Transesterification Of Rapeseed Oil Research Articles

CaO catalysts supported on ZSM-5 zeolite for biodiesel production via transesterification of rapeseed oil

This paper deals with the effect of Si/Al ratio and form of zeolite support on the catalytic properties of the CaO catalysts in transesterification reaction of rapeseed oil with methanol. The reaction was conducted at 180 and 220 °C. To get the intended purposes of the work a various calcium oxide (CaO) catalysts supported on the ammonium and hydrogen forms of ZSM-5 zeolites with different Si/Al ratios were prepared by impregnation method. The results showed that the most active zeolite-based catalyst was 10%CaO/ZSM-5 (Si/Al = 50) system in the transesterification reaction at both temperatures 180 and 220 °C, which exhibited triglycerides (TG) conversion equal to 72.7 and 95.2% and fatty acid methyl esters (FAME) yield of 56.9 and 91.1%, respectively. High reactivity of this catalyst is explained by its acid-base properties, crystallite size of active phase, large external surface area and uniform distribution of the CaO on catalyst surface compared to the other investigated CaO systems supported on ZSM-5 zeolites. In addition, the analysis of the product obtained in the transesterification process carried out on the 10% CaO/ZSM-5 (Si/Al = 280) catalyst at 220 °C confirmed the presence of the following methyl esters of higher fatty acids: methyl oleate, methyl linoleate, methyl linolenate, methyl stearate, methyl eicosenoate, methyl palmitate, methyl palmitoleate, methyl nervonate and methyl arachidate.

Application of snail shells as a heterogeneous catalyst for rapeseed oil butyl esters production

ABSTRACT Synthesis of fatty acid butyl esters using snail shells is attractive and increases the share of renewable resources because the snail shells are a waste of the food industry and 1-butanol can be obtained from renewable resources. Chemical and instrumental analysis methods (XRDA, FT-IR, EDS) were used for the evaluation of the chemical composition of snail shells. It was found that composition slightly depends on the kind and growing conditions, but in all the cases the main component in raw shells is CaCO3. After calcination for 5 h at a temperature of 850 °C, almost pure CaO (93.69 ± 0.43% %) is formed, which is used as a catalyst in the triglyceride transesterification process. SEM studies showed that the structure of the shells becomes porous after calcination, which increases the efficiency of the process. The Response surface methodology was used for the optimization of rapeseed oil transesterification with 1-butanol. It was found that the optimum transesterification conditions when the reaction temperature is 110°C are the following: 1-butanol-to-oil molar ratio of 10.6:1, a snail shell content of 7.53 wt%, and a reaction time of 10.77 h. Under these conditions, the 99.25 wt% yield of rapeseed butyl esters was obtained.

Biodiesel production through the transesterification of rapeseed oil over CaO‐MgO/SBA‐15 catalysts

AbstractDesigning a cost‐effective and environmentally friendly heterogeneous catalyst for biodiesel production is essential. To achieve this, new 0.3‐CaO‐MgO/SBA‐15 and 0.8‐CaO‐MgO/SBA‐15 catalysts were prepared by the impregnation method. The new 0.3‐CaO‐MgO/SBA‐15 catalyst had higher purity, larger surface area, and pore volume than 0.8‐CaO‐MgO/SBA‐15, resulting in great catalytic activity for biodiesel production by transesterification of rapeseed oil with methanol. A biodiesel yield of 97.8 wt % was attained under the optimal reaction conditions of 5 wt % catalyst concentration, 15:1 methanol/oil molar ratio, 95°C reaction temperature, and reaction time of 4 h. Most of the parameters and properties of the obtained biodiesel correspond to the EN 14212 standard. The 0.3‐CaO‐MgO/SBA‐15 catalyst could be considered a potential candidate for biodiesel production on industrial level application attributed to intriguing properties like cost‐effectiveness, ease of synthesis, and environmental greenness.

