Search Results (24)

The production of biodiesel from microalgae presents a sustainable and renewable solution to the growing global energy demands, with catalysts playing a critical role in optimizing the transesterification process. This study examines the emerging catalysts and innovative techniques utilized in converting microalgal lipids into fatty acid methyl esters, emphasizing their impact on reaction efficiency, yield, and environmental sustainability. Sulfuric acid demonstrates excellent performance in in situ transesterification, while NaOH/zeolite achieves high biodiesel yields using ultrasound- and microwave-assisted methods. Metal oxides such as CuO, NiO, and MgO supported on zeolite, as well as ZnAl-layered double hydroxides (LDHs), further enhance reaction performance through their high activity and stability. Enzymatic catalysts, particularly immobilized lipases, provide a more environmentally friendly option, offering high yields (>90%) and the ability to operate under mild conditions. However, their high cost and limited reusability pose significant challenges. Ionic liquid catalysts, such as tetrabutylphosphonium carboxylate, streamline the process by eliminating the need for drying and lipid extraction, achieving yields as high as 98% from wet biomass. The key novelty of this work lies in its detailed focus on the use of ionic liquids and nanocatalysts in microalgae-based biodiesel production, which are often underrepresented in previous reviews that primarily discuss homogeneous and heterogeneous catalysts. Full article

Mixed oxides were obtained via calcination at 550 °C from layered double hydroxides (LDHs), which were synthesized in a previous study via co-precipitation and co-precipitation followed by hydrothermal treatment using aluminum residues as the source of this element. After characterization, these oxides (Mg-Al-_LDH-CP and Mg-Al-_LDH-H, named according to the synthesis methods of the precursor LDHs) were applied as heterogeneous catalysts in the methyl transesterification of ethyl acetate (EA). The formation of mixed oxides was confirmed by the absence of basal peaks associated with the layered LDH structure in the XRD analysis, due to calcination. Further characterization revealed that Mg-Al-_LDH-CP exhibited the highest number of acidic sites, while Mg-Al-_LDH-H had the highest number of basic sites. The transesterification activity was evaluated in the reaction between ethyl acetate (EA) and methanol (MeOH). The best result, obtained under a molar ratio of 1:5:0.005 (EA:MeOH:catalyst) at 120 °C, was a 63% conversion after 360 min of reaction for the Mg-Al-_LDH-CP catalyst, which had a higher number of acidic sites and fewer basic sites. Additionally, the catalysts demonstrated robustness, maintaining catalytic activity over four cycles without a significant decrease in performance. These results indicate the feasibility of using mixed oxides derived from LDH, synthesized from aluminum residues, as heterogeneous catalysts in transesterification reactions, highlighting their potential for advancing more sustainable catalyst development. Full article

Biodiesel and biolubricants play strategic roles in green technologies, as they can be produced in biorefineries. The design of industrial facilities is essential to assess the industrial implementation of these processes, with few studies about this subject in the literature. The aim of this work was to produce biodiesel and a biolubricant from waste cooking oil through double transesterification with methanol and trimethylolpropane, obtaining high conversion values (>97 and 98%, respectively). The biolubricant (characterized according to the UNE-14214 standard) had a density of 951 kg·m⁻³, a viscosity of 127 cSt (at 40 °C), an acidity value of 0.43 mgKOH·g⁻¹, flash and combustion points of 225 and 232 °C, and an oxidation stability of 6 h through the Rancimat method. Also, a kinetic study was carried out (at temperatures ranging from 80 to 140 °C and with catalyst concentrations from 0.3 to 0.9% w/w and working pressures from 210 to 760 mmHg) to establish the main kinetic parameters, obtaining a second-order reaction and an activation energy of 17.8 kJ·mol⁻¹. Finally, a conceptual design was included, considering the main components of the facility. Thus, the projected plant worked in a discontinuous regime (producing 2 cubic meters per day), pointing out the feasibility of this plant at an industrial scale. Full article

In the current environmental scenario, the proposal of alternatives for petroleum-based products has considerably increased, with the aim of looking for bioproducts with interesting properties such as biodegradability, sustainability and efficiency, among others. In this sense, the role of biolubricants is promising, offering a wide range of possibilities through different methods and operating conditions. Specifically, double transesterification could be a suitable process in a biorefinery context. The aim of this work was to produce a biolubricant through double transesterification with methanol and neopentyl glycol (NPG) under different reaction conditions by using homogeneous catalysis (sodium methoxide). Different catalyst concentrations, among other changes in reaction conditions (temperature ranging between 100 and 140 °C and NPG/FAME ratios between 0.5 and 2), were used, obtaining high conversion values (96%) and a final product with a high viscosity (20.7 cSt), which allows for its use as engine oil (SAE 5W). In conclusion, biodiesel and biolubricant production was feasible through homogeneous catalysis, proving the feasibility of this process at the laboratory scale. Further studies, including the use of different heterogeneous catalysts, as well as the implementation of this process at a semi-industrial scale, are recommended. Full article

