Search Results (16)

Biodiesel is a sustainable and promising alternative energy source produced from renewable raw materials using various methods. One effective approach is simultaneous esterification and transesterification, which relies on suitable catalysts that can be either homogeneous or heterogeneous. Homogeneous catalysts (acid or base) offer high activity but are corrosive and difficult to recover, necessitating energy-intensive processes such as aqueous quenching and neutralization, which can lead to soap formation and stable emulsions. By comparison, heterogeneous catalytic systems overcome many of these challenges due to their ease of recovery, reusability, and simplified product separation, which collectively enhance economic viability and environmental sustainability. This review highlights recent progress in the application of zeolite-based solid catalysts for biodiesel synthesis, with particular emphasis on their use in converting waste cooking oil and other low-cost feedstocks, including non-edible oils, non-food biomass sources, algal resources, and genetically engineered microorganisms. Key factors such as catalytic activity, selectivity, catalyst loading, and reusability are discussed, highlighting the advantages of zeolites due to their unique crystal structure, high thermal stability, and ease of product recovery. Overall, this review underscores the challenges and opportunities in zeolite-based catalysis to provide a comprehensive understanding of its potential to enhance the efficiency and scalability of biodiesel production. Full article

The reactive double dividing-wall distillation column (R-DDWDC) can simultaneously integrate and effectively coordinate reaction–separation coupling (RSC) and separation–separation coupling (SSC), thereby offering greater technical advantages and development potential than the conventional reactive distillation column and the reactive single dividing-wall distillation column. However, the application of two dividing walls and the introduction of external recycle flows inevitably lead to multiple candidate configurations of the R-DDWDC, and this significantly adds complexity and computational burden to its synthesis and design. To address the issue, we propose an effective methodology for developing the R-DDWDC, which involves a two-step strategy: the first step is to determine the configuration of external recycle flows by searching for the RSC from non-sharp separation to sharp separation of reaction mixtures, and the second step is to adjust the arrangement of the dividing walls to intensify the SSC. The former serves to provide the greatest flexibility for the inclusion of the SSC, and the latter helps to achieve full coordination with the RSC, thereby allowing the determination of the optimal design with low complexity and computational intensity. The methodology is fundamentally a conceptual design and structural optimization framework that can be implemented using either generic process simulation platforms or custom computational programs. Four representative examples, including the metathesis of 2-pentene; the acetalization of ethanol with butanal; the transesterification of propylene glycol monomethyl ether with methyl acetate; and the esterification of lactic acid with methanol, are selected to assess the derived procedure, and the obtained results confirm its simplicity and efficiency. Because the procedure proposed in this work is independent of the number of components contained in reaction mixtures and their relative volatility rankings, it can be regarded as a general methodology for developing other complicated reactive dividing-wall distillation columns. Full article

Environmental and economic concerns due to the increasing use of fossil-based chemicals, especially fuel, may be alleviated by production of renewable fuels based on plant biomass, in particular, waste. Multistep cascades of enzymatic reactions are being increasingly sought to enhance the effectiveness of sustainable, environment-friendly processes. The biochemical transformation of lignocellulosic biomass and oils into fatty acid esters (“biodiesel”) involves biomass pretreatment, followed by polysaccharide hydrolysis and sugar fermentation to alcohol, either sequentially or simultaneously. Subsequent trans-esterification with waste or non-food-based oils is usually carried out in an organic solvent. Biocatalysis in aqueous emulsion offers significant advantages. This study presents a novel “one-pot” emulsion-based process for transforming unmodified cellulose and castor oil into biodiesel via hybridized yeasts with cellulose-coated micro-particles incorporating cellulolytic enzymes and lipases. The resultant consolidated bioprocess of saccharification, fermentation, and transesterification (cSFT) promotes effective substrate channeling and can potentially serve as a model for emulsion-based “one-pot” transformations of cellulose into valuable chemicals. Full article

The production of biodiesel via simultaneous esterification and transesterification reactions of residual fats such as palm oleins, with variable TG and FFA composition, using methanol and methane sulfonic acid (MSA) or an acid carbon-based structured catalyst (SO₃H-C) as homogeneous and heterogeneous catalysts respectively, has been investigated. The influence of various parameters, such as methanol to oil molar ratio, operating temperature, amount of catalyst, or nature and composition of the raw materials on the fatty acid methyl esters (FAME) yield was studied. It was determined that increasing the methanol to oil molar ratio resulted in an increase in the conversion of TG and FFA and a higher FAME yield; besides, reaction temperature has a strong effect. The best conditions tested to obtain the highest FAME yield (99.2%) was a methanol to oil molar ratio of 12:1, 120 °C (12 bar), a reaction time of at least 1 h, and 3% MSA as a homogeneous catalyst. The work demonstrated that an acidic solid catalyst, SO₃H-C, homemade prepared, could be used as a heterogeneous catalyst in the simultaneous process under the optimized reaction conditions, achieving a complete esterification conversion with some limitations with respect to the transesterification reaction and a FAME yield close to 90.5%. Full article