Rapeseed Oil Transesterification Using 1-Butanol and Eggshell as a Catalyst

Biodiesel can be produced both in homogeneous and heterogeneous ways. Heterogeneous synthesis allows to easily separate catalyst from esters. In this work, eggshells as a heterogeneous catalyst were used for triglyceride transesterification with 1-butanol. Response surface methodology was used for process optimization. It was obtained that eggshells are a suitable catalyst for transesterification processes. A longer process duration and higher catalyst amount have a high influence on ester yield. However, the amount of 1-butanol should not be maximized. Optimum transesterification reaction conditions were obtained when the process temperature was 110 °C, 1-butanol-to-oil molar ratio 11.3:1, eggshells amount 7.41 wt%, and process duration 11.81 h. Under these conditions, 98.78 wt% of ester yield was obtained.

Snail Shells as a Heterogeneous Catalyst for Biodiesel Fuel Production

Homogeneous catalysis is relevant for biodiesel fuel synthesis; however, it has the disadvantage of difficult separation of the catalyst. In the present work, heterogeneous catalysis was applied for rapeseed oil transesterification with methanol, while snail shells were used as a catalyst. CaO content in the catalyst was investigated. Transesterification reactions were carried out in a laboratory reactor, ester yield was analyzed using gas chromatography. Response surface methodology was used for process optimization. It was found that the optimum transesterification conditions when the reaction temperature is 64 °C are the following: a catalyst amount of 6.06 wt%, a methanol-to-oil molar ratio of 7.51:1, and a reaction lasting 8 h. An ester yield of 98.15 wt% was obtained under these conditions.

Process Characterization of the Transesterification of Rapeseed Oil to Biodiesel Using Design of Experiments and Infrared Spectroscopy

For optimization of production processes and product quality, often knowledge of the factors influencing the process outcome is compulsory. Thus, process analytical technology (PAT) that allows deeper insight into the process and results in a mathematical description of the process behavior as a simple function based on the most important process factors can help to achieve higher production efficiency and quality. The present study aims at characterizing a well-known industrial process, the transesterification reaction of rapeseed oil with methanol to produce fatty acid methyl esters (FAME) for usage as biodiesel in a continuous micro reactor set-up. To this end, a design of experiment approach is applied, where the effects of two process factors, the molar ratio and the total flow rate of the reactants, are investigated. The optimized process target response is the FAME mass fraction in the purified nonpolar phase of the product as a measure of reaction yield. The quantification is performed using attenuated total reflection infrared spectroscopy in combination with partial least squares regression. The data retrieved during the conduction of the DoE experimental plan were used for statistical analysis. A non-linear model indicating a synergistic interaction between the studied factors describes the reactor behavior with a high coefficient of determination (R²) of 0.9608. Thus, we applied a PAT approach to generate further insight into this established industrial process.

Bifunctional 1,2,4-Triazole/12-Tungstophosphoric Acid Composite Nanoparticles for Biodiesel Production.

Here, a composite nanoparticle with an acid-base bifunctional structure has been reported for the transesterification of rapeseed oil to produce biodiesel. Triazole-PWA (PWA = 12-tungstophosphoric acid) composite materials with a hexahedral structure are produced using the precipitation method, showing the average particle diameters of 200-800 nm. XPS and FT-IR analyses indicate well-defined chemical bonding of triazole moieties to the PWA. The functionalization and immobilization of PWAs are investigated due to strong interactions with triazole, which significantly improves the thermal stability and even surface area of the heteropoly acid. Furthermore, various ratios of triazole and PWAs are examined using NH3-TPD and CO2-TPD to optimize the bi-functionality of acidity and basicity. The prepared nanomaterials are evaluated during the transesterification of rapeseed oil with methanol to analyze the effect of triazole addition to PWAs according to the different ratios. Overall, the bifunctional triazole-PWA composite nanoparticles exhibit higher fatty acid methyl ester (FAME) conversions than pure PWA nanoparticles. The optimized catalyst with a triazole:PWA ratio of 6:1 exhibits the best FAME-conversion performance due to its relatively large surface area, balance of acidity, and strong basicity from the well-designed chemical nano-structure.

