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Dimethyl carbonate (DMC) is an interesting blending component for diesel fuel (D) owing to the high oxygen content (53 wt.%) and the absence of C–C bonds in its structure. Moreover, DMC can be produced from CO2 and methanol, which provides a renewable way to reduce anthropogenic CO2. This research has been addressed to assess the use of DMC as a solvent of sunflower oil (SO) and castor oil (CO), with the purpose of obtaining biofuels that can replace fossil diesel as much as possible. The blending of DMC with straight vegetable oils (SVOs) reduces their high viscosity, allowing their usage as drop-in biofuels without chemical treatments. Based on viscosity requirements of European Standard EN 590, the optimal DMC/SVO double blends have been tested as direct biofuels by themselves or mixed with fossil diesel in D/DMC/SVO triple blends. Relevant physico-chemical properties of fuels have been analyzed. Engine parameters such as power output, brake-specific fuel consumption (BSFC) and soot emissions have been studied to determine the effect of new biofuels on efficiency of a diesel engine. An outstanding engine efficiency is shown by the studied D/DMC/SVO triple blends, either with SO or CO as an SVO. The low calorific value of DMC is the main reason for reduction in power and BSFC, as the amount of diesel in the triple blends is reduced. Experimental results demonstrate that the use of these biofuels allows the replacement of up to 40% of fossil diesel, without compromising the power and BSFC of the engine, and accomplishing optimal cold flow properties and a marked drop in exhaust emissions.

Today, biofuels are indispensable in the implementation of fossil fuels replacement processes. This study evaluates ethyl acetate (EA) as a solvent of two straight vegetable oils (SVOs), castor oil (CO), and sunflower oil (SO), in order to obtain EA/SVO double blends that can be used directly as biofuels, or along with fossil diesel (D), in the current compression-ignition (C.I.) engines. The interest of EA as oxygenated additive lies not only in its low price and renewable character, but also in its very attractive properties such as low kinematic viscosity, reasonable energy density, high oxygen content, and rich cold flow properties. Revelant fuel properties of EA/SVO double and D/EA/SVO triple blends have been object of study including kinematic viscosity, pour point (PP), cloud point (CP), calorific value (CV), and cetane number (CN). The suitability of using these blends as fuels has been tested by running them on a diesel engine electric generator, analyzing their effect on engine power output, fuel consumption, and smoke emissions. Results obtained indicate that the D/EA/SO and D/EA/CO triple blends, composed by up to 24% and 36% EA, respectively, allow a fossil diesel substitution up to 60–80% providing power values very similar to conventional diesel.In addition, in exchange of a slight fuel consumption, a very notable lessening in the emission of pollutants as well as a better behavior at low temperatures, as compared to diesel, are achieved.

The present paper investigates the feasibility of using acetone (ACE) in triple blends with fossil diesel (D) and straight vegetable oils (SVOs) as alternative fuel for diesel engines. In this respect, ACE is selected as an oxygenated additivedue to its favorable propertiesto be mixed with vegetable oils and fossil diesel. In fact, the very low kinematic viscosity allows reduces the high viscosity of SVOs. ACE&rsquo, s oxygen content, low autoignition temperature, and very low cloud point and pour point values highlight its possibilities as an additive in D/ACE/SVO triple blends. Moreover, ACE can be produced through a renewable biotechnological process, an acetone&ndash, butanol&ndash, ethanol (ABE) fermentation from cellulosic biomass. The SVOs tested were castor oil (CO), which is not suitable for human consumption, and sunflower oil (SO), used as a standard reference for waste cooking oil. The viscosity measurement of the ACE/SVO double blend was considered crucial to choose the optimum proportion, which better fulfilled the specifications established by European standard EN 590. Moreover, some of the most significant physicochemical properties of D/ACE/SVO triple blends, such as kinematic viscosity, cloud point, pour point, and calorific value, were determined to assess their suitability as fuels. The blends were evaluated in a conventional diesel generator through the study of the following parameters: engine power, smoke emissions, and fuel consumption. Despite the low calorific value of ACE limits its ratio in the mixtures due to engine knocking problems, the experimental results reveal an excellent performance for the blends containing up to 16-18% of ACE and 22-24% of SVO. These blends produce similar engine power as to fossil diesel, but with slightly higher fuel consumption. Considerable reductions in emissions of air pollutants, as well as excellent cold flow properties are also obtained with these triple blends. In summary, the use of these biofuels could achieve a substitution of fossil diesel up to 40%, independently on the SVO employed.

