Methanolysis Of Oil Research Articles

MgO Supported Groundnut (Arachis hypogaea) Shell for Methanolysis of Waste Cooking Oil

The present work is primarily focused on use of an agriculture waste i.e. groundnut shell for preparation of Mg metal ion supported heterogeneous catalyst. Wet impregnation method was followed to prepare the catalyst and finally physiological characterization was done by XRD, FESEM, SEM-EDS, HR-TEM, TGA and BET surface area analysis. Nano range metal oxide ions were observed during HR-TEM analysis and formation of Epsomite was confirmed by XRD analysis. Mg grafting followed by calcination made the catalyst heat stable above 500 °C. Effect of Mg metal loading during methanolysis of waste cooking oil was extensively studied by developing a second order kinetic model. The catalytic activity was studied by using various weight proportions of waste shell and metal oxide. The most important factor i.e. reusability of catalyst was studied thoroughly and after seven cycle the decrease in methyl ester yield was found to be only 2.9%.

Biodiesel Production by Methanolysis of Soybean Oil over Sro Loaded Coal Fly Ash

Biodiesel Production by Methanolysis of Soybean Oil over Sro Loaded Coal Fly Ash

Stabilizing sunflower biodiesel with synthetic antioxidant blends

Biodiesel was prepared using base catalyzed methanolysis of sunflower oil. The oxidative stability of the neat biodiesel, as well as samples spiked with 0.15 wt% antioxidant was quantified by induction periods (IP) obtained with the Rancimat method according to the tangent method. The neat stabilizers, binary blends and a ternary mixture of poly(1,2-dihydro-2,2,4-trimethylquinoline) (Orox PK), tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane (Anox 20), and tris(nonylphenyl)phoshite (Naugard P) were tested. Of these, Anox 20 was the most effective stabilizer while Naugard P proved ineffective for the sunflower biodiesel. Synergistic improvement of oxidative stability was observed on partial substitution of this phenolic-based compound with the Orox PK. Combinations of the latter amine-based stabilizer with other phenolic antioxidants did not show any synergy, with perhaps the exception of DTBHQ. At a dosage of 0.15 wt%, only TBHQ, propyl gallate and pyrogallol, as well as their 2:1 blends with Orox PK, provided IP values that exceeded 8 h as required by the European Standard EN 14,214 for biodiesel.

Kinetic modeling and optimization of sunflower oil methanolysis catalyzed by spherically-shaped CaO/γ-Al2O3 catalyst

Kinetic modeling and optimization of sunflower oil methanolysis catalyzed by spherically-shaped CaO/γ-Al2O3 particles were conducted in batch stirred and packed-bed tubular reactors at 60 °C. The proposed three-parameter kinetic model describing the overall reaction with a variable mechanism was successfully applied to both batch and continuous reactions. The process optimization was done using the response surface methodology combined with a central composite design. The obtained optimal catalyst concentration, methanol-to-oil molar ratio and reaction time for the batch reaction were 0.55% (CaO to the oil), 9:1 and 5.22 h, respectively. In the continuous process, the catalyst was highly active stable and slightly leachable during 30 h. The deactivation of the catalyst was due to massive deposition of the organic molecules from the reaction mixture, which sheltered the catalytically active sites on the catalyst surface.

Enhancing Biodiesel Production Using Green Glycerol-Enriched Calcium Oxide Catalyst: An Optimization Study

The present article demonstrates a superior catalytic performance of glycerol-enriched calcium oxide for biodiesel production than other calcium-based counterparts. The proficiency of glycerol-enriched calcium oxide in catalyzing the methanolysis of crude Jatropha curcas oil containing high free fatty acids content was systematically researched by examining the effects of glycerol dose, temperature, time, methanol-to-oil molar ratio and calcium oxide (CaO) amount on the process. Acid value of oil was lowered by 49 times and the maximum oil conversion of 96.1% was reported after the methanolysis reaction that indicated the improved performance of calcium oxide, after its treatment with glycerol, in accelerating biodiesel production from crude oil with very high free fatty acids amount. An interaction between the reaction variables, their influence on the methanolysis and optimum conditions affecting the process were moreover determined by means of the regression analysis (response surface methodology). The statistical analysis suggested that both CaO amount and mole ratio of methanol-to-oil had a significant impact on the current biodiesel production process.