Kinetics and optimization of biodiesel production from rapeseed oil over calcined waste filter cake from sugar beet processing plant

A low-cost, highly active CaO-based catalyst was prepared from waste filter cake (WFC) from a sugar beet processing factory by calcination in air at 900 °C for 2 h, referred to as the calcined filter cake (CFC). It was used to catalyze the rapeseed oil transesterification with methanol under mild reaction conditions (methanol-to-oil molar ratio of 9:1, catalyst loading of 4–10 %, and reaction temperature of 40–60 °C). Rapeseed oil was characterized regarding the physicochemical properties and fatty acid profile. Low free fatty acid content (about 2.0 mg KOH/g) allowed the direct use of the base CFC catalyst for rapeseed oil transesterification. Rapeseed oil has more unsaturated fatty acids (about 93 %), with oleic acid as the most abundant, than saturated fatty acids (about 7 %). A simplified model combining the changing mechanism of the reaction and the triacylglycerols mass transfer limitation successfully describes the kinetics of transesterification. A good agreement between the model and the experiment was proved by the mean relative percentage deviation for the conversion degree of only ± 7.43 % (based on 42 data). The apparent reaction rate constant follows the Arrhenius equation with the activation energy of 51.9 kJ mol−1. The FAME content higher than 96.5 % can be obtained in wide ranges of the catalyst amount (4–10 %) and the reaction time (about 45–70 min). The following conditions were optimum: the reaction temperature of 59.2 °C, the catalyst loading of 9.1 % (based on the oil weight), and the reaction time of 47 min.

Simultaneous Extraction of Rapeseed Oil and Enzymatic Transesterification with Butanol in the Mineral Diesel Medium

Increasing environmental pollution is driving an increase in the production and use of biofuels. The cost price of biodiesel could be reduced by using low-quality oilseeds unfit for human consumption and by applying the simultaneous oil extraction and transesterification process, avoiding the oil pressure stage. The purpose of this study was to investigate the enzymatic biofuel production process (in situ) by using rapeseed with high oil acidity for simultaneous oil extraction and transesterification with a mixture of butanol and mineral diesel fuel. The investigation of the in situ process was performed using a mixture of butanol and mineral diesel and the most effective biocatalyst Lipozyme TL IM was selected. The novelty of this paper consists of the fact that mineral diesel was used as the oil extractant, and the amount chosen was such that, at the end, a mixture of fuel with a ratio 9:1 of mineral diesel to biodiesel was be produced. The experiments were carried out using ground rapeseeds under laboratory conditions. The efficiency of oil extraction was investigated by the FTIR spectrometry method, and the efficiency of transesterification was determined by the gas chromatography method. It was found that the optimal reaction duration was 7 h, reaction temperature was 40 °C, and lipase content was 6% (from the oil content in rapeseed). An oil extraction efficiency of 99.92 ± 0.04 (w/w) was observed at these conditions. A transesterification degree of 99.08 ± 0.08% (w/w) met with the requirements of the standards for biodiesel fuel. The physical and chemical properties of the produced fuel mixture met the requirements of the standards for mineral diesel and biodiesel; therefore, it can be used in diesel engines.

Enhanced transesterification of rapeseed oil to biodiesel catalyzed by KCl/CaO

Enhanced transesterification of rapeseed oil to biodiesel catalyzed by KCl/CaO

Application of dolomite as solid base catalyst for transesterification of rapeseed oil with butanol

The article presents the results of studies on the transesterification of rapeseed oil with butanol using a heterogeneous catalyst (0.315–0.1 mm) of the dolomite calcined at 850 °C. Experimental plan was prepared and results analyzed using response surface methodology. Interaction of four independent variables were analyzed and presented in the article. It was found that the biggest influence on ester yield have the temperature and the duration of the reaction. After optimizing the process, it was found that in 8 h the highest ester yield of 94.55 wt% is obtained using 5.24 wt% of dolomite, at 110 °C and 13.71:1 M ratio of butanol to oil.

