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.     

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.     

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.     

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.     

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 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.     

Transesterification of hazelnut oil by ultrasonic irradiation

Ultrasonic irradiation is considered an effective way to increase mass transfer between immiscible liquid–liquid phases in a heterogeneous system leading to faster transesterification and higher yield and saving excess methanol and catalyst. In this study, the transesteri?cation of hazelnut oil with methanol and ethanol was performed in the presence of potassium hydroxide or sodium methoxide as a catalyst using two types of ultrasonic irradiation with a probe (20 kHz, 200 W) and a bath (35 kHz, 400 W); a conventional production method was also used. The reaction time, alcohol:oil molar ratio, catalyst type (KOH or NaOCH₃), and catalyst amount (wt.% of oil) were studied as experimental parameters. The highest methyl ester conversion was obtained as 98.12% by using ultrasonic probe at a 5:1 methanol:oil molar ratio with KOH 1 wt.% of oil as catalyst in 20-min reaction time at autogenous temperature. The application of ultrasonic irradiation by using a probe decreased the level of energy consumption, showing that this method may be a promising alternative compared with the conventional production method.     

Synthesis and use of a catalyst in the production of biodiesel from Pongamia pinnata seed oil with dimethyl carbonate

The preparation of sodium methoxide-treated algae catalysts and their activity in the transesterification of Pongamia pinnata seed oil by dimethyl carbonate were investigated. We also investigated the effect of the sodium methoxide-treated algae catalyst on the biodiesel yield. The development of sodium methoxide-treated algae catalysts can overcome most problems associated with dissolution in dimethyl carbonate. The products were analyzed using gas chromatography-mass spectroscopy to identify the fatty acid methyl esters in the biodiesel produced. The molar ratio of Pongamia pinnata seed oil to dimethyl carbonate in transesterification in the presence of the sodium methoxide-treated algae catalyst was observed to play a substantial role in this study, wherein the Pongamia pinnata seed oil conversion increased with increasing catalyst concentration. The highest percent conversion rate was 97%. With intense research focus and development, an ideal catalyst can indeed be developed for optimal biodiesel production that is both economically feasible and environmentally benign.     

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.     

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.     

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.     

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.     

Production of bio-oil from algal biomass and its upgradation to biodiesel using CaO-based heterogeneous catalysts

The present article deals with the production of bio-oil from algal biomass as well as the preparation and characterization of noble CaO-based heterogeneous catalyst for upgradation of bio-oil to biodiesel. The bio-oil has been extracted from algal biomass using hexane as solvent in soxhlet apparatus and upgraded to biodiesel by transesterification using noble CaO-based heterogeneous catalysts. Catalyst with TiO₂:CaO molar ratio of 0.25 and calcination temperature of 700°C has been found to be most suitable among all the catalysts developed. Characterization of the catalysts has been done by using X-ray diffraction (XRD), scanning electron microscope (SEM), and thermo-gravimetric analysis (TGA). The input--output model has been developed to correlate experimental and predicted value of biodiesel yield. Optimization of process parameters has been done using response surface methodology. Various properties and elemental composition of algal bio-oil and biodiesel have been determined and compared with biodiesel.     

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.     

Optimization of biodiesel production from waste cooking oil using ion-exchange resins

Waste cooking oil is a potential substitution of refined vegetable oil for the production of biodiesel due to the low cost of raw material and for solving their disposal problem. In this study, optimization of esterification process of free fatty acids in artificially acidified soybean oil with oleic acid has been carried out using methanol as an agent and ion exchange resin as a heterogeneous catalyst. The esterification reaction has been investigated based on the mass balance of the developed model. The model has been validated against experimental data and effects of temperature and catalyst weight have been analyzed. Thereafter, optimization process has been fulfilled for two different objective functions as conversion of acid oil and benefit. Optimization results indicated that the maximum conversion of acid is 95.95%, which is achievable at 4.48-g catalyst loading and reaction temperature of 120°C. Maximum benefit was obtained as US$0.057 per batch of reaction at a catalyst amount of 1 g and temperature of 120°C.     

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.     

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.     

The effect of cerium oxide additive on the performance and emission characteristics of a CI engine operated with rice bran biodiesel and its blends

In this study, the rice bran oil (RBO) has been converted into methyl ester with an aid of transesterification reaction. Chemically, transesterification means conversion of triglyceride molecule or a complex fatty acid into alcohol and ester by removing the glycerin and neutralizing the free fatty acids. The B20 blend samples [80% diesel + 20% biodiesel] were prepared for each methyl ester obtained from RBO and then the cerium oxide (CeO₂) nanoparticles were added to the each B20 blend samples at a dosage of 50 ppm and 100 ppm with an aid of ultrasonicator. Moreover, in the absence of any engine modifications, the performance and emission characteristics of those blend samples have been investigated from the experimentally measured values such as density, viscosity, cloud point, pour point, and calorific value while the engine performance was also analyzed through the parameters like exhaust gas temperature (EGT), brake specific fuel consumption (BSFC), brake thermal efficiency (BTE), exhaust emission of carbon monoxide (CO), hydrocarbon (HC), and nitrogen oxide (NOx). The experimental results reveal that the use of CeO₂ blended biodiesel in diesel engine has exhibited good improvement in performance characteristic and reduction in exhaust emissions.     

Production and characterization of biodiesel from Eriobotrya Japonica seed oil: an optimization study

Biodiesel is now-a-days recognized as a real potential alternative to petroleum-derived diesel fuel due to its number of desirable characteristics. However, its higher production cost resulting mainly due to use of costly food-grade vegetable oils as raw materials is the major barrier to its economic viability. Present work is an attempt to explore the potential of Eriobotrya japonica seed oil for the synthesis of biodiesel using alkali-catalyzed transesterification. Optimization of production parameters, namely molar ratio of alcohol to oil, amount of catalyst, reaction time and temperature, was carried out using Taguchi method. Fatty acid composition of both oil and biodiesel was determined using GC and H¹ NMR. Alcohol to oil molar ratio of 6:1, catalyst amount of 1% wt/wt, 2 h reaction time and 50 ^°C reaction temperature were found to be the optimum conditions for obtaining 94.52% biodiesel. Highest % contribution was shown by the ‘amount of catalyst’ (67.32%) followed by molar ratio of alcohol to oil (25.51%). Major fuel properties of E. japonica methyl esters produced under optimum conditions were found within the specified limits of ASTM D6751 for biodiesel, hence it may be considered a prospective substitute of petro-diesel.     

Effect of calcination temperature on the application of sodium zirconate solid base catalyst for biodiesel production from Jatropha curcas oil

Influence of catalyst calcination temperature on the catalyst characteristics and catalytic transesterification of Jatropha curcas oil for biodiesel production was studied by using sodium zirconate (Na₂ZrO₃) solid base catalyst. Na₂ZrO₃ catalysts were prepared by impregnation method followed by calcination at temperatures of 700, 800, and 900°C. The prepared catalysts were characterized by X-ray diffraction analysis, Fourier transform infrared spectroscopy, and field emission scanning electron microscopy. Important parameters influencing the catalytic activity and fatty acid methyl ester yield were investigated. It was found that the increase in calcination temperature showed marked increase in activity due to the increased porosity and presence of tetragonal zirconia. Investigation of the reusability of the catalysts showed that the catalytic activity was retained even after five cycles of reaction.