The main goal of this work is to evaluate the ability of sulfonated carbon nanoparticles (SCNs) to induce photothermal catalysis of the biodiesel synthesis reaction (transesterification of natural triglycerides (TGs) with alcohols). Carbon nanoparticles (CNs) are produced by the carbonization of cross-linked resin nanoparticles (RNs). The RNs are produced by condensation of a phenol (resorcinol or natural tannin) with formaldehyde under ammonia catalysis (Stober method). The method produces nanoparticles, which are carbonized into carbon nanoparticles (CNs). The illumination of CNs increases the temperature proportionally (linear) to the nanoparticle concentration and exposure time (with saturation). Solid acid catalysts are made by heating in concentrated sulfuric acid (SEAr sulfonation). The application of either light or a catalyst (SCNs) (at 25 °C) induced low conversions (<10%) for the esterification reaction of acetic acid with bioethanol. In contrast, the illumination of the reaction medium containing SCNs induced high conversions (>75%). In the case of biodiesel synthesis (transesterification of sunflower oil with bioethanol), conversions greater than 40% were observed only when light and the catalyst (SCNs) were applied simultaneously. Therefore, it is possible to use sulfonated carbon nanoparticles as photothermally activated catalysts for Fischer esterification and triglyceride transesterification (biodiesel synthesis). Full article

Medium- and long-chain triacylglycerol (MLCT), as a novel functional lipid, is valuable due to its special nutritional properties. Its low content in natural resources and inefficient synthesis during preparation have limited its practical applications. In this study, we developed an effective Pickering emulsion interfacial catalysis system (PE system) for the enzymatic synthesis of MLCT by trans-esterification. Lipase NS 40086 served simultaneously as a catalyst and a solid emulsifier to stabilize the Pickering emulsion. Benefitting from the sufficient oil–water interface, the obtained PE system exhibited outstanding catalytic efficiency, achieving 77.5% of MLCT content within 30 min, 26% higher than that of a water-free system. The K_m value (0.259 mM) and activation energy (14.45 kJ mol⁻¹) were 6.8-fold and 1.6-fold lower than those of the water-free system, respectively. The kinetic parameters as well as the molecular dynamics simulation and the tunnel analysis implied that the oil–water interface enhanced the binding between substrate and lipase and thus boosted catalytic efficiency. The conformational changes in the lipase were further explored by FT-IR. This method could give a novel strategy for enhancing lipase activity and the design of efficient catalytic systems to produce added-value lipids. This work will open a new methodology for the enzymatic synthesis of structured lipids. Full article

The activity of MOF-5-based solids has been exploited in the simultaneous transesterification and esterification of acid vegetable oils. For this purpose, three different types of MOF-5 have been synthesized and characterized, and then tested in the above-mentioned reactions. It has been demonstrated that the “regular MOF-5” was a suitable catalyst for biodiesel synthesis from waste oil also, rich in FFA (Free Fatty Acids). Moreover, to identify the true structure that acts in the reactions and possible structural modifications due to the presence of alcohols, proper studies have been performed. The results have evidenced a distortion of the regular structure of MOF-5 due to the breakage of some zinc bonds between the cluster and organic framework. Full article