Modelling of synthesis of waste cooking oil methyl esters by artificial neural network and response surface methodology

ABSTRACTThis present study was carried out to investigate the application of artificial neural network (ANN) and response surface methodology (RSM) as modelling tools for predicting the waste cooking oil methyl esters (WCOME) yield obtained from alkali-catalysed methanolysis of waste cooking oil (WCO). The impact of process parameters involved was studied by a central composite rotatable design. A comparison of the two developed models for the methanolysis process was carried out based on pertinent statistical parameters. The calculated values of coefficient of determination (R2) of 0.9950 and the average absolute deviation (AAD) of 0.4930 for the ANN model compared with R2 of 0.9843 and AAD of 0.9376 for the RSM model demonstrated that the ANN model was more accurate than the RSM model. The actual maximum WCOME yield of 94 wt% was obtained at a reaction temperature of 55°C, a catalyst amount of 1 w/v, a reaction time of 70 min and a methanol-to-oil ratio of 6:1.Abbreviations/Nomenclature CV: coefficient of variance; FFA: free-fatty acid; R: correlation coefficient; R2: coefficient of determination

Biodiesel fuel production by Aspergillus niger whole-cell biocatalyst in optimized medium

Methanolysis of sunflower oil catalyzed by immobilized Aspergillus niger mycelium was studied in a packed-bed reactor. The optimal cultivation parameters for A. niger were determined using full factorial and steepest ascent experimental designs. Sunflower oil, yeast extract and soybean meal were selected as the best carbon and nitrogen sources and were used in the subsequent experiments. Intracellular lipase activity and cell mass concentration were respectively 3.2 and 2.4 times greater and cultivation period decreased by 24 h compared with the initial medium. The optimum values of these most significant parameters were as follows: sunflower oil (13.2 g/L), yeast extract (6.2 g/L), soybean meal (7.4 g/L) and incubation period (72 h) at 30 °C. With A. niger biocatalyst grown in optimized conditions, the biodiesel fuel yield reached 23.1% after sixth pass of recycled reaction mixture through the reactor.

Synthesis of char-based acidic catalyst for methanolysis of waste cooking oil: An insight into a possible valorization pathway for the solid by-product of gasification

Gasification-based char from a commercial small-scale gasification plant was converted into an acidic catalyst for methanolysis of waste cooking oil (WCO). The char-based acidic catalyst was synthesized by the sulfonation of gasification char with sulfuric acid. Functional groups, acid density, morphological and surface properties were characterized and measured by using Fourier transform infrared red spectroscopy, ammonia temperature programmed desorption, field emission scanning electron microscope and Brunauer-Emmett-Teller, respectively. Wood char based acid catalyst showed higher surface area of 337 m2/g and acid density of 2.94 mmol/g. The reaction variables such as methanol/oil molar ratio, catalyst loading, reaction time and temperature, were studied. The optimum reaction conditions, 9:1 methanol/oil ratio, 6 wt% catalyst loadincxg, 130 min reaction time at 65 °C, gave 96% of ester conversion. The recovered catalyst was washed and reused without any activation (calcination), still giving 81% of ester conversion after five reaction cycles. Furthermore, fuel properties of WCO methyl esters were determined as per the ASTM and EN biodiesel standards. The utilization of char from biomass gasification for the synthesis of an acid catalyst for biodiesel production allows achieving a twofold objective. On the one side, the valorization of a material which is presently wasted. On the other side, the production of a catalyst that can effectively convert WCO into biodiesel in a single step process, therefore allowing a simplified procedure and lower operational temperatures. In addition, the obtained catalyst showed an interesting efficiency in decreasing free fatty acid of WCO and a considerable recyclability of the catalyst.

