Transesterification Of Soybean Oil Research Articles

Non Catalytic Transesterification of Vegetables Oil to Biodiesel in Sub-and Supercritical Methanol: A Kinetic’s Study

Non catalytic transesterification in sub and supercritical methanol have been used to produce biodiesel from palm oil and soybean oil. A kinetic study was done under reaction condition with temperature and time control. The experiments were carried out in a batch type reactor at reaction temperatures from 210 °C (subcritical condition) to 290 °C (the supercritical state) in the interval ranges of temperature of 20 °C and at various molar ratios of oil to methanol. The rate constants of the reaction were determined by employing a simple method, with the overall chemical reaction followed the pseudo-first–order reaction. Based on the results, the rate constants of vegetables oil were significantly influenced by reaction temperature, which were gradually increased at subcritical temperature, but sharply increased in the supercritical state. However, the rate constants of soybean oil were slightly higher than that of palm oil. The activation energy for transesterification of soybean oil was 89.32 and 79.05 kJ/mole for palm oil. Meanwhile, the frequency factor values of both oils were 72462892 and 391210 min-1, respectively. The rate reaction for both of oil were expressed as -rTG = 72462892 exp(-89.32/RT)CTG for soybean oil and -rTG = 391210 exp(-79.05/RT)CTG for palm oil. © 2013 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0)

Using critical fluid carbon dioxide to optimize the enzymatic transesterification of soybean oil and ethyl ferulate to feruloyl soy glycerides

AbstractFeruloyl Soy Glyceride (FSG) is an all‐natural replacement for petroleum‐based ultraviolet absorbing ingredients currently used in sunscreens. It is produced by the Novozym® 435‐catalyzed transesterification of ethyl ferulate (EF) with triglycerides. By‐product fatty acid ethyl esters (FAEEs) are more soluble in CO2 than the EF and triglyceride starting materials. It was hypothesized that the preferential removal of the FAEEs over EF would drive the enzymatic reaction towards the desired FSG product. The effect of CO2 pressure and temperature on the solubilities of components of the FSG reaction mixture was studied to select optimized conditions for the enzymatic reaction and purification. Pressure–temperature conditions were then selected to use in a recycling system. The enzymatic products were analyzed for CO2 with and without recycling CO2. The solubilities of all components of the reaction mixture were proportional to CO2 density but the relative solubilities of individual components were not equal at all pressures and temperatures. At 60°C, the ratio of ethyl linoleate to EF was only 1.1 at 6.9 MPa but 3.1 at 13.8 MPa. The CO2 was recycled through the reactor at 13.8 MPa (removing more FAEE by‐products) and through the receiver at 6.0 MPa (removing less FAEEs). In the recycling treatment, the material left behind in the reactor had 99.6% FSG content. The use of the reduced pressure receiver in a recycling CO2 system effectively increased the amount of EF incorporated onto the soybean oil increasing the yield of the FSG product.

Biodiesel Production Using MgO–CaO Catalysts via Transesterification of Soybean Oil: Effect of MgO Addition and Insights of Catalyst Deactivation

Biodiesel Production Using MgO–CaO Catalysts via Transesterification of Soybean Oil: Effect of MgO Addition and Insights of Catalyst Deactivation

PANF supported polymeric ionic liquids: Amphiphilic microenvironment for efficient preparation of biodiesel

Efficient and green production is extremely essential to the development of society and environment, and supported polymeric ionic liquids as heterogeneous catalysts are the current research hotspot for chemists. In this study, imidazolium ionic liquids were supported on modified polyacrylonitrile fiber (PANF) by reversible addition fragmentation chain transfer (RAFT) polymerization, and a series of fiber-supported basic catalysts (PANF@VIm-nX) were obtained by ion exchange with different anions. The modified fibers were characterized by FT-IR, XRD, TGA, SEM, 13C CP-MAS NMR and ICP-MS. The results show that the modified fibers are successful and the catalysts have sufficient active sites and mechanical strength to meet the application requirements. Several supported poly(ionic liquid)s catalysts were used to promote the transesterification of methanol and soybean oil to produce biodiesel. The effects ofionicliquidswith different structures on the reaction yield were sufficiently investigated. The anions of ionic liquids and the length of hydrophobic alkyl chains have synergistic effects on the catalytic performance of the catalyst. The fiber catalyst (PANF@VIm-8OMe) with 8 carbon alkyl chains and OMe anion showed the optimal catalytic efficiency. The yield of biodiesel was as high as 95.4 % within 6 h with a catalyst dosage of 4 wt% and a methanol to oil ratio of 30:1 at 60 ℃. In addition, the fiber catalyst had excellent stability and durability, which could be recycled more than 6 times. Finally, the fiber could be twined on the stirring impeller of the reactor, indicating its potential industrial application prospect.

