Application of response surface methodology for the optimization of biodiesel production from yellow mustard (Sinapis alba L.) seed oil

In the present study, response surface methodology (RSM) involving central composite design (CCD) was applied to optimize the reaction parameters of biodiesel production from yellow mustard (Sinapis alba L.) seed oil during the single-step transesterification process. A total of 30 experiments were designed and performed to determine under the effects of variables on the biodiesel yield such as methanol to oil molar ratio (2:1–10:1), catalyst concentration (0.2–1.0 wt.% NaOH), reaction temperature (50–70°C), and reaction time (30–90 min). The second order polynomial model was used to predict the biodiesel yield and coefficient of determination (R²) was found to be at 0.9818. The optimum biodiesel yield was calculated as 96.695% from the model with the following reaction conditions: 7.41:1 of methanol to oil molar ratio, 0.63 wt. % NaOH of catalyst concentration, 61.84°C of reaction temperature, and 62.12 min of reaction time. It is seen that the regression model results were in agreement with the experimental data. The results showed that RSM is a suitable statistical technique for optimizing the reaction parameters in the transesterification process in order to maximize the biodiesel yield.     

Biodiesel production from a free fatty acid containing Karanja oil by a single-step heterogeneously catalyzed process

Karanja oil, containing 6.2% free fatty acids (FFAs), was considered for biodiesel production using a single-step solid-phase acid catalyzed process. Different types of zeolites and Amberlyst15 catalysts were tested and biodiesel was produced. Under similar conditions, the highest biodiesel yield was achieved using an Amberlyst15 catalyst, which contained 3–5% of moisture. The effects of operating parameters of the reaction such as reaction temperature, catalyst amount, and methanol-to-oil ratio were studied. An increase of methanol:oil ratio revealed a non-monotonic increase in biodiesel yields. Similar non-monotonic behavior was observed when Jatropha oil was used. Leaching and catalyst reusability were also considered. No significant effects of leaching were observed and catalyst reusability appeared to be affected by methanol interactions. The presence of a co-solvent, Tetrahydrofuran (THF), increased the biodiesel yield. Furthermore, an optimum amount of THF (THF:methanol volume ratio of 1:2) gave rise to the highest biodiesel yield. A biodiesel yield of 93% was achieved at 120 °C using a single-step process with Amberlyst15 as a catalyst, THF as a co-solvent, and a methanol:oil ratio of 30:1.     

Enzyme catalyzed biodiesel production from rubber seed oil containing high free fatty acid

Unrefined rubber seed oil contains high levels of free fatty acids and moisture, which make the conventional chemical catalyzed transesterification unsuitable. The method of enzyme catalyzed transesterification is well suited for biodiesel production from rubber seed oil as the enzymes are insensitive to the free fatty acids. In the present work, rubber seed oil was extracted from preserved rubber seed cake by mechanical means. The extraction process was designed and optimized through 2⁴ full factorial design. Extracted oil was subjected to enzymatic transesterification using four different lipases to identify the best one for the purpose. Transesterification process was optimized by considering three influencing variables for biodiesel production viz. methanol/oil molar ratio, catalyst concentration (% w/v) and solvent content (% v/v). A 2³ full factorial design was applied to design the experiments and optimize the biodiesel production. The interactive effects of the independent variables on biodiesel yield were analyzed and regression models were developed for each set of enzyme reactions. Among the four lipases, Thermomysis Lanugonosus Lipase was found to be the most suitable for the transesterification of rubber seed oil with a biodiesel conversion of 92.83% at a molar ratio of 4% and 5% (w/v) enzyme concentration in solvent free reaction medium.     

Homogeneous catalysed biodiesel synthesis from Alexandrian Laurel (Calophyllum inophyllum L.) kernel oil using ortho-phosphoric acid as a pretreatment catalyst

In this study, a non-edible seed oil of Alexandrian Laurel (Calophyllum inophyllum L.) with higher free fatty acid content has been harnessed to produce biodiesel by transesterification process. The 20.2% free fatty acid (FFA) content was first reduced to 12.9% by using TOP degumming process. Ortho-phosphoric acid was used to esterify the refined kernel oil. Transesterification reaction was performed with NaOH as an alkaline catalyst and methanol as an analytical solvent. The effects of methanol to oil molar ratio (MR), catalyst concentration (CC), reaction temperature (TP), reaction time (TM), and stirrer speed (SS) on biodiesel conversion were studied to optimize the transesterification conditions using DOE- approach. The experimental study revealed that 9:1 MR, 0.8 wt.% CC, 60°C TP, 75 min TM and 1000 rpm SS were the optimal process control variables. The study indicated that CC was the most important control parameter in optimal methyl ester production. The optimal treatment combination yielded 97.14% of biodiesel. The profile of biodiesel was determined using gas chromatography-mass spectrometry. ¹H NMR spectrum of Calophyllum inophyllum methyl ester (CIME) has been reported. The properties of the biodiesel have been found within specifications of the ASTM D6751 and EN 14214 standards and hence could be considered as a suitable alternative to diesel fuel for sustainable circulation of carbon.     