Outstanding performance of rehydrated Mg-Al hydrotalcites as heterogeneous methanolysis catalysts for the synthesis of biodiesel

Abstract There is still a need for active, selective and stable heterogeneous catalysts for the synthesis of biodiesel. In this work, magnesium-aluminium hydrotalcites with Mg/Al molar ratios within the 1.5–5 range were synthesized by coprecipitation and used as transesterification catalysts for the synthesis of biodiesel. The mixed oxides obtained after calcination recovered the hydrotalcite structure in the form of meixnerite after rehydration in boiling water. The solids were characterized by XRD, TGA, N2 adsorption-desorption, and SEM. Basic properties were assessed by means of Hammett indicators and CO2-TPD. Rehydrated materials with the highest Mg/Al ratios showed some distinctive features: low surface area, well defined flake-like crystals, high basicity and strong basic sites with H_ values above 11. They were also the most active catalysts allowing to achieve 51–75% sunflower oil methanolysis conversion after 8 h of reaction under mild conditions (60 °C, 1 atm), methanol/oil molar ratio of 12 using between 2 and 6 wt% of catalyst. The conversion increased up to 96% (92% fatty acid methyl esters yield) using 2 wt% catalyst and methanol/oil molar ratio of 48. Catalyst leaching was not a serious problem with these solids that could be reutilized maintaining very good activities. A general accordance between solids basic properties and their catalytic performance has been observed. These results are among the best reported in the literature for heterogeneous methanolysis catalysts and have been attributed to the high basicity of the rehydrated solids and the presence of strong and accessible basic sites probably consisting in interlayer hydroxide anions at the edges of the crystals.

Calcium Rich Food Wastes Based Catalysts for Biodiesel Production

Biodiesel produced from food wastes can help to solve several environmental issues: anthropogenic carbon emissions due to fossil fuels combustion and waste management. Biodiesel was produced using waste frying oils (WFO) and calcium rich food wastes such as mollusk, shrimp, eggs shells and cuttlebone to produce calcium based heterogeneous catalysts by calcination. The characterization of chalky white calcined powders by XRD showed diffraction lines typical of lime but some samples were slightly contaminated with calcite. The powders with low crystallinity showed high hydration rate presenting XRD features ascribable to nanocrystals of calcium hydroxide. The post reaction samples presented mainly lines due to calcium diglyceroxide and methoxide. Thermograms of used catalysts showed some weight loss of these calcium compounds, confirming the presence of such phases. All prepared catalysts were effective in catalyzing the methanolysis of soybean oil. A FAME yield around 96% was obtained after 2.5 h of reaction. When using WFO, the FAME yield was only 65% with simultaneous production of soap. The use of WFO and soybean oil mixtures attenuates the loss of catalytic performances. The obtained glycerin’s presented a light color characteristic of heterogeneous catalyzed processes. FTIR spectra of glycerin’s showed some features belonging to matter organic non glycerin and methanol. The catalyst reutilization without intermediate reactivation indicated that catalysts are somewhat stable. When WFO was used, the reused catalysts showed improved performance probably due to the formation of calcium diglyceroxide. Nevertheless, calcium diglyceroxide is bound to promote homogeneous catalysis and consequent deactivation.