Na-modified carbon nitride as a leach-resistant and cost-effective solid base catalyst for biodiesel production

Na-modified graphitic carbon nitrides were utilized for the transesterification of soybean oil and methanol. Graphitic carbon nitrides have not yet been widely applied in biodiesel production, despite their chemical stability and basicity. The catalysts were obtained via the co-thermal polymerization of NaOH and melamine. Catalyst prepared using conventional impregnation method was applied for comparison. The copolymerized catalyst with the optimum Na content showed over 90% biodiesel yield for 10 repeated cycles. The prepared catalysts were characterized by Fourier transform infrared spectrometry, X-ray diffraction, scanning electron microscopy/energy dispersive X-ray spectroscopy, CO2-diffuse reflectance infrared Fourier transform spectroscopy, and X-ray photoelectron spectroscopy. The elaborate rigid bonds between Na and N contributed to the leaching-resistance and catalytic activity. While the majority of Na species in impregnated catalysts existed in the form of Na-O, which was easily leached out to the reaction medium showing rapid catalyst deactivation over the repeated cycles. The basicity derived from the electron transfer from the Na to N atoms was confirmed from the density functional theory and CO2-diffuse reflectance infrared Fourier transform spectroscopy.

Chemical transesterification of soybean oil as a feedstock for stable biodiesel and biolubricant production by using Zn Al hydrotalcites as a catalyst and perform tribological assessment

Chemical transesterification of soybean oil as a feedstock for stable biodiesel and biolubricant production by using Zn Al hydrotalcites as a catalyst and perform tribological assessment

Potassium supported on zeolite-geopolymer hybrid materials as a new solid base catalyst for transesterification of soybean oil

The heterogeneous base catalysts were developed from zeolite-geopolymer hybrid material (Zeo-Geo) as a new support for potassium in transesterification of soybean oil. Zeo-Geo was prepared by mixing Al metal, metakaolin, and fumed silica in NaOH solution and curing at 60 °C, 24 h and 110 °C, 12 h. The Zeo-Geo contained a mixed phase of geopolymer and X-type zeolite. The xK/Zeo-Geo with x = 5, 10 or 15 wt% potassium were prepared by impregnation of Zeo-Geo with potassium acetate followed by calcination at 400 °C for 3 h. The phases of potassium were mainly K2O and K2CO3 and the basicity increased with potassium loading. The 15K/Zeo-Geo was the most active catalyst in transesterification of soybean oil with methanol, at 70 °C providing 97.64% biodiesel yield under the optimum condition: reaction time = 3 h, methanol to oil molar ratio = 16:1 and catalyst amount = 2 wt%. The catalyst was reused in 5 cycles without a significant activity loss and leaching of active species. From this study, 15K/Zeo-Geo has a potential for further development in large-scale production.

Efficient and economic transesterification of waste cooking soybean oil to biodiesel catalyzed by outer surface of ZSM-22 supported different Mo catalyst

With the aim of developing efficient heterogeneous catalysts for production of clean biodiesel through the transesterification process, a novel Mo catalyst supported on the outer surface of ZSM-22 (xMo/ZSM-22) was developed and synthesized successfully with the wet impregnation method. The characterization results showed that the Mo(VI) oxide species were highly dispersed on the surface of catalysts under the Mo-loading not higher than 5%, and the aggregation of the MoO3 nanoparticles were detected above the Mo-loading of 5%. Meanwhile, the maximum acid intensity was also exhibited in the 5Mo/ZSM-22 catalyst. As a result, the catalytic performance of Mo/ZSM-22 catalysts in the transesterification of waste cooking soybean oil (WCSO) was significantly improved compared with the untreated ZSM-22 catalyst. Especially, the 5Mo/ZSM-22 showed the good activity (XWCSO of 59.29%, SBiodiesel of 99.86%), which was mainly due to the well dispersed Mo species and the larger acidity. Additionally, the 5Mo/ZSM-22 catalyst exhibits good stability and the high biodiesel selectivity, and the fuel properties of the as-synthesized biodiesel meet ASTM D6751 standards. This work provides a useful synthesis strategy of transesterification catalysts for the preparation of biodiesel.