Optimization of esterification of fatty acid rubber seed oil for methyl ester synthesis in a plug flow reactor

To date, non-food vegetable oil has been considered as the primary source for biodiesel production. Rubber seed oil has high acid value (34 mgKOH/g) and can be used for biodiesel synthesis. The purpose of this study was to investigate esterification of fatty acid, which derived from rubber seed oil, in a plug flow reactor system at high temperature and low methanol consumption. Response surface methodology was applied for design experiment and optimization of esterification reaction. Temperature, methanol consumption, and sulfuric acid were chosen as variables to examine their influence in a conversion to methyl ester. At 140°C, at 5:1 methanol to fatty acid ratio (by mole), H₂SO₄ 1.5 (%v/w), and space time 20 min, the conversion to methyl ester attained 98.2%. Fourier transform infrared spectroscopy (FTIR) and gas chromatography-Mass spectrometry (GC-MS) were used for analysis and to confirm the formation of methyl ester. Methyl ester was characterized for biodiesel fuel properties in accordance to ASTM standard.     

Experimental evaluation of the catalytic efficiency of calcium based natural and modified catalyst for biodiesel synthesis

Transesterification of a mixture of vegetable oils with methanol using metal oxide catalysts derived from snail shell (SS) for biodiesel production was investigated. The metal oxides obtained from calcined snail shells in the temperature range of 650°–950 °C and modified by loading different potassium salts were used as a catalyst in the process. The catalysts were characterized by FT-IR, XRD, SEM-EDS, XPS and TGA. Catalytic activities of developed catalysts were also tested by Hammet indicator method and ion exchange method. The best calcination conditions were observed at 850°C for 4 hours based on biodiesel yield. The KF loaded snail shell gave highest biodiesel yield of 98 ± 1% in a batch reactor with highest basicity (15.9 mmoles/g) and basic strength measured by Hammet method. The optimized reaction conditions were: reaction temperature 65°C, reaction time 3 hours, methanol to oil molar ratio 9:1 and catalyst concentration 3wt%. Leaching and reusability tests confirm the stability of the catalyst as it encounters only 3% of leaching and small changes in catalytic activity up to five runs in terms of biodiesel yield.     

Optimization of extraction of oil and biodiesel from Thespesia populnea seed oil by alkali catalyst in India

Thespesia populnea oil was new source of biodiesel. Crude Thespesia populnea oil was used as feedstock for biodiesel production by alkali-catalyzed methanolysis. The reaction in the presence of NaOH as catalyst was carried out to investigate the optimum conditions and to study the effects of variables on the reaction. A methanol to oil ratio of 6:1, sodium methoxide catalyst concentration of 1.5%, mixing intensity of 250 rpm and reaction temperature of 60°C offered the best Thespesia populnea seed oil methyl esters (biodiesel) yield (92.6%). The methyl ester content under these optimum conditions was 92.6% w/w, and all of the measured properties of the Thespesia populnea biodiesel (TPME) met the international standards ASTM D 6751-02. The results reveal that all of the reaction variables in this study had positive effects on the reaction. The results of the present study indicated that TPME could be a potential alternative to petrodiesel     

Biodiesel synthesis and characterization using welted thistle plant (Carduus acanthoides) as source of new non-edible seed oil

In this work we applied base catalyzed transesterification to convert non-edible welted thistle oil (Carduus acanthoides) as new non-edible feedstock into biodiesel (Fatty acid methyl esters). The highest biodiesel yield of 88% was obtained using optimized reaction conditions of 70°C and 5:1 molar ratio (methanol:oil). The synthesized esters were characterize and confirmed by the application of NMR and FT-IR techniques. Gas chromatography and mass spectroscopy identified different fatty acids as palmatic acid (C16:0), oleic acid (C18:1), linoleic acid (18:2), arachidic acid (C20:0), eicosanic acid (C20:1), and erucic acid (C22:1) in the oil of welted thistle. Six corresponding methyl esters reported in welted thistle oil biodiesel includes 9-hexadecenoic acid, hexadecanoic acid, 9-octadecadienoic acid, 11-eicosanoic acid, eicosanoic acid and 13-docosenoicacid. Fuel properties, such as density @40°C Kg/L (0.8470), kinematic viscosity @ 40°C c St (4.37), flash point (95°C), cloud point (+4°C), pour point (?5°C), and sulfur contents (0.0112% wt) of the biodiesel produced were compatible with American Society for Testing and Materials D 6751 specifications.     

