Methanol To Oil Molar Ratio Research Articles

Magnetically recoverable Mg substituted zinc ferrite nanocatalyst for biodiesel production: Process optimization, kinetic and thermodynamic analysis

The purpose of this work is to develop a magnetically recoverable magnesium substituted zinc ferrite nanocatalysts for production of biodiesel from waste cooking oil. Microwave assisted combustion process were employed to synthesis the nanocatalyst. The catalyst were characterized by XRD, FTIR, HR-SEM, EDX, DRS and VSM analysis. The VSM study revealed a relatively high magnetic moment and high saturation magnetization property useful for magnetic separation of the catalyst from the reaction medium. Biodiesel conversion of 99.9% was achieved at the optimized reaction conditions like 3 wt% of Mg2+ doped ZnFe2O4 nanocatalyst (ZnMgF5 sample), reaction temperature about 65ᵒC, methanol-oil molar ratio of 18:1 and reaction time 30 min. Investigation on the transesterification kinetics using ZnMgF5 revealed the rate constants ranging from 0.0375 min−1 to 0.2382 min−1, activation energy Eg = 52 kJ mol−1 and frequency factor A = 2.31 × 107 min−1. The negative values of entropy (ΔS°) indicates, increased randomness of the system. Thermodynamic parameters ΔG° = 87.17 kJ mol−1 at 338 K and ΔH° = 49.31 kJ mol−1 indicate that the transesterification reaction is non-spontaneous and endothermic in nature. The magnetically separated catalyst retained 94% of biodiesel yield even after ten cycles of recovery showing a very good performance.

Statistical optimization of biodiesel production from waste cooking oil using CaO as catalyst in a Robinson-Mahoney type reactor

This study presents a statistical optimization conducted with operating variables affecting the biodiesel production using calcium oxide (CaO, industrial grade) as heterogeneous catalyst, and waste cooking oil as triglyceride source. The experiments are carried out in a commercial Robinson-Mahoney reactor (600 cm3) using a fixed catalytic basket to analyze the advantages (e.g. optimal contact between phases, facile catalyst recovery, heat transfer) and challenges of this design upon the establishing of a bench-scale transesterification process. As a pretreatment, the catalyst was calcined at 700 °C for 2 h. A Box-Behnken design (BBD) is used to account for the catalyst dosage (3,6 and 9 wt%), particle size (1.18, 1.41 and 2 mm) and the methanol-oil molar ratio (6, 9 and 12), at fixed temperature of 60 °C, stirring of 700 rpm and reaction time of 2 h. Reaction conversions greater than 98.5% w/w of triglycerides into methyl esters were achieved for the optimized conditions estimated through the BBD at 8.75% w/w catalyst dosage, 2 mm of particle size and 8.72:1 of methanol-oil molar ratio.

Conversion of Au(III)-polluted waste eggshell into functional CaO/Au nanocatalyst for biodiesel production

Developing an environmental-friendly and highly active catalyst in transesterification for biodiesel production is of great importance for a more economic biodisel process. Herein, we reported that waste eggshells were used to adsorb Au(III) in water and convert the Au(III)-polluted eggshells into the functional nanocatalyst-CaO/Au for the transesterification reaction between soybean oil and methanol to the preparation of biodiesel. By coupling of CaO and Au nanoparticles, CaO/Au nanoparticles showed superior catalytic activity for the transesterification reaction between soybean oil and methanol. An optimum performance was observed over CaO/Au nanocomposites in a methanol-oil molar ratio at 12 : 1 with catalyst content of 1.0 wt% at 70 °C for 3 h. Besides, the catalytic activity of CaO/Au nanocatalyst was almost unchanged after recycling for 5 times and the yield of biodiesel still kept at 88.9%. The proof-of concept study provided us a sustainable method for utilization of waste eggshells to remedy the metal ions-polluted wastewater and the synthesis of functional nanocomposite for biodiesel production, show great potential application of waste eggshell in adsorption and catalytic reactions.

