional diesel engines. These blends have been tested in a conventional diesel engine, operating as an electricity generator. The efficiency, consumption and smoke emissions in the engine have been measured. The results reveal that a substitution of fossil diesel up to 40% by volume can be achieved, independently of the SVO employed. Moreover, a significant reduction in the emission levels of pollutants and better cold flow properties has been also obtained with all blends tested.

By using 1,3-specific Pig Pancreatic lipase (EC 3.1.1.3 or PPL), covalently immobilized on AlPO₄/Sepiolite support as biocatalyst, a new second-generation biodiesel was obtained in the transesterification reaction of sunflower oil with ethanol and other alcohols of low molecular weight. The resulting biofuel is composed of fatty acid ethyl esters and monoglycerides (FAEE/MG) blended in a molar relation 2/1. This novel product, which integrates glycerol as monoacylglycerols (MG) into the biofuel composition, has similar physicochemical properties compared to those of conventional biodiesel and also avoids the removal step of this by-product. The biocatalyst was found to be strongly fixed to the inorganic support (75%). Nevertheless, the efficiency of the immobilized enzyme was reduced to half (49.1%) compared to that of the free PPL. The immobilized enzyme showed a remarkable stability as well as a great reusability (more than 40 successive reuses) without a significant loss of its initial catalytic activity. Immobilized and free enzymes exhibited different reaction mechanisms, according to the different results in the Arrhenius parameters (Ln A and Ea). However, the use of supported PPL was found to be very suitable for the repetitive production of biofuel due to its facile recyclability from the reaction mixture.

A new biofuel similar to biodiesel was obtained in the 1,3-selective transesterification reaction of sunflower oil with ethanol using as biocatalyst a Rhizopus oryzae lipase (ROL) immobilized on Sepiolite, an inorganic support. The studied lipase was a low cost powdered enzyme preparation, Biolipase-R, from Biocon-Spain, a multipurpose additive used in food industry. In this respect, it is developed a study to optimize the immobilization procedure of these lipases on Sepiolite. Covalent immobilization was achieved by the development of an inorganic-organic hybrid linker formed by a functionalized hydrocarbon chain with a pendant benzaldehyde, bonded to the AlPO₄ support surface. Thus, the covalent immobilization of lipases on amorphous AlPO₄/sepiolite (20/80 wt %) support was evaluated by using two different linkers (p-hydroxybenzaldehyde and benzylamine-terephthalic aldehyde, respectively). Besides, the catalytic behavior of lipases after physical adsorption on the demineralized sepiolite was also evaluated. Obtained results indicated that covalent immobilization with the p-hydroxybenzaldehyde linker gave the best biocatalytic behavior. Thus, this covalently immobilized lipase showed a remarkable stability as well as an excellent capacity of reutilization (more than five successive reuses) without a significant loss of its initial catalytic activity. This could allow a more efficient fabrication of biodiesel minimizing the glycerol waste production.