In this work, the experimental conditions for the transesterification reaction of sunflower oil, over commercial calcium oxide (CaO) as heterogeneous catalysts, have been optimized employing a multi-factorial design based on the response surface methodology (RSM). Hence, the effects of temperature, methanol/oil molar ratio and have been considered. The partial transesterification of sunflower oil produces one mol of monoglyceride (MG) and two moles of fatty acids methyl esters (FAME). This blend constitutes a new type of biofuel called Ecodiesel which can be applicable to diesel engines. This Ecodiesel integrates the glycerol as MG removing by-products and increasing the lubricity of the biofuel. Thus, the reaction conditions, obtained by Response surface methodology (RSM), that promote the highest values of selectivity to Ecodiesel are 65 °C of reaction temperature, 0.7 g of CaO and methanol/oil molar ratio of 5.3. On the other hand, in order to get a biofuel with lower viscosity, 65 °C and 0.7 g of CaO were also employed, although a lower methanol/oil molar ratio of 2 was employed. Operating under these selected experimental conditions, a high conversion value (70 %), a selectivity value to Ecodiesel of 35 % and a viscosity value around 15 cSt can be achieved. The biofuel thus obtained can be used in blends with diesel because in order to accomplish the viscosity limits stablished in the EN 14214. Consequently, this methodology could represent an advance in the technical and economic feasibility in the process of replacing fossil fuels by renewable fuels.

The main objective of this work is to contribute to a gradual replacement process of fossil diesel (D) with biofuels composed by diethyl carbonate (DEC) and either sunflower or castor oil, as straight vegetable oils (SVOs). DEC is a very interesting candidate as an oxygenated additive not only because of its low price and renewable nature, but also its favorable fuel properties, such as very low kinematic viscosity, high cetane number, high oxygen content, rich cold flow properties and good miscibility with fossil diesel and vegetable oils. In this work, the more suitable DEC/SVO biofuels are chosen based on kinematic viscosity, according to the European normative. Additionally, the most relevant physical–chemical properties of (bio)fuels such as density, calorific value, cloud point, pour point and cetane number are determined. The influence of DEC on engine performance and exhaust emissions is analyzed by fueling a conventional Diesel engine with the different D/DEC/SVO triple and DEC/SVO double mixtures. The tests results are also compared with commercial diesel. From the results, it is concluded that Diesel engine fueled with the blends studied exhibits an excellent performance in terms of power output, very similar to diesel. Additionally, the use of these blends can remarkably decrease smoke emissions down to 98%, with respect to fossil diesel. The addition of DEC shows a significant improvement in cold flow properties of fuel mixtures in the exchange of a slightly higher brake specific fuel consumption (BSFC) than diesel. Interestingly, the pure biofuels composed by DEC and SVO allow for a suitable engine operation and achieve the lowest emissions, which means these blends can be successfully employed in current engines without adding fossil diesel, i.e., their use entail a 100% renewability.

This research evaluates the possibility of using straight oils such as castor oil, which is not suitable for food use, and sunflower oil, used as a standard reference for waste cooking oils, in blends with gasoline as second-generation biofuels. To this end, a study of the rheological properties of biofuels obtained from these double blends has been carried out. The aim is to take advantage of the different properties of gasoline, i.e., its low viscosity and its high energy density to obtain blends whose rheological properties allow the substitution of fossil diesel in high extent. The incorporation of fossil diesel to these gasoline/oil mixtures produces diesel/gasoline/oil triple blends, which exhibited the suitable rheological properties to be able to operate in conventional diesel engines. Therefore, the behavior of these blends has been evaluated in a conventional diesel engine, operating as an electricity generator. The triple blends allow the substitution of fossil diesel up to 40% with sunflower oil, and up to 25% with castor oil, with excellent power results achieved for blends in which diesel is substituted up to 40%, and also in fuel consumption at high demand in comparison to conventional fossil diesel. Besides, a significant reduction in the emission of pollutants has also been obtained with these triple blends.