The use of biolubricants as an alternative to petroleum-based products has played an important role in the last decade. Due to the encouragement of global policies, which mainly support green chemistry and circular economy, there has been an increasing interest in bio-based products, including biolubricants, from scientific and industrial points of view. Their raw materials, production, and characteristics might vary, as biolubricants present different applications for a wide range of practical uses, making this field a continuously changing subject of study by researchers. The aim of this work was to study biolubricant production from vegetable oil crops from a bio-refinery perspective, paying attention to the main raw materials used, the corresponding production methods (with a special focus on double transesterification), the role of catalysts and some techno-economic studies. Thus, the main factors affecting quality parameters such as viscosity or oxidative stability have been covered, including catalyst addition, reaction temperature, or the use of raw materials, reagents, or additives were also analyzed. In conclusion, the search for suitable raw materials, the use of heterogeneous catalysts to improve the effectiveness and efficiency of the process, and the optimization of chemical conditions seem to be the most interesting research lines according to the literature. Full article

The increase in the price of crude oil, the environmental impact, or the depletion of fossil resources has increased the need for bio-based alternatives. This has led to the search for renewable, biodegradable, and environmentally friendly raw materials to obtain lubricants that meet these characteristics. This review deals with the state of the art of biolubricants along with their most common raw materials and molecular structures, processes of chemical modification of bio-oils, as well as the relationship between their structural features and physicochemical/tribological properties. This review concludes that the production of fatty acid alkyl esters from vegetable oils is the most promising chemical route to produce a wide range of biolubricants through double transesterification reactions. It also highlights the need to explore this route for the production of microalgae-derived biolubricants due to its environmental benefits during cultivation and production processes. Full article

Self-healing materials offer a potential solution to the problem of damage to fibre-reinforced plastics (FRPs) by allowing for the in-service repair of composite materials at a lower cost, in less time, and with improved mechanical properties compared to traditional repair methods. This study investigates for the first time the use of poly(methyl methacrylate) (PMMA) as a self-healing agent in FRPs and evaluates its effectiveness both when blended with the matrix and when applied as a coating to carbon fibres. The self-healing properties of the material are evaluated using double cantilever beam (DCB) tests for up to three healing cycles. The blending strategy does not impart a healing capacity to the FRP due to its discrete and confined morphology; meanwhile, coating the fibres with the PMMA results in healing efficiencies of up to 53% in terms of fracture toughness recovery. This efficiency remains constant, with a slight decrease over three subsequent healing cycles. It has been demonstrated that spray coating is a simple and scalable method of incorporating a thermoplastic agent into an FRP. This study also compares the healing efficiency of specimens with and without a transesterification catalyst and finds that the catalyst does not increase the healing efficiency, but it does improve the interlaminar properties of the material. Full article

The use of biolubricants as a replacement for petroleum-based products is becoming more and more important, due to the current global energy and crude oil scenario. Thus, the production of biolubricants (which could take place in biorefineries) should be as efficient as possible, obtaining high-quality products with suitable viscosity or oxidation stability values to compete with oil refineries. One of the ways to produce biolubricants is through double transesterification from vegetable oils, where the role of catalysts (usually homogeneous) is vital, as they can improve the yield of the process. However, they should be removed after the chemical reaction, which is difficult once the biolubricant is obtained. Otherwise, they could act as catalysts during oxidation, contributing to a further decrease in oxidation stability and provoking significant changes. To avoid this, antioxidant addition could be an interesting choice. The aim of this work was to assess TBHQ addition in frying oil biolubricants, monitoring properties such as viscosity, acid number, absorbance or TBHQ content (through voltammetry) during oxidation. TBHQ addition (2114 mg·L⁻¹) kept the main quality parameters during oxidation compared to control samples. In contrast, TBHQ content decreased during oxidation (to 160 mg·L⁻¹), which proved its antioxidant effect. Full article