Response surface optimization of biodiesel yield from pre-treated waste oil of rendered pork from a food processing industry

In this study, the waste oil of rendered pork (WO-RP) from a food processing industry was studied as a source of biodiesel. The WO-RP was characterized and was found to have a high acid value of 4.30 mg KOH/g. A pre-treatment using H2SO4 was done through the standard titration method that resulted in a reduction of acid value to 0.75 mg KOH/g. The transesterification process over the KOH catalyst was carried out and optimized using the central composite design (CCD) using the Design Expert 7.0 software. The optimum conditions were found at 3:1 methanol–oil molar ratio, 0.55% catalyst loading, and 45-min reaction time. At optimum conditions, the biodiesel yield was 95.28 ± 0.15%. Its chemical characteristics were tested in terms of acid value at 0.75 mg KOH/g, ash content at 0.01 wt%, density at 0.86 g/cm3, HHV at 39.98 MJ/kg, water content at 0.10%, and kinematic viscosity at 6.9 mm2/s. The FAME profile shows the presence of linoleic, palmitic, oleic and stearic acid as major fatty acid components and functional group shows carbonyl group with traces of carboxylic at 1719 cm−1 and the sharp peak of esters at 1749 cm−1 indicating that the derived product is biodiesel.

OPTIMIZATION OF THE PRODUCTION PROCESS OF BIODIESEL FROM JATROPHA CURCAS OIL

In this paper was assessed the potential of biodiesel production from Jatropha curcas oil. The proposed process was simulated in the software Aspen Plus™ involving the stages of trans-esterification reaction, methanol recovering, purification of the obtained methyl esters, catalyst removing, purifying of glycerol and the energy integration through heat exchange networks (HEN). The biodiesel process was carried out through the catalytic reaction of transesterification of Jatropha oil with methanol using a molar ratio of methanol oil of 6:1, and with 1% w/w of NaOH (related to oil mass) as catalyst. Under these conditions, it is technologically feasible to carry out the production of biodiesel. With energy integration through the synthesis of HENs, reductions of 100% and 41.3% of hot and cold utilities were achieved. This way, the utility cost decreases 70.92%. The net present value (NPV) for the integrated process was 70.64% higher than the one corresponding to the non-integrated process under the same production conditions.

Evaluation of dolomite as catalyst in the transesterification reaction using palm oil (RBD)

In this study, the catalytic activity of dolomite was evaluated for the transesterification of Colombian RBD palm oil with methanol, carried out in a batch reactor at 333,15K and 600rpm. The activated dolomites (calcined at 1073.15K for 2h) were characterized by scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), Hammett indicators method, and quantification of the surface area, average pore size and average pore volume BET. The influence of reaction variables such as catalyst amount (%wt /wt) and methanol / palm oil molar ratio (mole/mole) was investigated. Under the suitable reaction conditions, the amount of calcined dolomite equal to 4% (wt /wt) based on the weight of oil, the methanol-oil molar ratio equal to 9:1, and the reaction time = 1h, the methyl ester content of 82.67% of fatty acid methyl esters (FAME) can be achieved.

Optimization of Biodiesel Production from Dairy Waste Scum using Response Surface Methodology

Dairy waste scum was collected and oil was separated. TiO2 catalyst was synthesized and characterized using SEM, XRD and TGA analysis. Separated oil was transesterified using synthesized TiO2 heterogeneous catalyst. Reaction was optimized for the parameters such as catalyst loading, reaction temperature, time, methanol oil molar ratio and stirring speed. In this study, the effect of reaction parameters was studied using Response Surface Methodology (RSM). The optimized parameters are 0.9 wt% catalyst, 60 °C temperature, 90 minutes time, 9:1 methanol oil molar ratio and 300 rpm stirring speed to produce a maximum yield of 93.5%.

Synthesis and properties of porous CLEAs lipase by the calcium carbonate template method and its application in biodiesel production.