Microwave-Assisted Biodiesel Production Using UiO-66 MOF Derived Nanocatalyst: Process Optimization Using Response Surface Methodology

The present work is on the transesterification of soybean oil to biodiesel under microwave irradiation using a biomass and MOF−derived CaO−ZrO2 heterogeneous catalyst. The optimisation of different parameters was processed by adopting a central composite design for a response−surface methodology (RSM). The experimental data were fitted to a quadratic equation employing multiple regressions and investigated by analysis of variance (ANOVA). The catalyst was exhaustively characterised by XRD, TGA, FTIR BET, SEM, TEM, CO2 TPD and XPS. In addition, the synthesized biodiesel was characterized by 1H and 13C NMR, GCMS. The physicochemical properties of the biodiesel were also reported and compared with the ASTM standards. The maximum yield that was obtained after optimization using RSM was 97.22 ± 0.4% with reaction time of 66.2 min, at reaction temperature of 73.2 °C, catalyst loading of 6.5 wt.%, and methanol−to−oil ratio of 9.7 wt.%.

Biodiesel production by transesterification of waste cooking oil in the presence of graphitic carbon nitride supported molybdenum catalyst

Development of the active metal species with high utilization and accessibility of oil macromoleculars is one of the critical factors affecting heterogeneous metal-based catalysts for production of biodiesel. Here, we synthesized two-dimensional graphitic carbon nitride supported molybdenum (xMo/g-C3N4) catalysts for the facile transesterification of waste cooking soybean oil. Various characterization results of these catalysts show the crystal structure of g-C3N4 is not destroyed, however, Mo oxides phase, containing Mo6+ and Mo5+ state, is detected on the surface of the Mo/g-C3N4 with much Mo-loading, and the ratio of Mo6+/Mo5+ increases significantly with the increasing Mo loading. As expected, compared with the neat g-C3N4 catalyst, the g-C3N4 supported Mo catalyst exhibits a better catalytic performance; especially the 10%Mo/g-C3N4 catalyst has the optimal waste cooking soybean oil conversion of 71.1% and biodiesel selectivity of 99.5%. Furthermore, the experimental parameters and catalytic reusability for the transesterification reaction over 10%Mo/g-C3N4 catalyst are investigated. Moreover, the possible deactivation mechanism and regeneration method of as-prepared catalyst are also proposed. This work provides a valuable tactics for the production of clean and low-cost biodiesel from waste cooking soybean oil in the presence of efficient solid catalyst.

Evaluation of the effect of Si/Mo and oil/alcohol ratios in the production of biodiesel from soybean oil

Mo-KIT-6 catalysts precursors obtained by direct hydrothermal synthesis using different Si/Mo molar ratios (10, 20, 30) were evaluated in the production of biodiesel from the transesterification of soybean oil with methanol. A 2 2 + 3PtCt factorial design was used to evaluate the influence of alcohol/oil and Si/Mo ratios on biodiesel yield. ANOVA statistical analysis showed that Si/Mo ratio was the most significant variable. The factorial design showed that the optimal conditions for maximizing the biodiesel yield are: using the 10_Mo-KIT-6 catalyst, and an alcohol/oil ratio of 20/1 at 150 °C for 3 h. However, using the 20_Mo-KIT-6 catalyst with an alcohol/oil ratio of 15/1 the biodiesel yield is close to the maximum, having the advantage of using a lower amount of methanol, which means that the separation of non-reacted alcohol will consume less energy.

Optimization of biodiesel production via transesterification of soybean oil using α-MoO3 catalyst obtained by the combustion method

A catalyst based on MoO3 was synthesized by a simple and fast pilot-scale combustion reaction method and applied to the conversion of soybean oil to biodiesel via transesterification. For that, the statistical analysis of the catalyst amount and temperature, factors that influence the process, was evaluated by means of central composite design 22. MoO3 was characterized in terms of structure by X-ray diffraction (XRD), textural characterization Brunauer-Emmett-Teller (BET), density by helium pycnometry (DE), particle size analysis (DG) and acidity tests by temperature-programmed desorption of ammonia (NH3-TPD), chemical analysis by X-ray fluorescence (EDX), morphology by scanning electron microscopy (SEM) and catalytic properties. The transesterification products were characterized by gas chromatography (GC), acidity index (AI) and kinematic viscosity (KV). The results indicate the catalyst formation with a surface area of 1.36 m2g−1, and density of 4.5 g/cm3 which consists of a single crystalline phase of orthorhombic configuration, with total NH3 acidity of 33.61 μ.mol/g. Morphological characterization revealed that the catalyst is formed by irregular plates of various sizes and shapes, with a wide sizes range of agglomerated particles. In the soybean oil transesterification reactions, the catalyst was active showing 96.9% conversion to ethyl esters. The experimental design was meaningful and predictive, with a reliability level of 95%. The statistical analysis identified temperature as a significant variable for the adopted planning. To conclude, a new single-phase catalyst (α-MoO3) has been developed and successfully applied to the biodiesel Synthesis from soybean oil. These results have a positive and promising impact for biodiesel production by transesterification of soybean oil against ethanol.

