Solvent assisted decomposition of the tetrahedral intermediate of the transesterification reaction to biodiesel production. A density functional study

B3LYP/6-31 + G(d) calculations were employed to investigate the mechanism of the transesterification reaction between a model monoglyceride and the methoxide and ethoxide anions. The gas-phase results reveal that both reactions have essentially the same activation energy (5.9 kcal mol⁻¹) for decomposition of the key tetrahedral intermediate. Solvent effects were included by means of both microsolvation and the polarizable continuum solvation model CPCM. Both solvent approaches reduce the activation energy, however, only the microsolvation model is able to introduce some differentiation between methanol and ethanol, yielding a lower activation energy for decomposition of the tetrahedral intermediate in the reaction with methanol (1.1 kcal mol⁻¹) than for the corresponding reaction with ethanol (2.8 kcal mol⁻¹), in line with experimental evidences. Analysis of the individual energy components within the CPCM approach reveals that electrostatic interactions are the main contribution to stabilization of the transition state.     

Optimization of the production of biodiesel from soybean oil by ultrasound assisted methanolysis

This paper evaluates and optimizes the production of biodiesel from soybean oil and methanol using sodium hydroxide as catalyst. The study and optimization was carried out at low catalyst concentration (0.2 to 0.6 w/w). The reaction was carried out with application of low-frequency high-intensity ultrasound under atmospheric pressure and ambient temperature in a batch reactor. Response surface methodology (RSM) was used to evaluate the influence of methanol to oil ratio and catalyst concentration on soybean oil conversion into biodiesel. Analysis of the operating conditions by RSM showed that the most important operating condition affecting the reaction was the methanol to oil ratio, while catalyst amount showed little significance in the transesterification reaction. Total consumption of oil was obtained when alcohol to oil ratio of 9:1 and catalyst concentration of 0.2 w/w were applied.     

Conventional and in situ transesterification of sunflower seed oil for the production of biodiesel

In the present work the alkaline transesterification of sunflower seed oil with methanol and ethanol, for the production of biodiesel fuel was studied. Both conventional and in situ transesterification were investigated using low frequency ultrasonication (24 kHz) and mechanical stirring (600 rpm). Use of ultrasonication in conventional transesterification with methanol gave high yields of methyl esters (95%) after a short reaction time (20 min) similar to those using mechanical stirring. Use of ultrasonication in conventional transesterification with ethanol gave similar yields to those using mechanical stirring but significantly lower than respective yields using methanol. In the in situ transesterification the use of ultrasonication and mechanical stirring led to similar high yields (95%) of methyl esters after approximately 20 min of reaction time. In the presence of ethanol use of ultrasonication led to high ester yields (98%) in only 40 min of reaction time while use of mechanical stirring gave lower yields (88%) even after 4 h of reaction time.

 In situ transesterification gave similar ester yields to those obtained by conventional transesterification being an alternative, efficient and economical process. In all cases a concentration of 2.0% NaOH gave higher ester yields.

 Reaction rate constants were calculated, using first order reaction kinetics, to be equal to 3.1 × 10^− 3 s^− 1 for conventional transesterification using methanol and 2.0% NaOH, and 9.5 × 10^− 4 s^− 1 using ethanol.     

Theoretical study of the transesterification of triglycerides to biodiesel fuel

The transesterification of various triglycerides was considered in terms of the activation energy obtained from quantum computational chemistry. According to these values, the effect upon the reactivity of the structure of the triglyceride is not particularly large. Moreover, the transesterification reaction is completed via a transition state, in which ring formation consisting of the carbon of the carboxyl and alkoxy groups appears, even if a long-chain alcohol is used as a reactant. Finally, an ideal reaction pathway, in which the ester bond at the center of the triglyceride is transesterified before peripheral ester bonds, was shown by an activation energy analysis and electrostatic potential (ESP) distribution.     

Advances on the development of novel heterogeneous catalysts for transesterification of triglycerides in biodiesel

This paper describes experimental work done towards the search for more profitable and sustainable alternatives regarding biodiesel production, using heterogeneous catalysts instead of the conventional homogenous alkaline catalysts, such as NaOH, KOH or sodium methoxide, for the methanolysis reaction. This experimental work is a first stage on the development and optimization of new solid catalysts, able to produce biodiesel from vegetable oils. The heterogeneous catalytic process has many differences from the currently used in industry homogeneous process. The main advantage is that, it requires lower investment costs, since no need for separation steps of methanol/catalyst, biodiesel/catalyst and glycerine/catalyst. This work resulted in the selection of CaO and CaO modified with Li catalysts, which showed very good catalytic performances with high activity and stability. In fact FAME yields higher than 92% were observed in two consecutive reaction batches without expensive intermediate reactivation procedures. Therefore, those catalysts appear to be suitable for biodiesel production.     