In this work, porous cross-linked enzyme aggregates (p-CLEAs) were synthesized by the in situ co-precipitation method using CaCO3 microparticles as templates. The preparation procedure involved the immobilization of crude lipase as CLEAs via precipitation with ammonium sulfate and entrapping these lipase molecules into the CaCO3 templates, followed by DTT (dithiothreitol)-induced assembly of lipase molecules to form lipase microparticles (lipase molecules were assembled into microparticles internally using disulfide bonds within the lipase molecules as the molecular linkers and stimulated by dithiothreitol); finally, the removal of CaCO3 templates was performed by EDTA to form pores in CLEAs. The scanning electron microscopy analysis of p-CLEAs showed a porous structure. p-CLEAs showed obvious improvement in thermal stability (after incubation at 65 °C, p-CLEAs lipase retained 86% relative activity, while free lipase retained only 33.67%) and pH stability (p-CLEAs relative activity was over 90% while for free lipase, the relative activity ranged from 72% to 89% from pH 6 to 9) than free lipase and could hold relatively high activity retention without activity loss at 4 °C for more than six months. The application of p-CLEAs in producing biodiesel showed a higher degree of conversion. The conversion of fatty acid methyl ester (FAME) was 89.7%; this value was higher by approximately 7.4% compared to that of the conventional CLEAs under the optimized conditions of a methanol–oil molar ratio of 6 : 1, with a p-CLEAs lipase dose of 20% and water content of 3% at 45 °C for 24 h. The FAME conversion remained greater than 70% even after reusing the p-CLEAs lipase for 8 reactions. The results demonstrated that the p-CLEAs lipase is suitable for applications in the preparation of biodiesel.

Kinetic modeling of canola oil transesterification catalyzed by quicklime

This work aimed to study and model the kinetics of transesterification of canola oil with methanol catalyzed by calcined quicklime (CaO + MgO). The influence of three main variables was studied at 328 K: reagents order addition (has a negligible effect on the reaction), methanol-oil molar ratio (has minor effect on reaction rate after 1.5 h of reaction) and catalyst loading (high effect on reaction rate) to achieve at least a triglycerides conversion of 96.5% in concordance with norm EN 14103. A kinetic model based on an Eley-Rideal mechanism was found to well fit (R2 = 0.9886) the experimental data. Thus, it was concluded that for the quicklime catalyzed transesterification of canola oil with methanol to occur, first the methanol must be chemisorbed and the resulting methoxy species react with triglycerides in the interface liquid-solid. The whole process is limited by this step since methanol readily adsorbs onto the catalytic surface.

Biodiesel production by transesterification of a mixture of pongamia and neem oils

ABSTRACTExploitation of edible oils for biodiesel production has become a debatable issue. This article aims at developing a statistical model for optimized biodiesel production from a mixture of two non-edible oils, namely, pongamia and neem oils. Central composite design was used to design batch experiments in order to examine main and interaction effects of reaction time, catalyst concentration (NaOH) and methanol–oil molar ratio on biodiesel yield. Based on the experimental data, a reduced cubic model was chosen to represent the response surface (R2 = 0.995). Analysis of variance indicated that catalyst concentration had a significant effect on the biodiesel yield (F = 746.91, p < 0.0001). Numerical optimization (using fmincon in Matlab®) of the reduced cubic model predicted maximum biodiesel yield of 86.2% at reaction time: 77 minutes, catalyst concentration: 0.67% (w/w) and methanol–oil molar ratio: 6:1. A close agreement between the predicted and observed biodiesel yields (86.3%) in validation experiment (under optimal settings) confirmed the accuracy and applicability of the model for industrial process optimization. The properties of biodiesel produced under optimal settings, i.e. flash point, cloud and pour points, were within the specifications of ASTM 6751 and EN 14214 biodiesel standards.