Anaerobic Biodegradation of Ethylic and Methylic Biodiesel and Their Impact on Benzene Degradation

The aim of the present work was to study the anaerobic biodegradation of benzene in the presence of ethylic and methylic biodiesel. Biodiesel was produced by methanolysis and ethanolysis of virgin sunflower oil and ethanolysis of waste frying oil, and further characterized according to the European Biodiesel Standard EN 14214 for water content, fatty acid esters content, acid value, kinematic viscosity at 40°C, and oxidation stability at 110°C. Microcosms were set up in order to assess the biodegradation of the different biodiesel types and their impacts on benzene biodegradation. Methane production and benzene biodegradation were monitored for 85 days. Denaturing gradient gel electrophoresis was used to assess impacts on archaeal and bacterial community fingerprints. The results showed that the three types of biodiesel were readily biodegraded, even in the presence of benzene. In microcosms with only biodiesel, the highest biodegradation rate and extent was observed for sunflower methylic biodiesel followed by sunflower ethylic biodiesel and waste frying oil ethylic biodiesel. Similar results were observed in the presence of benzene. The presence of any biodiesel type negatively impacted benzene biodegradation with soybean ethylic biodiesel impacting rates the least. Microbial community fingerprint analyses showed that biodiesel composition selected distinct communities according to the alcohol employed in the transesterification reaction.

Synthesis and characterization of spherically-shaped CaO/γ-Al2O3 catalyst and its application in biodiesel production

Loading CaO onto spherically-shaped γ-Al2O3 support was applied for the preparation of a cost-effective and environmentally-friendly heterogeneous catalyst for biodiesel production. Physico-chemical, textural and morphological characterization was performed using optical emission spectroscopy (ICP OES), Hg-porosimetry, N2 physisorption, scanning electron microscopy (FESEM), X-ray diffraction (XRPD), Fourier transform infrared spectroscopy (ATR FTIR) and Hammett indicators. The effects of catalyst preparation conditions (different precursor salts and calcination temperatures) on the catalyst activity, and the reaction conditions (methanol-to-oil molar ratio and catalyst loading) on the reaction rate and esters yield were studied. In addition, catalyst stability was investigated. The most active catalyst was derived from the nitrate precursor after calcination at 475°C (inert atmosphere). Under mild reaction conditions (60°C, 5h, 900rpm, methanol-to-oil molar ratio of 12:1 and catalyst loading (CaO wt% to the oil) of 0.5%), the equilibrium ester content of 94.3% was obtained in the methanolysis of sunflower oil in a batch reactor. The catalyst remained sufficiently active in two consecutive cycles without any pretreatment. Mechanical erosion caused by stirring and massive deposition of organic molecules from the reaction mixture caused the decrease of catalytic activity while CaO leaching was negligible.

Ultrasonic-assisted continuous methanolysis of Jatropha curcas oil in the appearance of biodiesel used as an intermediate solvent

A environmental friendly system for fast transesterification of Jatropha curcas oil was developed for the production of biodiesel using an ultrasonic-assisted continuous tank reactor in the presence of fatty acid methyl ester (FAMEs) used as a green (intermediate) solvent with potassium hydroxide used as a catalyst. This research provide a new biodiesel production process, the optimal condition for the reaction were established: reaction temperature 25°C oil to methanol molar ratio was 1:5, catalyst concentration 0.75wt% of oil, solvent concentration 7.5%, flow rate 241.68±0.80ml/min, ultrasonic amplitude 60% and ultrasonic cycles 0.7s, transesterification was completed within 1.09min (residence time). The purity and conversion of biodiesel was 98.75±0.50% analyzed by the reverse phase HPLC method.

Effect of water on lipase NS81006-catalyzed alcoholysis for biodiesel production

Abstract Biodiesel production catalyzed by free lipase has been drawing attention for its lower cost and faster reaction rate compared to immobilized lipase. It has been found that free lipase NS81006 could efficiently catalyze alkyl esters production and a certain amount of water is demonstrated to be necessary for the catalytic process. The effect of water content on liquid lipase NS81006-mediated methanolysis and ethanolysis for biodiesel production was first explored respectively in this paper. It was found that with water content ranging from 3% to 10% (based on oil weight), there was no significant difference in the final alkyl ester yield either in NS81006-mediated methanolysis or ethanolysis process, while the quality of biodiesel varied obviously. The acid value as well as the contents of monoglyceride and diglyceride were much lower in the lower water-containing system. With the water content decreasing from 10% to 3%, the acid value reduced from 8.24 to 4.89 mg KOH/g oil, and the content of MAG and DAG dropped to 0.31 and 0.22, from 0.62 and 0.74, respectively. Lipase could maintain rather good stability with proper alcohol adding strategy and the gradual reduction in biodiesel yield in the repeated uses resulted from the accumulation of by-product glycerol. The continuous running of lipase-mediated methanolysis of waste cooking oil was successfully realized at 30L reactor and a final methyl ester yield of over 90% could be obtained.