Variation of physical properties during transesterification of sunflower oil to biodiesel as an approach to predict reaction progress

Biodiesel as a pure, non-toxic, biodegradable and renewable alternative for fossil diesel fuel has attracted much attention in recent decade. Thus, demands for researches in this field are growing up every day. In order to simplify the mentioned research a new method was introduced to determine progress and end point in transesterification of sunflower oil to biodiesel (methyl esters) by the use of physical property variation during reaction. This method can be replaced by expensive and time-consuming, quantitative analysis stage. In the present work first transesterification of sunflower oil at 65 °C with MeOH to oil molar ratio of 6:1 and 1 wt.% of KOH as catalyst under vigorous mixing at different durations was carried out to determine how conversion and physical properties change. It was concluded that this reaction proceeded over 90% in 5 min and most of the changes occurred in this short period. In the second step, to verify physical properties variation in all ranges, six blends of produced biodiesel and sunflower oil were prepared in different wt.%, as incomplete reaction mixture. Finally appropriate functions were fitted on the extracted data and were evaluated. Refractive index and specific gravity were selected as good physical properties to predict reaction progress.     

Extraction,transesterification and process control in biodiesel production from Jatropha curcas

Biodiesel has gained worldwide popularity as an alternative energy source due to its renewable, non‐toxic, biodegradable and non‐flammable properties. It also has low emission profiles and is environmentally beneficial. Biodiesel can be used either in pure form or blended with conventional petrodiesel in automobiles without any major engine modifications. Various non‐edible and edible oils can be used for the preparation of biodiesel. With no competition with food uses, the use of non‐edible oils as alternative source for engine fuel will be important. Among the non‐edible oils, such as Pongamia, Argemone and Castor, Jatropha curcas has tremendous potential for biodiesel production. J. curcas, growing mainly in tropical and sub‐tropical climates across the developing world, is a multipurpose species with many attributes and considerable potentials. In this article, we review the oil extraction and characterization, the role of different catalysts on transesterification, the current state‐of‐the‐art in biodiesel production, the process control and future potential improvement of biodiesel production from J. curcas.     

A comparative study of KOH loaded on double aluminosilicate layers, microporous and mesoporous materials as catalyst for biodiesel production via transesterification of soybean oil

Transesterification of soybean oil (TSO) with methanol to methyl esters (biodiesel) was found to proceed in the presence of KOH loaded on aluminosilicate layers (bentonite, kaolinite), microporous materials (zeolite Y, clinoptiloite), mesoporous materials (MCM-41, Al-MCM-41), some oxides (Al₂O₃, TiO₂, SiO₂), and silica gel as heterogeneous catalysts. Effect of reaction parameters such as KOH wt.%, amount of catalyst, reaction time, reaction temperature, molar ratio of methanol to oil and TSO yields up to 99% will be discussed in this presentation. Utilization of bentonite and kaolinite as cheap and eco-friendly solid supports is promising.     

Microwave assisted transesterification of rapeseed oil

Rapeseed is one of the important vegetable oil sources for biodiesel production due to its high oil content (around 40%). In this study rapeseed oil was converted to biodiesel by transesterification using microwave heating. Experiments were carried out in the presence of two different alkali catalysts which are sodium hydroxide and potassium hydroxide. Effects of various reaction parameters such as catalyst ratio, reaction temperature and time were investigated. Mono-, di- and triglyceride content of biodiesel were determined by gas chromatography analysis. Yield and purity (ester content) percentages of biodiesel were specified in weight, which are 88.3–93.7% and 87.1–99.4%, respectively. The results indicated that microwave heating has effectively increased the biodiesel yield and decreased the reaction time.     

Optimization of transesterification for methyl ester production from chicken fat

In this study, low cost feedstock chicken fat was used to produce methyl ester. After reducing the free fatty acid level of the chicken fat less than 1%, the transesterification reaction was completed with alkaline catalyst. Potassium hydroxide, sodium hydroxide, potassium methoxide and sodium methoxide were used as catalyst and methanol was used as alcohol for transesterification reactions. The effects of catalyst type, reaction temperature and reaction time on the fuel properties of methyl esters were investigated. The produced chicken fat methyl esters were characterized by determining their viscosity, density, pour point, flash point, acid value, methanol content, heat of combustion value, total-free glycerin, mono-di-tri glycerides, copper strip corrosion and ester yield values. The measured fuel properties of the chicken fat methyl ester met EN 14214 and ASTM D6751 biodiesel specifications when using potassium hydroxide and sodium hydroxide catalysts with high ester yield.     