Lipase immobilization on amino-silane modified superparamagnetic Fe3O4 nanoparticles as biocatalyst for biodiesel production

In this work, superparamagnetic Fe3O4 nanoparticles were synthesized by chemical co-precipitation using ionic liquid of 1-Butyl-3-methylimidazolium tetrafluoroborate ([BMIN]BF4) as templates. Then, the magnetic Fe3O4 nanoparticles were treated with 3-aminopropyltriethoxysilane (APTES) and obtain the surface amino-functionalized magnetic nanoparticles (APTES-Fe3O4) were used as immobilization material. Lipase was covalently bound to the APTES-Fe3O4 magnetic nanoparticles by using glutaraldehyde as a coupling reagent. A fatty acid methyl ester (FAME) conversion of 89.4% could be achieved by lipase immobilized on APTES-Fe3O4 magnetic nanoparticles under optimized conditions of methanol-oil molar ratio of 6:1, with a catalyst dose of 20%, 2% water content and 250 rpm agitation speed at 45 °C for 24 h. The FAME conversion remained greater than 70% even after reusing the catalyst for 5 reactions. In addition, the lipases immobilized on APTES-Fe3O4 magnetic nanoparticles could be recovered easily by external magnetic field for further use.

Biodiesel production from oil-rich feedstock: A neural network modeling

ABSTRACTBiodiesel produced from oil-rich feedstocks is known as a green replacement for conventional petroleum diesel. Transesterification is the common method used for biodiesel production. Hence, in this contribution, neural network modeling and least square support vector machine (LSSVM) modeling were used to predict the transesterification of castor oil with methanol to form biodiesel. Also, genetic algorithm was used for the optimization of predictive model. Input and output parameter of predictive models for the prediction of biodiesel production yield and estimation of the efficiency of biodiesel production are catalyst weight (C), methanol-to-oil molar ratio (MOR), time (S), temperature (T), and fatty acid methyl ester (FAME) yield, respectively. Proposed LSSVM modeling predicts biodiesel production yield or FAME yield within ±2% relative deviation with a high value of coefficient of determination (0.99583) and a low value of absolute deviation (1.27) in which the mentioned statistical parameters represent the accuracy and robustness of the model.

Biodiesel production from date seed oil (Phoenix dactylifera L.) via egg shell derived heterogeneous catalyst

This work explains the preparation of an efficient catalyst from waste chicken egg shells for exploring environment-friendly and cost-effective biodiesel production process for socio-economic growth. XRD, BET, TGA, and TPD-CO2 analysis were employed to evaluate the physicochemical properties of the prepared catalysts. The catalytic performance of the synthesized catalysts was tested in biodiesel production via transesterification from date seed oil under different reaction conditions. It was found that catalyst prepared at 900°C exhibited excellent transesterification activity and provided maximum yield of fatty acid methyl esters up to 93.5% under optimal reaction conditions, i.e. reaction time of 1.5h, methanol–oil molar ratio of 12:1, and catalyst amount of 5wt.%. In addition, the catalyst exhibited substantial stability and reusability during biodiesel conversion.

Optimization of the Transesterification of Waste Cooking Oil with Mg-Al Hydrotalcite Using Response Surface Methodology

Nowadays, biodiesel has become a very promising alternative to fossil diesel fuel, regarding environmental concerns and fuel resource depletion. Biodiesel is usually produced through homogeneous or heterogeneous transesterification of different fatty raw materials. Although main research has been carried out with homogenous catalysts, heterogeneous catalysts may be of interest due to ease of recovery and recycling, as well as readiness for continuous processing. In this work, calcined Mg-Al hydrotalcite (HT) was used for the heterogeneous transesterification of waste cooking oil. Three reaction parameters, namely, reaction time, amount of catalyst, and methanol-to-oil molar ratio, were optimized by means of Response Surface Methodology (RSM) at constant temperature (65 °C), using a Box-Behnken design. Optimal fatty acid methyl ester (FAME) content (86.23% w/w FAME/sample) was predicted by the model with an R-squared value of 98.45%, using 3.39 g of HT (8.5% w/w oil) and an 8:1 methanol-oil molar ratio, for a duration of 3.12 h. It was observed that calcination of HT, while avoiding the previous washing step, allowed the presence of chemical species that enhanced the effect of the catalyst. It can be concluded from this field trial that calcined and nonwashed Mg-Al hydrotalcite may be considered an effective basic catalyst for the production of biodiesel from waste cooking oil. Also, RSM proved to be a useful tool for predicting biodiesel yield.