Two inorganic solids have been evaluated as supports of Lipozyme RM IM, a Rhizomucor miehei lipase immobilized on a macroporous anion exchange resin, in order to improve its application as a biocatalyst in the synthesis of biofuels. The experimental conditions have been optimized to get the selective transesterification of sunflower oil, by using a multi-factorial design based on the response surface methodology (RSM). In this way, the effects of several reaction parameters on the selective ethanolysis of triglycerides to produce Ecodiesel, a biodiesel-like biofuel constitute by one mole of monoglyceride (MG) and two moles of fatty acid ethyl ester (FAEE), have been evaluated. Thus, it was obtained that a 6:1 oil/ethanol molar ratio, 0.215 g of biocatalyst supported in silica-gel (0.015 g Lipase/0.2 g silica-gel), 50 µL of 10 N NaOH, together with previous optimized reaction parameters, 35 °C reaction temperature and 120 min of reaction time, gave the best results (conversions around 70%; selectivity around 65%; kinematic viscosities about 9.3 mm2/s) in the reaction studied. Besides, Lipozyme RM IM, supported on silica-gel, biocatalyst exhibited a very good stability, remaining its activity even after 15 cycles.

This research aims to promote the use of second-generation biofuels based mainly on Castor oil, which is not adequate for food use, and Sunflower oil as a standard reference for recycled oils. They have been applied in the production of Ecodiesel, a biofuel that integrates glycerol as monoglyceride, employing sodium methoxide as homogeneous catalyst and ethanol as solvent, but operating in milder conditions than in the synthesis of conventional biodiesel in order to obtain a kinetic control of the selective transesterification. The behavior of biofuels has been evaluated in a conventional diesel engine, operating as an electricity generator. The contamination degree was also evaluated from the opacity values of the generated smokes. The different biofuels here studied have practically no differences in the behavior with respect to the power generated, although a small increase in the fuel consumption was obtained in some cases. However, with the biofuels employed, a significant reduction, up to 40%, in the emission of pollutants is obtained, mainly with the blend diesel/castor oil/alcohol. Besides, it is found that pure Castor oil can be employed directly as biofuel in triple blends diesel/biofuel/alcohol, exhibiting results that are very close to those obtained using biodiesel or Ecodiesel.

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.

In this study, the evaluation of the catalytic behavior of several wild bacterial strains in the 1,3-selective ethanolysis of triglycerides with ethanol to produce a new type of biodiesel (Ecodiesel) that integrates glycerol as monoacylglycerols was carried out. The Ecodiesel production not only avoids the elimination of glycerol, which is largely generated as a by-product in the biodiesel industry, but also results in an increase in the biofuel yield. The wild microbial strain samples were obtained from several lipophilic organisms. In addition to evaluate the enzymatic extracts, the minimum grade of purification of the strains, necessary to obtain similar results to those attained with commercial lipases was studied. This purification treatment included a dialysis followed by a lyophilization process. Such extracts were directly used as biocatalysts in the transesterification reaction of sunflower oil with ethanol, attaining much better results (yield close to 100%) than those obtained with strains which were not submitted to the purification process (yields lower than 10%). Furthermore, the results here obtained are similar to those obtained with commercial lipases but were achieved under mild conditions and lower reaction time (2 h). In addition, the stability of the enzymatic extracts was corroborated by subsequent reactions, showing no loss of activity. Thus, this study brings to light that enzymatic extracts obtained by a very simple purification process can be economically competitive with the conventional biodiesel production methods.

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.

By-products and waste from olive production (agriculture) and the olive oil industry (mills and refineries) are an important environmental issue in Mediterranean areas. Industrial waste and by-products contain highly valuable components that can also be phytotoxic. This article reviews recent research on the valorisation of olive by-products under the bioeconomy strategy. The alternatives are classified according to the 'bioeconomy value pyramid', which prioritises higher value uses over the current energy and compost valorisation. Special attention is paid to the use of these by-products for animal feed that can be improved by reducing the content of saturated fatty acids (SFAs) and increase the polyunsaturated fatty acids amount considered beneficial in response to their use; this makes the food healthier for humans while simultaneously reducing feeding costs and the environmental impact of livestock.