Catalysis and Inhibition of Transesterification of Rapeseed Oil over MgO–CaO

Catalysis and Inhibition of Transesterification of Rapeseed Oil over MgO–CaO

Enhancing the sustainability of biodiesel fuels by inherently safer production processes

Biodiesel is an emerging green fuel that is finding increasing applications. The further improvement of the sustainability of biodiesel production processes is a key element in the energy transition scenario. Among the social pillars of sustainability, safety is a specific requirement. However, several major accidents were experienced in biodiesel facilities, involving the inventory of hazardous substances. In the present study, an inherent safety methodology is proposed as a specific design criterion for the screening of technology alternatives, supporting the selection of the safest and most sustainable production process. Four reference process alternatives for the transesterification of rapeseed oil to produce biodiesel were conceptualized. Inherent Safety Key Performance Indicators (IS-KPIs) were defined to assess the safety performance of the alternative process technologies and to support the selection of the safest design option. A sensitivity analysis was performed in order to verify the robustness of the results with respect to possible uncertainties. The results allowed the comparative assessment of the inherent safety performance of the main biodiesel production technologies, enabling a deeper understanding of the safety-critical aspects of the novel processes proposed for industrial application. The IS-KPIs were integrated in a wider system of KPIs, addressing also the environmental and economic aspects, obtaining an overall assessment of the sustainability performance of the alternative design options considered.

Effectiveness of Eggshells as Natural Heterogeneous Catalysts for Transesterification of Rapeseed Oil with Methanol

Heterogeneous catalysis has an advantage of easy separation of the catalyst after biodiesel is produced. CaO is known to be an efficient heterogeneous catalyst for biodiesel production. Taking into account that CaO is a key component of eggshells, the effectiveness of eggshells as a heterogeneous catalyst for rapeseed oil transesterification with methanol was investigated and optimal conditions of biodiesel production were determined applying RSM methodology. The influence of three independent variables on ester content was analyzed and a quadratic model was created. It was determined that this model is statistically significant. The optimum transesterification conditions when eggshells are used as a heterogeneous catalyst, and the process temperature of 64 °C, were determined as: the methanol-to-oil molar ratio 10.93:1; the catalyst amount 6.80 wt%; the reaction duration 9.48 h. The ester yield of 97.79 wt% was obtained under these conditions.

Effect of emulsification of biodiesel fuel on gas emission and thermal property

The aim of the present study is to produce the stable biodiesel emulsion fuels and to disclose the effect of emulsification of biodiesel fuel on the emission and thermal property characteristics. Emphasis is placed on the conditions related to the effective of glycerin fatty acid ester as a hydrophobic emulsifier in biodiesel emulsion and the characteristics of exhaust gases and water content. Here, biodiesel fuel is obtained via transesterification of rapeseed oil with methanol and ethanol and its emulsification, i.e., stable homogeneous mixture of water and biodiesel fuel is performed with the aid of Glycerin fatty acid ester (CR-310) as surfactant. It is found that (i) nitrogen oxides (NOx), for biodiesel fuel, is reduced with the increase in engine speed, while carbon oxides CO is slightly increased, (ii) emulsion fuel stabilizes over water content between 5 and 20% for over 1 month, (iii) production of NOx for diesel and bio-diesel fuels is suppressed due to water suspension and this trend becomes larger with an increase in engine speed and (iv) in contrast, CO emission is increased with an increase in water content and the corresponding effect of engine speed is minor.

Transesterification of Waste Rapeseed Oil to Biodiesel

Transesterification of Waste Rapeseed Oil to Biodiesel

Use of NaNO3/SiAl as Heterogeneous Catalyst for Fatty Acid Methyl Ester Production from Rapeseed Oil