Waste resources are an attractive option for economical the production of biodiesel; however, oil derived from waste resource contains free fatty acids (FFA). The concentration of FFAs must be reduced to below 1 wt.% before it can be converted to biodiesel using transesterification. FFAs are converted to fatty acid methyl esters (FAMEs) using acid catalysis, which is the rate-limiting reaction (~4000 times slower than transesterification), with a low conversion as well, in the over biodiesel production process. The study is focused on synthesizing and using a bifunctional catalyst (7% Sr/ZrO₂) to carry out esterification and transesterification simultaneously to convert waste cooking oil (WCO) into biodiesel using microbubble-mediated mass transfer technology. The results reveal that a higher conversion of 85% is achieved in 20 min using 7% Sr/ZrO₂ for biodiesel production. A comprehensive kinetic model is developed for the conversion of WCO in the presence of a 7% Sr/ZrO₂ catalyst. The model indicates that the current reaction is pseudo-first-order, controlled by the vapor–liquid interface, which also indicates the complex role of microbubble interfaces due to the presence of the bifunctional catalyst. The catalyst could be recycled seven times, indicating its high stability during biodiesel production. The heterogeneous bifunctional catalyst is integrated with microbubble-mediated mass transfer technology for the first time. The results are unprecedented; furthermore, this study might be the first to use microbubble interfaces to “host” bifunctional metallic catalysts. The resulting one-step process of esterification and transesterification makes the process less energy-intensive and more cost-efficient, while also reducing process complexity. Full article

Liquid Eversa was evaluated in hydrolysis of acylglycerols from soybean oil deodorizer distillate (SODD), as well as simultaneous esterification/transesterification of SODD with low-to-high free fatty acids (FFAs) content using ethanol as acyl acceptor. Hydrolysis of SODD at mild temperature (37 °C) and without pH control (water:SODD mass ratio of 4:1) increased its FFAs content from 17.2 wt.% to 72.5 wt.% after 48 h reaction. A cold saponification of SODD allowed a saponification phase (SODD-SP) to be recovered with 93 wt.% saponification index and 2.25 wt.% FFAs content, which was used to find the experimental conditions for simultaneous esterification/transesterification reactions by experimental design. Temperature of 35 °C, enzyme concentration of 8.36 wt.%, and molar ratio of 3.64:1 (ethanol:SODD-SP) were found as the best conditions for fatty acid ethyl esters (FAEEs) production from SODD-SP (86.56 wt.% ester yield after 23 h reaction). Under the same reaction conditions, crude SODD (17.2 wt.% FFAs) and hydrolyzed SODD (72.5 wt.% FFAs) yielded products containing around 80 wt.% FAEEs. Caustic treatment could increase the ester content to around 90 wt.% and reduce the FFAs content to less than 1 wt.%. Our results show the good performance of liquid Eversa in aqueous (hydrolysis reactions) and organic (esterification/transesterification reactions) media. Full article

This research aims at developing an efficient and reusable catalyst to improve biodiesel production processes. To achieve this, a vanadium-substituted polyoxometalate (POM) acid, namely H₆PV₃MoW₈O₄₀, was firstly prepared, and then the heterogenzation of the homogeneous Keggin-type heteropoly acids was performed by the partial proton substitution by monovalent large cesium cations with the formation of solid Cs₂H₄PV₃MoW₈O₄₀ catalysts. Several techniques, such as X-ray diffractometer, Fourier transform infrared, coupled plasma–atomic emission spectrometry, Diffuse reflectance ultraviolet–visible spectrum, thermal gravimetric analysis and N₂ adsorption–desorption techniques, were employed to characterize the as-prepared solid catalyst. The solid acid catalyst had the capacity to catalyze both the transesterification of soybean oil and esterification of free fatty acids (FFAs) simultaneously, providing an efficient production process for the production of biodiesel from low-quality oils. Under the operational conditions of a methanol/oil molar ratio of 30:1, a catalyst dosage of 5 wt.%, a reaction temperature of 140 °C, and a reaction duration of 8 h, an oil conversion of 92.2% was attained with the total FFA transformation to biodiesel. Furthermore, the catalyst could be reutilized for several cycles with no significant drop in its activity, thus having great potential for application with a bright perspective in the production of biodiesel, especially from low-quality oil feedstocks. Full article

The main aim of this work was to investigate the suitability of a KI/KIO₃ impregnated hydroxyapatite (HAP) catalyst derived from natural phosphate rocks for biodiesel production. This study evaluated the effect of impregnation concentrations (1–6% w/w) on the catalyst performance in biodiesel production. The biodiesel was produced from waste cooking oil (WCO) under simultaneous esterification-transesterification reactions at 60 °C for 6 h. The results showed that the biodiesel yield increased by increasing impregnation concentration and the maximum yield (91.787%) was achieved at an impregnation concentration of 5% w/w. The KI/HAP catalyst showed better performance (91.78% biodiesel yield, 59.1% FAME yield and surface area of 13.513 m²/g) as compared to the KIO₃/HAP catalyst (90.07% biodiesel yield, 55.0% FAME yield and surface area of 10.651 m²/g). Full article