Biodiesel is a biofuel obtained from vegetable oils or animal fats by transesterification with methanol, so that it offers a very promising alternative respect to diesel fuel, since it is able to provide a suitable substitute for the fossil diesel in unmodified internal combustion engines, pure or in blends. However, a major barrier exists to consolidate this conventional biodiesel, as the more suitable biofuel for the replacement of fossil fuel. This drawback is related to the significant amount of glycerol obtained as a byproduct in the transesterification process, which exceeds at least 10% by weight of oil used as raw material. Thus, future widespread use of biofuels depends on developing new process technologies to produce high quality transportation fuels from biologically derived feedstocks, which avoid this key handicap. These new biofuels, like the biodiesel, need to be also compatible with the fossil fuel as well as with existing transportation infrastructures to be economically feasible. In this respect, various alternative methods are currently under development to convert vegetable oils into a high quality diesel fuel, fully compatible with petroleum derived diesel fuel but avoiding the existing glycerol glut. The present review aims to explore the current state of available technologies and recent information in research, production practices and engineering developed to produce alternative high-quality diesel fuel from vegetable oils, by hydrotreating of triglycerides in conventional oil refineries (green diesel) as well as those novel biofuels that integrate glycerol into their composition ( Gliperol®, DMC-Biod® and Ecodiesel®) and the respective technologies for their productions. These very recent biofuels obtained from oils and fats, seek to achieve greater atom efficiency (ideally 100%) because nor glycerol neither other byproduct is generated, avoiding any purification treatment, so that the overall production process of the biofuel is in large extension simplified.

The obtaining of Ecodiesel, a biofuel applicable to diesel engines which keeps the glycerin as monoglyceride (MG), was achieved through a selective ethanolysis process of sunflower oil, by application of Lipozyme RM IM, a Rhizomucor miehei lipase immobilized on macroporous anion exchange resins. This biocatalyst that was already described in the synthesis of conventional biodiesel has also shown its efficiency in the present selective enzymatic process, after optimization of the influence of various reaction parameters. Thus, an adequate activity is obtained that is maintained throughout five successive reuses. Quantitative conversions of triglycerides (TG) with high yields to fatty acid ethyl esters (FAEE) were obtained under mild reaction conditions that correspond to the transformation of TG in a mixture of two moles of FAEE and a mole of MG, thus avoiding the glycerol production. Thus, the selective transesterification reaction of sunflower oil with absolute ethanol can be carried out under standard conditions with oil/ethanol volume ratio 12/3.5 (mL), at constant pH obtained by the addition of 50 μl of aqueous solution of 10 N NaOH, reaction temperature of 40 °C and 40 mg of Lipozyme RM IM. Under these experimental conditions six successive reactions can be efficiently carried out.

A new biodiesel-like biofuel is obtained by the enzymatic ethanolysis reaction of sunflower oil with ethanol, in free solvent media, by using BIOLIPASE-R, a multipurpose alimentary additive from Biocon®-Spain that is a low cost lipase from a strain of Rhizopus oryzae. This biofuel is composed by two parts of fatty acid ethyl esters (FAEE) and one of monoglyceride (MG), which in this form integrates glycerol, through the application of the 1,3-selective lipases. Thus, this process minimizes waste generation and maximizes the efficiency of the process because no residual glycerol is produced. Response surface methodology (RSM) is employed to evaluate the main reaction parameters (reaction temperature, oil/ethanol ratio and pH) on the sunflower oil conversion. Water content and amount of lipase were also previously investigated. Regarding the results, we found that it operates optimally with a water content of the reaction medium of 0.15%, 0.05%–0.1% lipase by weight relative to the weight of oil used, 20 °C, volume ratio (mL/mL) oil/ethanol 12/3.5 and pH 12 (by addition of 50 µL of 10 N NaOH solution). These results have proven a very good efficiency of the biocatalyst in the studied selective process., Grants from the Spanish Ministry of Economy and Competitiveness (Project ENE 2011-27017), Spanish Ministry of Education and Science (Projects CTQ2010-18126 and CTQ2011-28954-C02-02), FEDER funds (Regional Development European Funds) and Junta de Andalucía FQM 0191, PO8-RMN-03515 and P11-TEP-7723 are gratefully acknowledged by the authors. We are also grateful to Biocon®-Spain, for kindly supplying the BIOLIPASE-R., We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI).