The use of heterogeneous catalysts to produce fatty acid methyl esters (FAME) through transesterification with methanol might contribute to both green chemistry and a circular economy, as the process can be simplified, not requiring additional stages to recover the catalyst once the reaction takes place. For this purpose, different catalysts are used, including a wide range of possibilities. In this research the use of NaNO3/SiAl as a heterogeneous catalyst for FAME production through transesterification of rapeseed oil with methanol is considered. A thorough characterization of the catalyst (including XDR and XPS analysis, SEM microscopy, lixiviation and reusability tests, among others), specific optimization of transesterification by using the final catalyst (considering catalyst amount, stirring rate, methanol/oil ratio, and temperature), and quality determination of the final biodiesel (following the UNE-EN 14214 standard) were carried out. In conclusion, 20 mmolNa·gsupport−1 (that is, NaNO3/SiAl 20/1) offered the best results, with a high activity (exceeding 99% w/w of FAMEs) without requiring higher impregnation amounts. The best chemical conditions for this heterogeneous catalyst were 5% w/w catalyst, 700 rpm, 9:1 methanol/oil ratio, and 65 °C, obtaining Ea = 73.3 kJ·mol−1 and a high-quality biodiesel, similar to those obtained through homogeneous catalysis. Consequently, this catalyst could be a suitable precursor for FAME production.

Triglycerides transesterification over Mg-Al and Mg-Fe mixed oxides catalysts: Influence of extrusion additives

Nowadays, biodiesel is one of the most common used biofuels. After establishing its use and industrial production, research efforts are focused on developing and optimising catalytic materials. The present work studies the use of different additives for catalyst extrudation of Mg-Al and Mg-Fe mixed oxides, paying particular attention to catalyst characterisation and activity during rapeseed oil transesterification in a continuous regime (10 MPa and 120–180 °C). According to our results, it is clear that there is a relation between the used extrusion additives and the catalyst properties and activity. The use of glycerol increased catalyst compaction resulting in lower catalytic properties but higher strength values for the Mg-Al and Mg-Fe extrudates (10.7 and 4.5 N/mm, respectively). On the other hand, the use of an additive mixture composed of isopropanol, polyethylene glycol and tetraethyl orthosilicate provides Mg-Fe and Mg-Al extrudates with a solid combination of catalyst activity (70% ester formation at 10 MPa and 180 °C) and good stability, without significant metals leaching Mg < 2.0 mg/Kg and Fe < 0.3 mg/Kg.

Experimentally Calculated Study of the Effectiveness on the Process of Non-Catalytic Synthesis of Biodiesel in Reactors of Various Type

It was experimentally established that the dependence of the partial pressure of methanol on the molar fraction of methanol in oil shows a pronounced negative deviation from Raoul’s law, which significantly changes the idea of the influence of a large excess of methanol during non-catalytic synthesis of biodiesel. The efficiency of use of a molar excess of methanol is reduced as it grows, and with a more than 10-fold molar excess of the amount of reacted methanol, is practically constant. The comparison of biodiesel production processes in the range 220–235 °C showed that a slight change in the process temperature more effectively affects the biodiesel yield than an increase in the molar excess of methanol. A mathematical model of the process of transesterification of rapeseed oil in reactors of various types (batch and tubular reactors) is developed. A satisfactory correlation between the experimental and calculated data was observed. The calculation showed that the rate constants of the reverse reactions at 230 °C were not significant.

MgO doped magnetic graphene derivative as a competent heterogeneous catalyst producing biofuels via transesterification: Process optimization through Response Surface Methodology (RSM)

In the last few decades, production of alternative fuels has been a global concern among the environmental scientists in view of scarcity of fossil fuels and increasing global warming. Biodiesels are being synthesized as green fuel by transesterification of different oils and fats over diverse synthetically developed novel heterogeneous catalysts. In this present work,a magnetically reusable hybrid nanocatalyst of basic nature has been designed for the production of biodiesels by transesterification of waste corn oil and rapeseed oil in presence of methanol. During the synthesis of catalyst, magnetic CuFe2O4 nanoparticles were amalgamated with graphene oxide (GO) by using pistachio leaf extract and subsequently MgO nanoparticles were impregnated over it. The catalyst was physicochemically characterized by FT-IR, SEM, TEM, EDX, elemental mapping, XRD, VSM and TGA studies. The reaction parameters like reaction time, the methanol/oil molar ratio and the catalyst loading were optimized through Response Surface Methodology (RSM) using Box-Behnken experimental design. In addition, the catalysts was magnetically retrieved quite easily and reused five times in succession without considerable loss in its reactivity in the transesterification reaction.