Transesterification of Caesalpinia eriostachys seed oil using heterogeneous and homogeneous basic catalysts

Caesalpinea eriostachys seed oil, as a source of triglycerides with potential application for biodiesel production in Mexico is introduced. Its lipid profile obtained by Gas Chromatography-Mass Spectrometry (GC-MS) revealed saturated and unsaturated glycerol esters as the constituents. Therefore, heterogeneous and homogeneous catalyzed transesterification reactions were assayed employing ZnAl hydrotalcites and KOH, as the catalysts, respectively. The transesterification reactions yielded 59% for Zn/Al(2), 79% for Zn/Al(4), and 90% for KOH, depicting typical behavior, as in biodiesel production data from literature, where Zn-Al hydrotalcites or KOH were assayed. The caloric, density, viscosity values, and fatty acid methyl esters profile from reaction products were concordant to EN 14214, suggesting C. eriostachys as a promising feedstock for biodiesel production.     

Ferric-manganese doped sulphated zirconia nanoparticles catalyst for single-step biodiesel production from waste cooking oil: Characterization and optimization

Biodiesel of waste cooking oil origin is gaining attention as a replacement for current fossil fuels, as its low-priced, recycled feedstock shall prevent food source competition, which is estimated to happen with current biodiesel production processes. As a result, waste cooking oil has been claimed to be a highly potential feedstock for biodiesel production. In the present research work, Fe-Mn doped sulphated zirconia catalyst was synthesized and used in simultaneous esterification and transesterification of waste cooking oil to biodiesel synthesis. The catalyst was prepared through the impregnation method and characterized by using XRD, TPD-NH_3, FT-IR, BET, and TEM. Response surface methodology (RSM) in conjunction with the central composite design (CCD) was applied to statistically evaluate and optimize the biodiesel preparation process. It was found that the synthesis of biodiesel achieved an optimum level of 97.2% waste cooking oil methyl ester’s (WCOME’s) yield at the following reaction conditions: methanol/oil molar ratio: 10:1, catalyst concentration: 3.0 wt %, and reaction temperature: 160 °C. The extremely high WCOME’s yield of 97.2% was proved to be due to high acidity, surface area, and large pore diameter; reactants can easily diffuse into the interior pore of the catalyst and allow them to be in contact with active sites that enhance catalytic activity.     

Prospect of castor oil biodiesel in Bangladesh: Process development and optimization study

In this study, castor oil (CO) has been investigated as a potential source for biodiesel production in Bangladesh. Castor oil has been extracted from the seeds by mechanical press and the Soxhlet extraction method. Maximum oil content of 55.7% has been found by the Soxhlet extraction method. The physicochemical properties such as free fatty acid (FFA) content, kinematic viscosity, saponification value, and density of the oil have been measured by different standard methods. The FFA content and viscosity have been found considerably higher such as 33.5% and 253 mm²/s, respectively. Biodiesel has been prepared using a three-step method comprising of saponification of oil followed by acidification of the soap and esterification of FFA. The overall yield of FFA from CO is found to be around 89.2%. The final step is esterification that produces fatty acid methyl ester (FAME) and a maximum 97.4% conversion of FFA to biodiesel has been observed. The effect of the oil to methanol molar ratio, catalyst concentration, reaction temperature, and time has been investigated for esterification reaction and optimized using the response surface methodology. ¹H NMR of crude castor oil and castor oil methyl ester (COME) was studied and analyzed that confirms the complete conversion of castor oil to biodiesel. Finally, the biodiesel, produced under optimum conditions, was characterized using the various standard method and found comparable with petro-diesel and biodiesel standard.     