Lipase-catalyzed transesterification is prevalent in industrial production and is an effective alternative to chemical catalysis. However, due to lipases’ unique structure, the reaction requires a biphasic system, which suffers from a low reaction efficiency caused by a limited interfacial area. The use of emulsion particles was found to be an effective way to increase the surface area and activity. This research focuses on cellulose as a natural surfactant for oil-in-water emulsions and evaluates the ability of lipase, introduced into the emulsion’s aqueous phase, to integrate with the emulsion microparticles and catalyze the transesterification reaction of high molecular weight esters dissolved in the particles’ cores. Cellulose-coated emulsion particles’ morphology was investigated by light, fluorescence and cryogenic scanning electron microscopy, which reveal the complex emulsion structure. Lipase activity was evaluated by measuring the hydrolysis of emulsified p-nitrophenyl dodecanoate and by the transesterification of emulsified methyl laurate and oleyl alcohol dissolved in decane. Both experiments demonstrated that lipase introduced in the aqueous medium can penetrate the emulsion particles, localize at the inner oil core interface and perform effective catalysis. Furthermore, in this system, lipase successfully catalyzed a transesterification reaction rather than hydrolysis, despite the dominant presence of water. Full article

One of the indispensable applications of lipases in modification of oils and fats is the possibility to tailor the fatty acid content of triacylglycerols (TAGs), to meet specific requirements from various applications in food, nutrition, and cosmetic industries. Oleic acid (C18:1) and stearic acid (C18:0) are two common long fatty acids in the side chain of triglycerides in plant fats and oils that have similar chemical composition and structures, except for an unsaturated bond between C9 and C10 in oleic acid. Two lipases from Rhizomucor miehei (RML) and Rhizopus oryzae (ROL), show activity in reactions involving oleate and stearate, and share high sequence and structural identity. In this research, the preference for one of these two similar fatty acid side chains was investigated for the two lipases and was related to the respective enzyme structure. From transesterification reactions with 1:1 (molar ratio) mixed ethyl stearate (ES) and ethyl oleate (EO), both RML and ROL showed a higher activity towards EO than ES, but RML showed around 10% higher preference for ES compared with ROL. In silico results showed that stearate has a less stable interaction with the substrate binding crevice in both RML and ROL and higher tendency to freely move out of the substrate binding region, compared with oleate whose structure is more rigid due to the existence of the double bond. However, Trp88 from RML which is an Ala at the identical position in ROL shows a significant stabilization effect in the substrate interaction in RML, especially with stearate as a ligand. Full article

Biodiesel obtained through the transesterification in methanol of vegetable oils, such as soybean oil (SO) and waste cooking oil (WCO), cannot be used as a biofuel for automotive applications due to the presence of polyunsaturated fatty esters, which have a detrimental effect on oxidation stability (OS). A method of upgrading this material is the catalytic partial hydrogenation of the fatty acid methyl ester (FAME) mixture. The target molecule of the partial hydrogenation reaction is monounsaturated methyl oleate (C18:1), which represents a good compromise between OS and the cold filter plugging point (CFPP) value, which becomes too high if the biodiesel consists of unsaturated fatty esters only. In the present work, polymer-supported palladium (Pd-pol) and nickel (Ni-pol) nanoparticles were separately tested as catalysts for upgrading SO and WCO biodiesels under mild conditions (room temperature for Pd-pol and T = 100 °C for Ni-pol) using dihydrogen (p = 10 bar) as the reductant. Both catalysts were obtained through co-polymerization of the metal containing monomer M(AAEMA)₂ (M = Pd, Ni; AEEMA⁻ = deprotonated form of 2-(acetoacetoxy)ethyl methacrylate)) with co-monomers (ethyl methacrylate for Pd and N,N-dimethylacrilamide for Ni) and cross-linkers (ethylene glycol dimethacrylate for Pd and N,N’-methylene bis-acrylamide for Ni), followed by reduction. The Pd-pol system became very active in the hydrogenation of C=C double bonds, but poorly selective towards the desirable C18:1 product. The Ni-pol catalyst was less active than Pd-pol, but very selective towards the mono-unsaturated product. Recyclability tests demonstrated that the Ni-based system retained its activity and selectivity with both the SO and WCO substrates for at least five subsequent runs, thus representing an opportunity for waste biomass valorization. Full article

NiAl layered double hydroxides (LDHs) are promising bifunctional catalysts comprising tunable redox and Lewis acidic sites. However, most studies of NiAl LDH employ alkali hydroxide carbonate precipitants which may contaminate the final LDH catalyst and leach into reaction media. Here, we report an alkali-free route to prepare Ni_xAl LDHs with a composition range x = 1.7 to 4.1 using (NH₄)₂CO₃ and NH₄OH as precipitants. Activation of LDHs by calcination–rehydration protocols reveal Ni_xAl LDHs can be reconstructed under mild hydrothermal treatment (110 °C for 12 h), with the degree of reconstruction increasing with Ni content. Catalyst activity for tributyrin transesterification with methanol was found to increase with Ni content and corresponding base site loadings; TOFs also increased, suggesting that base sites in the reconstructed LDH are more effective for transesterification. Hydrothermally reconstructed Ni_4.1Al LDH was active for the transesterification of C₄–C₁₂ triglycerides with methanol and was stable towards leaching during transesterification. Full article