In this research have been achieved the optimized experimental conditions to obtain the partial transesterification of sunflower oil with methanol, using CaO as an alkaline heterogeneous catalyst, to produce one mole of monoglicride (MG) and two moles of fatty acids methyl esters (FAME). This blend constitutes a new type of biofuel (Ecodiesel), applicable to diesel engines, which integrates the glycerine as monoglyceride (MG). Thus, similar results to those previously described by enzymatic partial alcoholysis of triglycerides are obtained through the kinetic control of the chemical reaction, so that the same type of biodiesel is obtained by using CaO, instead of the more expensive lipases. In order to obtain an improvement in conversion and kinematic viscosity, the influence on catalytic performance of several kinetic parameters was separately evaluated. It was obtained that a 6:1 molar ratio of methanol to oil, 7 wt% CaO catalyst, 65 °C reaction temperature, 60 min time reaction and 0.3% water content respect to oil, gave the best results. Besides, CaO catalyst maintained sustained activity after being repeatedly used for 20 cycles.

It is currently a much debated topic the potential economic benefits of biomass use for biodiesel production in arid lands. In this respect, the main focus has been directed to determine which different plant species are highly adapted and capable to produce significant amounts of triglycerides to be used in the biodiesel industry under arid conditions. However, very few studies have addressed the technological changes that will be needed to convert triglycerides into biofuels without making a large consumption of scarce water, as it is demanded by current technology. Beside, with current conventional transesterification technology, the production of glycerine as a byproduct is also a serious problem because of the large water requirements needed for its removal from biodiesel, before it can be used in motor engines. The main methods commonly employed to reduce the viscosity of vegetable oil in order to be used in diesel engines are its high dilution with petrodiesel (

By using pig pancreatic lipase (EC 3.1.1.3 or PPL) as a biocatalyst, covalently immobilized on amorphous AlPO 4 support, a new second generation biodiesel was obtained in the transesterification reaction of sunflower oil with ethanol. The resulting biofuel is composed of fatty acid ethyl esters and monoglycerides (FAEE/MG) blended in a 2:1 molar ratio. This novel product, which integrates glycerol as monoacylglycerols (MG) into the biofuels composition, has similar physicochemical properties as conventional biodiesel and also avoids the removal step of the by-product by washing of the biodiesel with water. Immobilization of PPL was achieved by covalent attachment of the ε -amino group of the lysine residues of PPL with the aldehyde groups of p -hydroxybenzaldehyde linked on a hybrid organic-inorganic functionalized AlPO 4 surface. With this procedure, the PPL biocatalyst was strongly fixed to the inorganic support surface (94.3%). Nevertheless, the efficiency of the immobilized enzyme was relatively lower compared to that of the free PPL, but it showed a remarkable stability as well as a great capacity of reutilization (25 reuses) without a significant loss of its initial catalytic activity. Therefore, this enzymatic method allows the production of a biodiesel which integrates the glycerol, allows a more efficient fabrication method and minimizes the waste production as compared to the conventional alkali-catalyzed process.

Biodiesel, a renewable fuel, has great potential in fulfilling an ever-increasing transport fuel demand. The conventional alkaline process for biodiesel production is energy-consuming and generates undesirable by-products. Lipases, due to their catalytic efficiency and specificity, have emerged as a great tool for converting a wide range of feedstock oils to biodiesel. Through enzymatic catalysis, applying lipases (in both free and immobilized form), is viable to producing a cleaner and greener biodiesel under milder conditions, since it produces fewer wastes than the conventional chemical process. Limitations associated with the industrial viability of enzymatic methodology are mainly due to high enzyme production and purification costs, the relatively slower reaction rate, and lipases inactivation caused by methanol and glycerol, which may be overcome by molecular technologies. This chapter summarizes several recent developments that display the current state and perspectives for enzymatic biodiesel production. Also, it indicates the key operational variables that influence lipase activity and stability together with the technological solutions for industrial implementation of the enzymatic-biodiesel production process.