A process model to estimate the cost of industrial scale biodiesel production from waste cooking oil by supercritical transesterification

This paper describes the conceptual design of a production process in which waste cooking oil is converted via supercritical transesterification with methanol to methyl esters (biodiesel).Since waste cooking oil contains water and free fatty acids, supercritical transesterification offers great advantage to eliminate the pre-treatment capital and operating cost.A supercritical transesterification process for biodiesel continuous production from waste cooking oil has been studied for three plant capacities (125,000; 80,000 and 8000 tonnes biodiesel/year). It can be concluded that biodiesel by supercritical transesterification can be scaled up resulting high purity of methyl esters (99.8%) and almost pure glycerol (96.4%) attained as by-product.The economic assessment of the biodiesel plant shows that biodiesel can be sold at US$ 0.17/l (125,000 tonnes/year), US$ 0.24/l (80,000 tonnes/year) and US$ 0.52/l for the smallest capacity (8000 tonnes/year).The sensitive key factors for the economic feasibility of the plant are: raw material price, plant capacity, glycerol price and capital cost.Overall conclusion is that the process can compete with the existing alkali and acid catalyzed processes.Especially for the conversion of waste cooking oil to biodiesel, the supercritical process is an interesting technical and economical alternative.     

Experimental investigation of performance and emission characteristics of diesel engine using Jatropha biodiesel with alumina nanoparticles

Biodiesels have come up as a very strong alternative for diesel fuel. Biodiesels such as Jatropha Oil Methyl Ester (JOME) are comparable in performance with that of the diesel engine. The thermal efficiency of engines fuelled with biodiesels was found lower than conventional diesel fuel but due to the bio-origin, the emission characteristics are much better. However, biodiesel increases the NOx emissions as these are rich in oxygen, hence nanoparticles are used in this experiment to curb the high temperatures and reduce the NOx formation. The experiment on naturally aspired diesel engine was conducted with four prepared test fuels other than neat diesel and neat biodiesel. The 50 and 150 of alumina nanoparticles were added separately to the pure diesel and pure Jatropha biodiesel to form the nano emulsions using ultrasonicator. The properties of nanoemulsion were evaluated using dynamic light scattering technique using zetasizer. The performance and emission characteristics of multi-cylinder diesel engine with these nanoemulsions were compared with that of neat fuels. The results showed that using nanoparticles with diesel and biodiesel can contribute in a more efficient, economical, and eco-friendly engine operation.     

Multi-objective optimization of a novel crude lipase-catalyzed fatty acid methyl ester (FAME) production using low-order polynomial and Kriging models

In this paper, conventional response surface methodology (RSM) based on low-order polynomials and an alternative Kriging-based method are used for the model-based single and multi-objective optimization of fatty-acid methyl ester (FAME) production catalyzed by a novel crude lipase from the yeast Cryptococcus diffluens (D44). The coefficient of determination for the two modeling approaches was calculated as 0.97 for the Kriging method, and 0.86 for RSM; showing a more reliable representation of experimental data by Kriging. Both models were used to perform single (maximizing FAME titer and temporal productivity separately) and multi-objective (maximizing FAME titer and temporal productivity simultaneously) optimizations of four important operating conditions (reaction time and temperature; amount of crude enzyme; and volume of methanol used). In all cases, the highest temperature considered (60°C) gave the best results. A reduction of reaction time in half was seen to be necessary to achieve optimum productivity compared to titer, when the two objectives were considered separately. The observed trade-off between the two objectives was quantified via multi-objective optimization using Pareto-front analysis.     

Promotional effect of transition metal doping on the properties of KF/CaO catalyst for biodiesel synthesis

A series of heterogeneous KF/CaO catalysts modified with transition metals (lanthanum, cerium, and zirconium) were prepared via wet impregnation method and applied to the trsansesterification process of waste cooking oil (WCO) as feedstock with methanol to biodiesel production. The structure, performance of the solid catalysts was characterized by X-ray diffraction (XRD), temperature programmed desorption of CO₂ (CO₂-TPD), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS). The effect of methanol/oil molar ratio, ¹reaction time, reaction temperature, catalyst amount, and stability was investigated. The results showed that 10 wt% of lanthanum, cerium, and zirconium improved the catalytic activity of KF/CaO catalyst. The maximum catalytic activity using the lanthanum doping of 10wt% on KF/CaO catalyst was reached 98.7% under the optimal reaction condition of methanol/oil molar ratio of 12:1, reaction for 1 h at reaction temperature of 65°C, and 4% (wt/wt oil) catalyst amount. In addition, the FAME yield of KF/CaO/La catalyst remained higher than 95% after 10 cycles. The promotional effect of lanthanum doping could be attributed to the enhancement of the basicity strength of KF/CaO catalyst and block the leach of Ca²⁺ in the transesterification reaction.     