Polyoxometalate based mesoporous acidic catalyst from biogenic silica for vegetable oil methanolysis: Structure activity relationship study

A superacidic mesoporous catalyst WOX/RHS-MCM-41 was synthesized using high purity biogenic silica extracted from an agro-waste, rice husk ash. Catalyst acidity was enhanced by dispersion of surface WOX groups on mesoporous support and was used for methanolysis of soybean oil and free fatty acid. Catalyst activity was found to depend upon the structure of WOX species formed over catalyst surface. Characterization with XRD, SEM, TEM, UV–vis DRS, Raman spectroscopy and acidity determination revealed that formation of highly dispersed amorphous polyoxotungstate phase on the catalyst surface developed with a specific tungsten loading and originated strong acidic sites showing high activity. Kinetic analysis revealed that pseudo-first order kinetics was followed up to the optimum reaction time with an activation energy 42.7kJmol−1. Catalyst showed high activity giving ∼90% FAME yield and reusability for multiple cycles without regeneration. The high catalytic activity was retained even in presence of free fatty acid also.

Kinetic study of soybean oil methanolysis using cement kiln dust as a heterogeneous catalyst for biodiesel production

Biodiesel may be produced through transesterification reaction between triglycerides and light alcohols in presence of different catalysts. This paper presents a study of kinetics of soybean methanolysis using cement kiln dust (CKD) as a heterogeneous catalyst. All reactions took place at a constant methanol to oil molar ratio of 12:1 and catalyst loading of 3.5%. The study consists of three phases; the first one is to consider the reaction following irreversible homogeneous kinetic models (1st and 2nd orders) due to using high excess of methanol. The second is to add the backward reaction term to the power law models. Finally, models for heterogeneous catalysts such as Eley–Rideal and Langmuir–Hinshelwood models are suggested to describe reaction kinetics. Least squares method, Runge–Kutta methods for ordinary differential equations and Levenberg–Marquardt algorithm for minimizing objective function were used to obtain the parameters of each suggested model in each phase. Calculation of determination coefficient (R2) and minimization of squared error summation method were used to determine which model is the best one to fit the experimental data. Eley–Rideal kinetic model was the best model amongst the suggested models. Fisher and Chi-square criteria were used to check the reliability of generated rate equation. The rate differential equation was solved to obtain the main engineering factors controlling the reaction.

Soybean oil methanolysis over scallop shell-derived CaO prepared via methanol-assisted dry nano-grinding

Calcium oxides with a specific surface area between 4.5m2g−1 and 62.5m2g−1 were obtained by calcination of scallop shells, following by methanol-assisted dry nano-grinding. Three distinct phases are formed on the surface of these catalysts during nano-grinding: calcium methoxide, calcium hydroxide, and calcium oxide. The effects of specific surface area and active surface phase composition on the catalytic activity of calcium oxide during methanolysis of soybean oil were investigated. The properties of the calcium oxide before, during, and after methanol assisted dry nano-grinding were studied by XRD, FTIR, and nitrogen gas adsorption based on the BET method. The ground calcium oxides were found to be effective in catalyzing the methanolysis of soybean oil, with the optimal catalyst producing a 72.3% ester yield after 20mins of reaction. The improvements in rate of reaction were attributed to the rapid formation of calcium diglyceroxide during the initial stages of methanolysis. A combination high specific surface area and effective active phases on the surface of the calcium oxide catalysts is correlated with reductions in mass transfer limitations in the early steps of the reaction, indicated by the rapid formation of calcium diglyceroxide.