Biodiesel production has received considerable attention in the recent years as biodegradable and non-polluting fuel. In this work, an inexpensive purified 1,3-specific lipase from Thermomyces lanuginosus (Lipopan 50 BG from Novozymes AS, Denmark) was utilised as biocatalyst in an alternative approach to obtain a novel second generation biodiesel-like biofuel. This novel product, which integrates glycerol as monoacylglycerols (MG) into the biofuels composition, can avoid the removal step/s of such byproduct, mandatory in the production of conventional biodiesel. A multi-factorial design and response surface methodology (RSM) were employed to evaluate the effects of several conditions (temperature, molar ratio of ethanol to oil and pH) on the conversion of sunflower oil into a blend of Fatty Acid Ethyl Esters (FAEE), MG and diacylglycerols (DG). The effects of water content and concentration of lipase on conversion into FAEE and MG were also studied. Results obtained indicate that pH, molar ratio of ethanol to oil and water content were significant factors influencing the conversion in the systems under the investigated conditions. Low temperatures (20 °C), high pH values (close to 12), and an oil/ethanol volume ratios of 3.4/1 were found to be the key controlling parameters which provide optimised results after 1 h reaction (conversions around 70%; kinematic viscosities about 8.5 mm2 s−1).

A comprehensive study of critical parameters in the pig pancreatic lipase (PPL) catalysed transesterification of sunflower oil to novel biofuels integrating glycerol into their composition is reported. The influence of oil/alcohol ratio, temperature, quantity of enzyme and water added and pH have been investigated. The enzymatic activity of PPL was found to be greatly influenced by the pH, reaching notable activities at high pH values (10-12), in contrast to other lipases. The addition of small quantities of NaOH (up to 0.1 mL) as coadjuvant in the transesterification reaction enhances the activity of the enzymes. This remarkable behaviour, reported for the first time, may pave the way for the utilisation of these relatively cheap enzymes in large scale commercial biodiesel production. Besides, a novel biofuels containing glycerol into their composition as mono- and diglycerides using PPL as biocatalyst has been developed.

The application of biocatalysts in the transesterification process of triglycerides (TG) allows integrating the glycerol in the form of monoglyceride (MG), sharply increasing the yield and the environmental sustainability of the conventional biodiesel production process. This is known as Ecodiesel. To overcome the inconvenient of the high cost of the currently employed highly purified commercial enzymes, the use of scarcely purified extracts obtained from standard strains of the same species of commercial lipases currently applied in this process is being investigated. Thus, Candida antarctica type B (CALB) was chosen to determine the optimal conditions of culture of this yeast. The standard strain was obtained from the Spanish Type Microbial Cultures Collection (CECT) and has been used to carry out several studies to elucidate its optimum growth conditions. Through a process of lyophilization with prior dialysis of the liquid cultures, the enzymatic extracts were obtained. The different obtained cultures have been applied as biocatalysts in the 1,3-selective transesterification reaction of sunflower oil with ethanol to obtain Ecodiesel (FAEE + MG). Selectivity and reaction yields were obtained by gas chromatography. Acceptable yields are obtained during the reaction time as well as in successive reactions, demonstrating the feasibility of using these CALB enzymatic extracts as biocatalysts

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 AlPO 4/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. © 2014 by the authors., Grants from the Spanish Ministry of Economy and Competitiveness (Project ENE 2011-27017), Spanish Ministry of Education and Science (Projects CTQ2010-18126 and CTQ2011-28954-C02-02), FEDER funds and Junta de Andalucía FQM 0191, PO8-RMN-03515 and P11-TEP-7723 are gratefully acknowledged by the authors. We are also gratefully to Biocon®-Spain, for the kindly supply of the BIOLIPASE-R®. We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI)