Conventional and in situ transesterification of castor seed oil for biodiesel production

In the present study, biodiesel production from Ricinus communis L. red and BRS-149 nordestina varieties seed oil is reported. Reactions were made through conventional and in situ processes using ethanol and evaluating the addition of n-hexane as co-solvent. The content of ethyl esters was quantified by ¹H NMR. The highest conversions were obtained from crude oil (conventional reaction) after pre-esterification, using ethanol and a molar ratio of alcohol to oil of 60; furthermore, the addition of n-hexane was not significant on yield. Under these conditions, best conversion was around 95% for both varieties.     

Cerbera odollam (sea mango) oil as a promising non-edible feedstock for biodiesel production

This paper explores the feasibility of converting Cerbera odollam (sea mango) oil into biodiesel. The first part of this study focused on the extraction of oil from the seeds of C. odollam fruits, whereas the second part focused on the transesterification of the extracted oil to fatty acid methyl esters (FAME). The transesterification reactions were carried out using three different catalysts; sodium hydroxide (NaOH) as a homogenous catalyst, sulfated zirconia alumina and montmorillonite KSF as heterogeneous catalysts. The seeds were found to contain high percentage of oil up to 54% while the yield of FAME can reach up to 83.8% using sulfated zirconia catalyst.     

Effects of process variables for biodiesel production by transesterification

In this study, biodiesel production from various vegetable oils by transesterification was studied, to determine the optimum conditions. Experiments were carried out by using different kinds of catalysts (sodium hydroxide, potassium hydroxide, barium hydroxide, pyrolitic coke and wood ash) and feedstocks (corn oil, sunflower oil, soybean oil, olive pomace oil and cottonseed oil) at 65 °C and an agitation speed of 1000 rpm. The neutralization step with controlled pH was performed by treatment with phosphoric acid. An experimental design was used to evaluate the effects of the parameters such as types of vegetable oils, kinds of catalysts, reaction time, alcohol/oil volumetric ratio and amount of catalyst, on the methyl ester conversion. Using response surface methodology, a quadratic polynomial equation was obtained by multiple regression analysis. It was found that catalyst concentration was the most effective parameter. Sodium hydroxide and potassium hydroxide exhibited a superior catalytic behavior, whereas pyrolitic coke and wood ash had to be used in excess amount or for prolonged reaction times. Moreover, the properties such as viscosity, density, calorific value, acid value, and refractive index of the biodiesel were measured. The tri‐, di‐, monoacylglycerols and glycerol residuals in the methyl esters produced were also quantified by GC analysis.     

Application of KF/MgO as a heterogeneous catalyst in the production of biodiesel from rapeseed oil

Biodiesel was synthesized from rapeseed oil by transesterification over Magnesium oxide loaded with KF. The catalytic activity strongly depends on the loading amount of KF and calcined temperature. We found that the reaction reached a 79.37% yield when the loading amount was at 35 wt% and calcined at 500 °C. The simply dried 30% KF/MgO at 80 °C was found to give equally good results from the catalyst calcined at 500 °C, avoiding the usual activation at high temperature. The catalysts were characterized by the Hammett indicator method, BET, TG/DTG, XRD, NMR, EDS, and FT-IR. According to the instrumental analysis, the activity in the transesterification probably belonged to coordinately unsaturated F⁻ and liberation of hydroxide during preparation. The effects of methanol/oil ratio and catalyst amounts on the conversion were also studied in this paper.     

Production of biodiesel through transesterification of Jatropha oil using KNO3/Al2O3 solid catalyst

The purpose of the work to study biodiesel production by transesterification of Jatropha oil with methanol in a heterogeneous system, using alumina loaded with potassium nitrate as a solid base catalyst. Followed by calcination, the dependence of the conversion of Jatropha oil on the reaction variables such as the catalyst loading, the molar ratio of methanol to oil, reaction temperature, agitation speed and the reaction time was studied. The conversion was over 84% under the conditions of 70 °C, methanol/oil mole ratio of 12:1, reaction time 6 h, agitation speed 600 rpm and catalyst amount (catalyst/oil) of 6% (w). Kinetic study of reaction was also done.     