Heterogeneous H6PV3MoW8O40/AC-Ag catalyst for biodiesel production: Preparation, characterization and catalytic performance

The heterogenization of Keggin-structure heteropoly acids (HPAs) has been proposed as a strategy to improve their application in biodiesel production in an attempt to comply the green and clean production demand. Herein, the commercial activated carbon (AC) was firstly modified with different metal ions (Cs+, K+ and Ag+), and then the H6PV3MoW8O40 acid was incorporated into as-modified AC supports, so as to prepare HPAs-based solid catalysts. By screening tests, the 35%H6PV3MoW8O40/AC-Ag hybrid solid catalyst showed highly catalytic performance for transesterification of soybean oil. The best oil conversion of 91.3% was achieved under optimized conditions: methanol/oil molar ratio of 30:1, reaction time of 10 h, reaction temperature of 140 °C and catalyst dosage of 8 wt.%. Characterization results of XRD, IR, ICP and TG indicated that H6PV3MoW8O40 was highly dispersed on the AC-Ag support as the loading was less than 35%. Proton exchange with Ag may contribute to the highly dispersion of H6PV3MoW8O40 on the support and thus enhance the interaction of the heteropoly acids with the support, thereof leading to the increased catalytic stability. The as-prepared 35%H6PV3MoW8O40/AC-Ag catalyst was easily recycled and had good resistance to free fatty acid (FFA) and water, which were usually included in the low-quality oils. Moreover, as a bifunctional catalyst, the solid acid catalyst could simultaneously catalyze the transesterification of soybean oil and esterification of FFAs, and a probable mechanism of the catalytic process was also proposed. All the features of this novel solid catalyst are more advantageous than the homogenous H6PV3MoW8O40 catalyst, successfully creating an efficient and sustainable approach of biodiesel production especially from the low-quality oils.

Transesterification of Soybean Oil through Different Homogeneous Catalysts: Kinetic Study

The search for alternatives to fossil fuels has been widely covered, especially in the past two decades. Thus, the role of biodiesel has been important, and its implementation in biorefineries seems feasible due to the sustainability of the process. This way, the knowledge of kinetics is vital to design industrial facilities and to compare the efficiency of catalysts (both typical and innovative ones) during transesterification or other similar processes taking place in a biorefinery, such as biolubricant production through transesterification with superior alcohols. In this work, a thorough kinetic study of homogeneous catalysts (base catalysts, such as KOH, NaOH or CH3OK, and acid catalysts (H2SO4, H3PO4 and p-toluenesulfonic acid, CH3C6H4SO3H)) applied to the transesterification of soybean oil was carried out to provide extensive kinetic data about this process. As a conclusion, a pseudo-first-order reaction mechanism was applied in all cases, with activation energies of 65.5–66 and 92.3 kJ·mol−1 for KOH and CH3C6H4SO3H, respectively, proving the higher activation energy for acid catalysis compared to base catalysis.

Optimization of Biodiesel Production Via Transesterification of Soybean Oil Using Α-Moo3 Catalyst Obtained by the Combustion Method

Optimization of Biodiesel Production Via Transesterification of Soybean Oil Using Α-Moo3 Catalyst Obtained by the Combustion Method

Template-free fabrication of magnetic mesoporous poly(ionic liquid)s: efficient interfacial catalysts for hydrogenation reaction and transesterification of soybean oil

Novel mesoporous poly(ionic liquid)s prepared by template-free method smoothly catalyzed the Pickering emulsion reactions.

Synthesis, Characterization and Use of Alumina Doped with TiO2 and ZrO2 to Produce Biofuels from Soybean Oil by Thermal Cracking, Transesterification and Hydroesterification

In this work, different metal oxides containing Ti, Zr and Al were prepared and characterized and their catalytic activities for cracking, transesterification, and hydroesterification reactions of soybean oil were evaluated. It is described the synthesis of the solids by co-precipitation, and their characterization by thermogravimetry, X-ray diffraction, Brunauer-Emmet-Teller surface area determination, Fourier-transformed Raman spectroscopy, and the determination of Lewis and Brønsted acid sites by pyridine adsorption and detection through Fourier transform infrared spectroscopy (FTIR). The hydrocarbons obtained by soybean pyrolysis were analyzed by fractional distillation, acid number, FTIR, density (at 20 °C), viscosity (at 40 °C), and calculation of the cetane number. The results suggest that all of the solids exhibit catalytic activity at the second stage of the cracking reaction (deoxygenation), lowering the final acidity of the products. The solids also exhibited catalytic activity for transesterification and hydroesterification of triacylglycerides, leading to good yields in methyl fatty acid esters.