Application of Coconut-Shell Activated Carbon as Heterogeneous Solid Catalyst for Biodiesel Synthesis

Biodiesel is a bio-based fuel for diesel engine synthesized from renewable oils isolated from oil crops or animal. Biodiesel can be produced through transesterification where the process involves a catalyst and an alcohol. The most common catalyst for this process is homogeneous liquid catalyst. However, this catalyst system suffers from environmental problems. In order to eliminate the problem, we developed potassium loaded on coconut-shell activated carbon (K/AC) as heterogeneous solid catalyst which is easily regenerated, leading to more secure and more environmental friendly application. The purpose of the present work is to demonstrate the biodiesel synthesis from palm oil using K/AC catalyst in stirred tank reactor. Reaction variables such as methanol-oil molar ratio and temperature were optimized to reach the highest conversion for 4 hours reaction time. The highest reaction conversion, 26.98%, was obtained at methanol-oil molar ratio of 6:1 and reaction temperature of 60 °C. Furthermore, the value of collision factor, activation energy and standard enthalpy change of reaction obtained are 5.40 x 103dm6.(mol.gcat.min)-1, 16.113 cal/mol and 5499.40 cal/mol, respectively.

Biodiesel production from waste cooking oil using onsite produced purified lipase from Pseudomonas aeruginosa FW_SH-1: Central composite design approach

Increasing energy demands, decreasing fossil fuel resources, instability of crude oil prices and pollution problems have compelled to switch over bio-based fuel for transportation, for example, biodiesel. In present study, waste cooking oil (WCO) was evaluated as feedstock for biodiesel production using free lipase in liquid. The response surface methodology (RSM) was used to optimize the interaction between four factors: the reaction temperature, methanol-oil molar ratio, dosage of lipase as biocatalyst and rotational speed. Using this method, the model predicted the optimal conditions reaching up to 86% FAME yield with temperature 44.2 °C, methanol-oil molar ratio (3.05:1), amount of lipase 0.782 g and rotation speed of 170 rpm with incubation period of 24 h. The reactions carried out under optimized conditions confirmed the validity of the model. The use of WCO in lipase catalyzed process can diminish the cost of biodiesel production and will allow lowering the direct use of edible oils to produce biodiesel instead. Thus, present study shows great practical potential to replace fossil fuel with renewable fuel (biodiesel).

Biodiesel production from waste cooking oil in a magnetically fluidized bed reactor using whole-cell biocatalysts

Biodiesel production from catalytic transesterification of waste cooking oil (WCO) was investigated in a magnetically fluidized bed reactor (MFBR) over Pseudomonas mendocina cells immobilized in magnetic microspheres. The effects of methanol to oil molar ratio (MOMR), magnetic field intensity, biocatalysts concentration and reactant flow rate on biodiesel production were investigated. Optimization of the selected parameters was carried out for maximum biodiesel production using response surface methodology with support of Design-Expert software. The parameters optimized with response surface methodology were MOMR of 3.74:1, magnetic field intensity of 136.63 Oe, biocatalysts concentration of 10.21wt.% and reactant flow rate of 16.97mL/min. An experimental biodiesel yield of 91.8% was obtained at 35°C after 48h with these optimized parameters. Moreover, the magnetic whole-cell biocatalysts (MWCBs) exhibited good reusability in MFBR that 87.5% biodiesel yield could still be achieved after 10 cycles. The results suggested that MWCBs catalyzed transesterification in the MFBR system would have broad application prospects in biodiesel production.