Bifunctional solid catalysts facilitate the esterification of free fatty acids (FFA) into alkyl esters alongside the transesterification reaction, which allows for the use of waste vegetable oils with high water and FFA contents for biodiesel production. This makes the process economically viable and greener, as the waste fats and oils are readily available. The concurrent esterification and transesterification of waste palm oil (WPO) and waste sunflower oil (WSO) with methanol was investigated in the presence of calcium oxide on alumina catalyst in a conventional batch process. The catalyst characterization showed the existence of calcium oxide aluminates (calcined at 750 °C), which exhibited crystalline phases with porous/spongy-like particles. The high concentration of CaO in CaO/Al₂O₃ was a favorable support material in the heterogeneously-catalyzed transesterification reactions. The optimum catalyst parameters for the production of fatty acid methyl esters (FAMEs) were observed at 65 °C for 4 h with a methanol-to-oil ratio of 9:1, 60% (waste palm oil, or WPO) and 80% (waste sunflower oil, or WSO), CaO/Al₂O₃ (% wt/wt) catalyst ratio as well as 4% CaO/Al₂O₃ concentration (% wt.) for WSO and WPO. The simultaneous esterification/transesterification reactions at optimum conditions on WPO and WSO led to high yield of FAMEs of 89, 61 and 55% for WPO and 54, 75 and 98% for WSO at catalyst ratios (wt %) of 60, 70 and 80% respectively. The use of bifunctional heterogeneous catalyst (CaO/Al₂O₃) with waste vegetable oil can result in high performance and the upscaling of biodiesel production. Full article

Non-edible vegetable oils are characterized by high contents of free fatty acids (FFAs) that prevent from using the conventional basic catalysts for the production of biodiesel. In this work, solid acid catalysts are used for the simultaneous esterification and transesterification with methanol of the FFAs and triglycerides contained in sunflower oil acidified with oleic acid. Molybdenum oxide (MoO₃), which has been seldom considered as a catalyst for the production of biodiesel, was used in bulk and alumina-supported forms. Results showed that bulk MoO₃ is very active for both transesterification and esterification reactions, but it suffered from severe molybdenum leaching in the reaction medium. When supported on Al₂O₃, the MoO₃ performance improved in terms of active phase utilization and stability though molybdenum leaching remained significant. The improvement of catalytic performance was ascribed to the establishment of MoO₃-Al₂O₃ interactions that favored the anchorage of molybdenum to the support and the formation of new strong acidic centers, although this effect was offset by a decrease of specific surface area. It is concluded that the development of stable catalysts based on MoO₃ offers an attractive route for the valorization of oils with high FFAs content. Full article

In this work, the simultaneous transesterification and esterification reactions of olive pomace oil with methanol catalyzed by zinc stearate were studied. This catalyst is a crystalline solid at room temperature, but it is soluble in the reaction medium at reaction temperature. Zinc stearate has surfactant properties that cause the formation of an emulsion in the reaction system. The stability of the emulsion formed in the oil–methanol–catalyst system was compared to that in the FAME (fatty acid methyl esters)–methanol–catalyst system. It was observed that the emulsion formed in the presence of high amounts of FAME is much more unstable, which makes the catalyst easy to separate from the reaction products. The kinetics of esterification and transesterification were also studied. All the kinetic and equilibrium constants were determined with a complete model, considering the three stepwise reactions corresponding to the transesterification of triglycerides and the esterification of free fatty acids. The parameters obtained were used to model the operating conditions that would allow obtaining biodiesel that meets the quality standards. Full article

A new protocol for biodiesel production is proposed, based on a binary ZnO/TBAI (TBAI = tetrabutylammonium iodide) catalytic system. Zinc oxide acts as a heterogeneous, bifunctional Lewis acid/base catalyst, while TBAI plays the role of phase transfer agent. Being composed by the bulk form powders, the whole catalyst system proved to be easy to use, without requiring nano-structuration or tedious and costly preparation or pre-activation procedures. In addition, due to the amphoteric properties of ZnO, the catalyst can simultaneously promote transesterification and esterification processes, thus becoming applicable to common vegetable oils (e.g., soybean, jatropha, linseed, etc.) and animal fats (lard and fish oil), but also to waste lipids such as cooking oils (WCOs), highly acidic lipids from oil industry processing, and lipid fractions of municipal sewage sludge. Reusability of the catalyst system together with kinetic (Ea) and thermodynamic parameters of activation (ΔG^‡ and ΔH^‡) are also studied for transesterification reaction. Full article