Removal of dicofol from water by immobilized cellulase and its reaction kinetics

Researches on the removal of dicofol catalyzed by immobilized cellulase were conducted. Factors, such as acidity, temperature, enzyme activity, and initial concentration of dicofol, which could influence the removal were studied. The optimal pH for dicofol removal by immobilized cellulase was approximately 4–7, broader than that for free enzymes. The removal efficiencies for immobilized and free cellulase both decreased with increasing initial concentration of dicofol. The K_m for immobilized cellulase was slightly lower than that of free cellulase, suggesting that substrate affinity may be enhanced by immobilization. The optimum temperatures for immobilized and free cellulase were 45 °C and 50 °C. The removal reaction for immobilized cellulase was found to be a first-order reaction. The activation energy was 64.3 kJ mol⁻¹. The continuous oxidation of dicofol carried out in the static system of immobilized cellulase showed that the removal efficiency of immobilized cellulase remained after six cycles of operation. Thus, the catalytic efficiency of cellulase was improved greatly. As evidenced by infrared and gas chromatography–mass spectrometry data, the mechanism of reaction might involve an attack by the OH free radical of cellulase at a weak location of the dicofol molecule, resulting in the removal of three chlorine atoms from dicofol, thus oxygenizing dicofol and producing 4,4′-dichloro-dibenzophenone.     

Nanocatalyzed biodiesel synthesis from the oily contents of Marine brown alga Dictyota dichotoma

This research article demonstrates biodiesel synthesis through the methanolysis of the oily contents (4.02 ± 0.27% w/w on dried basis) of Dictyota dichotoma collected from the coast of Hawksbay, Pakistan. The metal oxides (CaO, MgO, ZnO, and TiO₂) used as nanocatalysts were refluxed (5% K₂SO₄), calcinated (850 °C) and characterized by Atomic Force Microscopy (AFM) which produced 93.2% w/w FAME (biodiesel) at relatively mild condition (5% catalyst, 65 °C, 3 h, 18:1 molar ratio) using CaO. Whereas, MgO, ZnO, and TiO₂ produced 92.4%, 72.5%, and 31.8% w/w FAME, respectively at elevated condition (225 °C). Thus, CaO was considered to be the best catalyst among the others. This tri-phase reaction require continuous fast mixing and the yield depends on the reaction parameters like catalyst amount, temperature, reaction time and molar ratio (methanol: oil). The reusability of these heterogeneous catalysts simplified the purification step, reduced the waste generation and make the final product technically and economically viable.     

Garcinia gummi-gutta (L.) Robs.: A promising feedstock for biodiesel production

In the present study crude Garcinia gummi-gutta seed oil was evaluated as a potential feedstock for biodiesel production. Due to the high acid value (29.73 mg KOH/g) the oil was converted to biodiesel by using acid catalyzed esterification process. Further, biodiesel properties of the sample were evaluated, which fulfilled the biodiesel specifications laid by ASTM D6751, EN 14214 and IS 15607. The biodiesel possessed excellent cetane number (66.09) and a high flash point (158°C). In addition, the calorific value (41.03 MJ/kg) was very close to diesel fuel. The results suggest that the G. gummi-gutta can be an alternative source for diesel and can be used as a potential feedstock for biodiesel in India.     

不同载体对淀粉酶固定化的比较研究

采用海藻酸钠微胶囊法和壳聚糖交联法对淀粉酶进行固定化，比较两种淀粉酶固定化方法的优劣。结果表明，两种固定化酶的活力回收分别为33．2％、26．6％，比活力分别为27．1U／mg蛋白、24．2U／mg蛋白，最适pH分别为5．0、8．0。海藻酸钠微胶囊法热稳定性、pH稳定性、操作稳定性、贮存稳定性明显高于壳聚糖交联法，因此海藻酸钠微胶囊法较佳，具有一定应用价值。     

Evaluating the potential of biodiesel (via recycled cooking oil) use in Singapore,an urban city

Singapore has pledged to attain 7–11% Business-As-Usual carbon emissions reduction by 2020. About 19% of CO₂ contribution stemmed from road transport in 2005. Commercial vehicles, which uses mainly diesel, consumed 695 million litres diesel in 2012. An estimated 115,585 tonnes or 127 million litres cooking oils (derived from seeds/fruits) were consumed in 2010, in which the bulk of used cooking oil is re-incorporated into the food preparation process while only a small amount is being recycled into biodiesel or disposed into the sewerage. Nevertheless, the present research reveals that biodiesel derived from spent cooking oil has potential to be a viable fuel supplement. Surveys were carried out involving three market segments – suppliers, processors and end-users – to identify the barriers and obstacles in mass production of biodiesel. A key enabler of biodiesel as a fuel supplement towards a greener environment lies in government mandate/policies in promoting greater biodiesel usage.