Optimization of the methanolysis of lard oil in the production of biodiesel with response surface methodology

Methanolysis of lard oil to biodiesel was optimized using central composite design (CCD) of response surface methodology to delineate the effects of five levels, four factorson the yield of biodiesel. A total of 30 individual experiments were conducted and designed to study these process variables. A statistical model predicted that the highest conversion yield of lard biodiesel would be 96.2% at the following optimized reaction conditions: reaction temperature of 65°C, catalyst amount of 1.25%, time of 40min, methanol to oil molar ratio of 6:1 at 250rpm. Experiments performed at the predicted optimum conditions yielded 96% which was in good agreement with the predicted value. This study shows that lard oil as a low cost feedstock is a good source of raw material for biodiesel production and a sustainable biodiesel production could be achieved with proper optimization of the process variables.

Sudanese Clays for Heterogeneous Methanolysis of Castor Oil

Sudanese Clays for Heterogeneous Methanolysis of Castor Oil Abdul Rahim Yacob, Ahmed Mahgoub Saied Mohmedahmed Abstract Objective: To modify two Sudanese clays, called Jourdiqua and Jabbalmarra, with different loading of HCl, 0.1, 0.2, 0.3. 0.4, 0.5 and 1.00 M in order to increase their catalytic activities and then used in methanolysis of castor oil .Methods/statistical Analysis: Both raw and modified clay samples were used as catalysts under reaction conditions; 5wt% of catalyst to oil, molar ratio of methanol to oil of 27:1, 4 hours reaction time and temperature of 67 C°. The unmodified and modified clay samples were characterized by, Thermo gravimetric analysis-differential Thermo gravimetric (TGA-DTG), Brunauer-Emmett-Teller (BET), inductively coupled plasma-emission spectroscopy (ICP-ES), atomic absorption spectroscopy (AAS), X-ray powder diffraction (XRD), Fourier transform infra-red (FTIR) and field electron scanning emission microscopy (FESEM). Finding: Application/Improvement: BET analysis showed increase in specific surface area for both Jourdiqua and Jabbalmarra clays. Elemental analysis by ICP-ES showed decrease content in elements of Al, Mg, Na and K for both clays, due to the acid leaching. The biodiesel conversion was monitored using nuclear magnetic resonance (NMR) spectroscopy. An increase in conversion was observed for Jourdiqua clay from 51% to 90% when treated with 0.5 M HCl, the optimized concentration for the modification, while for Jabbalmarra 22.5% conversion was obtained with raw clay and after modification gave conversion of 82% in reaction conditions of temperature 65oC, reaction time of 4 hours, molar ratio of methanol to oil of 18:1 and catalyst loading of 9%. It was observed that acid modification with 0.5 M HCl have improved tremendously the catalytic capability of the raw clays. Full Text: PDF DOI: 10.15640/jcb.v5n2a1

Methanolysis of Jatropha curcas oil using K$_{2}$CO$_{3}$/CaO as a solid base catalyst

Biodiesel, fatty acid methyl ester produced by the transesterification of vegetable oil with methanol, is a promising alternative to petroleum-based diesel fuel. In the present study, the methanolysis of high free fatty acid (FFA) $Jatropha$ $curcas$ oil in a transesterification reaction using K$_{2}$CO$_{3}$/CaO solid base catalyst was studied. The various reaction parameters in the transesterification reaction were also discussed. The catalyst was characterized by means of Fourier transform infrared, X-ray diffraction, temperature programmed desorption of CO$_{2}$, scanning electron microscopy, particle size analyzer, true density, and surface area analyzer. The optimum conversion of jatropha oil was 92% when the transesterification reaction was carried out at 70 $^{\circ}$C with 10:1 molar ratio of methanol to oil at reaction time of 3 h and catalyst amount of 6 wt%. The efficiency of catalysts in the methanolysis of jatropha oil was also investigated.