Highly stable gasified straw slag as a novel solid base catalyst for the effective synthesis of biodiesel: Characteristics and performance

A novel solid base catalyst derived from gasified straw slag for producing biodiesel was prepared by simple pulverization and sieving. This catalyst exhibited high stability, low leaching of the catalytic species, and good catalytic activity, caused by high-temperature melting in the biomass gasifier. SiO2, CaO, K2O, MgO, FeO, and Al2O3 were the common constituents (calculated as oxides) as per XRF analysis and EA. XRD and TEM-EDS analysis indicated that the catalyst comprises three crystallites: quartz, leucite, and åkermanite. The catalyst was strongly basic with a basic site concentration of 0.3974mmol⋅g−1, including strongly basic low-coordination oxygen anions, moderately basic OH groups, and metal–oxygen pairs, as identified by CO2-TPD and IR. TGA results indicated that the catalyst is thermally stable up to 400°C, which is greater than the typical reaction temperature. BET analysis results indicated that the slag exhibits a broad pore distribution with pore diameters of 5–15 and 45–75nm. The catalyst exhibited high catalytic activity and stability, exhibiting a fatty acid methyl ester (FAME) conversion of 95% for transesterification conducted at 200°C for 8h with a catalyst dose of 20% and a methanol–oil molar ratio of 12:1. The FAME conversion remained greater than 85% even after reusing the catalyst for 33 reactions without any appreciable loss of catalytic activity. Small amounts of K and Mg (<10ppm) leached into the product from the catalyst. These results indicated that the gasified straw slag catalyst demonstrates promise for producing biodiesel.

Enzymatic biodiesel production from palm oil and palm kernel oil using free lipase

Biodiesel from biological materials is receiving attention as alternative fuel. This investigation compared quality of biodiesel produced from lipase-transesterified palm oil (PO) and palm kernel oil (PKO) based on fatty acid methyl esters (FAME) and fuel properties. Biodiesel yield was optimized using three-level four-factor of Design Expert Software with enzyme load (2.5–7.5%), methanol-oil molar ratio (3-1, 1), and temperature (30–40°C) as variables. Biodiesel properties FAME, Flash Point (FC), Pour Point (PP) and kinematic viscosity were compared with American (ASTM D6751) and European (EN 14214) Standards. PO (>90%) biodiesel yield was higher than PKO (<90%), both with maximum yields observed at 40°C, 3:1 and 5–7.5%. FAME in PO-biodiesel (POBD) and PKO-biodiesel (PKOBD) include Hexadecanate and 9-Octadecenoate, while POBD had more unsaturated FAME (Dodecanoate). POBD and PKOBD had PP 6.7°C and 17.7°C respectively, while POBD Kinematic viscosity (813kg/m3) agreed with both standards. This study showed that POBD could be a better fuel alternative with further improvement of fuel properties.

Kinetic studies on oil extraction and biodiesel production from underutilized Annona squamosa seeds

The present investigation involves the production of biodiesel from non-edible Annona squamosa oil. Oil extraction has been done using aqueous HCl, H2SO4, and H3PO4 solutions with hexane at various temperatures. The optimum acid concentration is 20wt.% H2SO4 containing hexane with the maximum oil yield of 28.5%. The reaction order has been found to be first-order kinetics and the activation energy is 44.054kJmol−1. Solid acid catalyst prepared by impregnation with phosphoric acid has proved to be an efficient catalyst for the transesterification process. An optimum conversion of 85% has been achieved at 65°C; methanol–oil molar ratio 18:1; 5wt.% catalyst. The conversion of triglycerides into methyl esters obeys the first-order mechanism and Ea=9.042kJmol−1. Physico-chemical characteristics have been determined as per American Oil Chemists Society (AOCS) methods and the fuel properties complied the limits prescribed in the ASTM D6751 standards.