This study describes the results obtained in the synthesis of a biofuel that avoids the production of glycerol by applying supported KF as alkaline heterogeneous catalyst, to generate two moles of fatty acid methyl esters and one mole of monoglyceride from one mol of triglyceride. In this respect, the selective transesterification process of sunflower oil with methanol was carried out with KF (10 wt%) supported on three different solids, Al2O3, ZnO and MgO. The standard experimental conditions employed in the heterogeneous selective methanolysis reaction were: 12 mL of sunflower oil, 2.7 mL of methanol, 0.8 g of catalyst, at 65 °C temperature and one hour of reaction time. In all cases 100% conversion was obtained, with high selectivity values, greater than 90%, and quite suitable viscosity values, 4.5-8.5 cSt. In this way, the best catalytic behavior in the first use was obtained by using Al2O3 as support. However, although in the five consecutive reuses all catalysts exhibited a continuous decrease in their catalytic activities; the lower one was for KF catalyst using MgO as support. In summary, these three KF supported catalysts are very suitable to obtain a new biofuel, similar to conventional biodiesel, applicable to diesel engines. © 2014 by the authors., Grants from the Spanish Ministry of Economy and Competitiveness (Project ENE 2011-27017), Spanish Ministry of Education and Science (Projects CTQ2010-18126 and CTQ2011-28954-C02-02), FEDER funds and Junta de Andalucía FQM 0191, PO8-RMN-03515 and P11-TEP-7723 are gratefully acknowledged by the authors. We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI)

Background: Novozym 435, a commercial lipase from Candida antarctica, recombinant, expressed in Aspergillus niger, immobilized on macroporous acrylic resin, has been already described in the obtention of biodiesel. It is here evaluated in the production of a new biofuel that integrates the glycerol as monoglyceride (MG) together with two fatty acid ethyl esters (FAEE) molecules by the application of 1,3-selective lipases in the ethanolysis reaction of sunflower oil. Results: Response surface methodology (RSM) is employed to estimate the effects of main reaction. Optimum conditions for the viscosity, selectivity, and conversion were determined using a multifactorial design of experiments with three factors run by the software Stat Graphics version XV.I. The selected experimental parameters were reaction temperature, oil/ethanol ratio and alkaline environment. On the basis of RSM analysis, the optimum conditions for synthesis were 1/6 oil/EtOH molar ratio, 30°C, and 12.5 μl of NaOH 10 N aqueous solutions, higher stirring than 300 rpm, for 2 h and 0.5 g of biocatalyst. Conclusions: These obtained results have proven a very good efficiency of the biocatalyst in the studied selective process. Furthermore, it was allowed sixteen times the successive reuse of the biocatalyst with good performance

By using pig pancreatic lipase (EC 3.1.1.3 or PPL) as a biocatalyst, covalently immobilized on amorphous AlPO4 support, a new second generation biodiesel was obtained in the transesterification reaction of sunflower oil with ethanol. The resulting biofuel is composed of fatty acid ethyl esters and monoglycerides (FAEE/MG) blended in a 2:1 molar ratio. This novel product, which integrates glycerol as monoacylglycerols (MG) into the biofuels composition, has similar physicochemical properties as conventional biodiesel and also avoids the removal step of the by-product by washing of the biodiesel with water. Immobilization of PPL was achieved by covalent attachment of the ε-amino group of the lysine residues of PPL with the aldehyde groups of p-hydroxybenzaldehyde linked on a hybrid organic-inorganic functionalized AlPO4 surface. With this procedure, the PPL biocatalyst was strongly fixed to the inorganic support surface (94.3%). Nevertheless, the efficiency of the immobilized enzyme was relatively lower compared to that of the free PPL, but it showed a remarkable stability as well as a great capacity of reutilization (25 reuses) without a significant loss of its initial catalytic activity. Therefore, this enzymatic method allows the production of a biodiesel which integrates the glycerol, allows a more efficient fabrication method and minimizes the waste production as compared to the conventional alkali-catalyzed process., Grants from the Spanish Ministry of Economy and Competitiveness (Project ENE 2011-27017), Spanish Ministry of Education and Science (Projects CTQ2010-18126 and CTQ2011-28954-C02-02), FEDER funds and Junta de Andalucía FQM 0191, PO8-RMN-03515 and P11-TEP-7723 are gratefully acknowledged by the authors., We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI).

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., This research was supported by the Spanish Ministry of Economy and Competitiveness (Project ENE 2011-27017), Spanish Ministry of Education and Science (Projects CTQ2010-18126 and CTQ2011-28954-C02-02), FEDER funds and Junta de Andalucía PO8-RMN-03515 and TEP-7723.