Novel and biodegradable acrylic acid-grafted poly(1,4-butylene adipate-co-terephthalate)/organically modified layered double hydroxide (g-PBAT/m-LDH) nanocomposites were synthesized through the polycondensation and transesterification process, with the covalent linkages between the polymer and the inorganic materials. X-ray diffraction and transmission electron microscopy were used to characterize the structure and morphology of the g-PBAT/m-LDH nanocomposites. The experimental results show that the m-LDH was exfoliated and widely distributed in the g-PBAT matrix. The addition of m-LDH into the g-PBAT extensively improved the storage modulus at −90 °C, when compared to that of the pure g-PBAT matrix. The effects of the minor comonomer of the butylene terephthalate (BT) unit and the addition of m-LDH on the crystallization behavior, and the polymorphic crystals of the g-PBAT at numerous crystallization temperatures, were examined, using a differential scanning calorimeter (DSC). The data indicate that the minor comonomer of the BT unit into g-PBAT can significantly change the starting formation temperatures of the α-form and ꞵ-form crystals, while a change in the starting formation temperatures of the α-form and ꞵ-form crystals using the addition of m-LDH into g-PBAT is not evident. Full article

Biodiesel, which is composed of mono-alkyl esters of long carbon-chained fatty acids, is used as an alternative fuel to petro-diesel. The water content of the reactant mixture of feedstock oil influences the extent of transesterification and thus the fuel characteristics. Lower water content in feedstock oil is generally suggested for successful transesterification. This experimental study removed water from the reactant mixture of feedstock palm oil and methanol during transesterification using various systems composed of either electrodes or molecular sieves with rotary vibration. The effect of input electrical energy, number of electrodes, vibration modes, and operating time on the amount of water removed from the reactant mixture and the fuel properties of the final biodiesel product were analyzed and compared with those achieved using molecular sieves. The results show that the biodiesel—after water was removed during transesterification—appeared to have increased kinematic viscosity, cetane index, distillation temperature, and acid value, while the heating value, flash point, ignition point, and water content decreased with an increase in the input electrical energy of the electrodes responsible for electrolyzing water away. Electrolysis by the double-pair electrodes was more effective at reducing acid value and water content than that performed by the single-pair electrodes under the same input electrical energy. The biodiesel was found to have the lowest water content (0.0304 wt.%) and the highest water-removal rate (0.011 wt.%) when water was removed during transesterification by the double-pair electrodes with an input electrical energy of 9 J/(g palm oil). The water-removal rate of the rotary-vibrating molecular sieves was 11.24 times that of the single-pair electrodes. The biodiesel was found to have increased kinematic viscosity with higher input electrical energy, reaching 5.15 mm²/s when the double-pair electrodes with an input electrical energy of 11 J/(g palm oil) were used. Longer carbon-chained fatty acids, ranging from C20 to C24, amounted to 0.74 wt.% of the biodiesel produced using the double-pair electrodes, which was greater than that seen for the single-pair electrodes. However, the molecular sieve method consumed more energy than the double-pair electrodes did to remove the same amount of water from the palm oil reactant mixture via transesterification. Full article

Vegetable oils and their derivatives have great potential as renewable and sustainable raw materials for the production of polyurethanes and bio-based polyols. For industry an important process is their modification. Chemical reactions that are carried out on vegetable oils and their derivatives are: transesterification, auto-oxidation, hydrogenation, epoxidation, hydroxylation, acrylation, isocyanation and others. One of the modifications are reactions performed on double bonds and/or carbonyl moieties of plants oils and their derivatives. These reactions result in products that are actively used as binders in coating materials due to their unique structural properties. In this manuscript, we describe important technological methods for the introduction of hydroxyl groups: opening of oxirane rings by nucleophilic reagents such as: water, alcohols, glycols, amino alcohols, carboxylic acids; direct hydroxylation of unsaturated bonds with carboxylic peracids in combination with hydrolysis of carboxyl groups and hydration; hydroformylation of unsaturated bonds with subsequent hydrogenation and alkoxylation; and ozonolysis of unsaturated bonds in combination with subsequent hydrogenation and alkoxylation. Full article