Preparation, characterization and evaluation of x-MoO3/Al-SBA-15 catalysts for biodiesel production

Biodiesel is an alternative source of renewable energy that can be produced by a transesterification of vegetable oils. Mesoporous molecular sieves, such as SBA-15, due to high surface area and thermal stability are promising precursors for heterogeneous catalysts in the transesterification reaction. In this work, Al-SBA-15 precursor was obtained by direct hydrothermal synthesis, impregnated with different MoO3 contents (5, 10 and 15 wt%) by the pore saturation method, and evaluated as heterogeneous catalyst in the production of biodiesel from a transesterification of soybean oil with methanol. Al-SBA-15 precursor as well as MoO3/Al-SBA-15 catalyst were characterized for its structural characteristic by X-ray diffraction, textural characteristic by N2 adsorption analysis, and thermal stability by thermogravimetric analysis. An experimental planning 22 + 3 CtPt was used to evaluate the influence of MoO3 content and reaction time on biodiesel yield from soybean oil and methanol. The biodiesel content in the final product was obtained by gas chromatography. An average biodiesel yield of 96% was obtained with the catalyst 10%MoO3/Al-SBA-15 under the following reaction conditions: 20:1 methanol/soybean oil molar ratio, and 3 wt% of catalyst loading at 150 °C in 3 h. After five consecutive reaction cycles, the biodiesel yield decreased by about 34%. The density and acidity of the biodiesel produced are within the specified values for commercialization according to international standards.Graphical abstract

Evaporative light scattering detection based reversed-phase ultra-high-performance liquid chromatography method to quantify intermediates and end products of biodiesel production

A fast method based on reversed-phase ultra-high-performance liquid chromatography using evaporative light scattering detection (RP-UHPLC-ELSD) was developed for monitoring the intermediates and end products of biodiesel production. Gradient elution of water, acetonitrile, and a mixture of acetonitrile:2-propanol:n-hexane was used. With a minimal and easy sample preparation, fatty acid methyl esters (FAME), fatty acid ethyl esters (FAEE), free fatty acids (FFA), monoacylglycerols (MAG), diacylglycerols (DAG), and triacylglycerols (TAG) were successfully separated. The developed method was used to monitor an ethylic enzymatic transesterification of soybean oil and to characterize the ester content of methyl and ethyl biodiesel. The ester content obtained was compared with the reference method by gas chromatography and flame ionization detector (GC-FID), with similar results for both methyl and ethyl biodiesel. The presented method is a simple and fast alternative, a 17 min run, to monitor the transesterification process, simultaneously quantifying all the analytes produced in the reaction: biodiesel and its intermediates. Limits of detection (LOD, between 29 and 307 ng) and quantification (LOQ, between 48 and 614 ng), linearity (R2>0.99), precision (between 0.30 and 6.58%), and accuracy (between 81.6 and 119.9%) were determined for the twenty-one compounds.

Kinetics of the production of alkyl esters by transesterification of soybean oil

AbstractBiodiesel was produced by transesterification from soybean oil using methanol (methanolysis) and ethanol (ethanolysis) under conditions including NaOH/alcohol 0.50% wt, molar ratio alcohol:oil = 6:1, 600 rpm, 333 K. The evolution of biodiesel and glycerol esters concentrations were obtained by gas chromatography and liquid chromatography, respectively, as a basis for the evaluation of the kinetics of the process. A mathematical model was developed to represent the batch transesterification operations, referring to a mechanism including reactive acylglycerols and intermediates, esters, and glycerol. Considering the importance of the composition of fatty esters in biodiesel, their evolution during processing was quantified. The specific reaction rates for methanolysis and ethanolysis were 0.245 and 0.275 min−1, respectively. The concentration evolution of each fatty ester of the biodiesel was predicted by the solutions of the model equations, based on specific reaction rate constants quantified in the orders of magnitude k = 0.225–0.245 min−1 for methanolysis, and k = 0.225–0.275 min−1 for ethanolysis. Selectivity and yield values of the fatty esters were calculated: it was found Si = 23.5%–25.6% and Ri = 66.3%–89.1% for methanolysis and Si = 21.8%–26.7% and Ri = 74.1%–90.6% for ethanolysis. Based on the model, predictions of the kinetic behavior of acylglycerols reactants (triacylglycerois) and intermediates (monacylglycerois, diacylglycerois) were established.