Biodiesel production through transesterification over natural calciums

Transesterification of palm kernel oil (PKO) with methanol over various natural calciums, including limestone calcite, cuttlebone, dolomite, hydroxyapatite, and dicalcium phosphate, has been investigated at 60 °C and 1 atm. The study showed that dolomite, mainly consisting of CaCO₃ and MgCO₃, is the most active catalyst. The calcination temperature largely affected the physicochemical properties, as evidenced by N₂ adsorption-desorption measurement, TGA, SEM and XRD, and the transesterification performance of the resultant catalysts. It was found that the calcination of dolomite at 800 °C resulted in a highly active mixed oxide. CaO was suggested to be the catalytically active site responsible for the methyl ester formation. Under the suitable reaction conditions, the amount of dolomite calcined at 800 °C = 6 wt.% based on the weight of oil, the methanol/oil molar ratio = 30, and the reaction time = 3 h, the methyl ester content of 98.0% can be achieved. The calcined dolomite can be reused many times. The analyses of some important fuel properties indicated that the biodiesel produced had the properties that meet the standard of biodiesel and diesel fuel issued by the Department of Energy Business, Ministry of Energy, Thailand.     

Sunflower biodiesel production and application in family farms in Brazil

There are limited options available for compact small-scale biodiesel production equipment that produces biodiesel of similar quality as that obtained from an industrial-scale production system. The aim of the present study was to evaluate equipment optimization for producing 40–200 L/day of biodiesel. The equipment was used to produce biodiesel for personal consumption. The produced biodiesel was tested in three microtractors, the principal agricultural machines used in family farms in the Vale do Rio Pardo region of Southern Brazil. Our results demonstrated that the equipment produced biodiesel of sufficient quality according to the limits established by the Brazilian Petroleum National Agency (ANP). In conclusion, this biodiesel can be used in microtractors with little wear on engine parts.     

Preparation of KF/CaO nanocatalyst and its application in biodiesel production from Chinese tallow seed oil

KF/CaO nanocatalyst was prepared by using impregnation method and used to convert Chinese tallow seed oil to biodiesel. The effects of different preparation conditions on biodiesel yield were investigated and the structure of the catalyst was characterized. Transmission electron microscopy (TEM) photograph showed that the catalyst had porous structure with the particle size of 30-100 nm. Brunauer-Emmet-Teller (BET) analysis indicated that the catalyst specific surface area was 109 m² g⁻¹ and average pore size was 97 nm. X-ray diffractometer (XRD) analysis demonstrated that the new crystal KCaF₃ was formed in catalyst, which enhanced catalytic ability. Under the optimal conditions, the biodiesel yield was 96.8% in the presence of as-prepared KF/CaO catalyst, showing potential applications of catalyst in biodiesel industry.     

Kalsilite based heterogeneous catalyst for biodiesel production

Kalsilite (KAlSiO₄) was used as a heterogeneous catalyst for transesterification of soybean oil with methanol to biodiesel. Kalsilite showed relatively low catalytic activity for transesterification reaction. The catalytic activity of this catalyst was significantly enhanced by introducing a small amount of lithium nitrate by the impregnation method. A biodiesel yield of 100% and a kinematic viscosity of 3.84 cSt were achieved at a mild temperature of only 120 °C over this lithium modified kalsilite catalyst (2.3 wt.% Li).     

Process optimization design for jatropha-based biodiesel production using response surface methodology

Biodiesel of non food vegetal oil origin is gaining attention as a replacement for current fossil fuels as its non-food chain interfering manufacturing processes shall prevent food source competition which is expected to happen with current biodiesel production processes. As a result, non edible Jatropha curcas plant oil is claimed to be a highly potential feedstock for non-food origin biodiesel. CaO–MgO mixed oxide catalyst was employed in transesterification of non-edible J. curcas plant oil in biodiesel production. Response surface methodology (RSM) in conjunction with the central composite design (CCD) was employed to statistically evaluate and optimize the biodiesel production process. It was found that the production of biodiesel achieved an optimum level of 93.55% biodiesel yield at the following reaction conditions: 1) Methanol/oil molar ratio: 38.67, 2) Reaction time: 3.44 h, 3) Catalyst amount: 3.70 wt.%, and 4) Reaction temperature: 115.87 °C. In economic point of view, transesterification of J. curcas plant oil using CaO–MgO mixed oxide catalyst requires less energy which contributed to high production cost in biodiesel production. The incredibly high biodiesel yield of 93.55% was proved to be the synergetic effect of basicity between the active components of CaO–MgO shown in the physicochemical analysis.