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.     

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.     

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.     

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.     

Rice bran: A prospective resource for biodiesel production in Bangladesh

The increasing demand of renewable energy sources has pressed the need to search for biofuels. The world is not only thrusting for potential sources of biofuels but also surveilling not to hamper the food supply, particularly in the Third World countries, such as Bangladesh. Rice bran oil is a prominent source of biofuels. Rice, the main cereal in Bangladesh, is cultivated all the year round. Rice hull containing bran is mostly wasted and merely used as feedstock for cattle and for cooking purposes. This study considered rice bran as a prospective source of biodiesel in Bangladesh. The properties of oil collected from rice bran were investigated to ensure the production of biodiesel by transesterification. An economic analysis relative to Bangladesh was conducted, and the production rate of biodiesel under different percentage of catalyst was investigated.     

Application of TiO2 nanoparticles for eco-friendly biodiesel production from waste olive oil

An environmentally benign, simple, and efficient process has been developed for biodiesel production from waste olive oil in the presence of a catalytic amount of TiO₂ nanoparticles at 120°C with a conversion of 91.2% within 4 h. The present method affords nontoxic and noncorrosive medium, high yield of biodiesel, clean reaction, and simple experimental and isolation procedures. The catalyst can be recycled by simple filtration and reused without any significant reduction in its activity.     

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.     

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.     

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.     

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.     

Production of soybean ethanol-based biodiesel using CaO heterogeneous catalysts promoted by Zn,K and Mg

This article focuses on the optimization of the production of fatty acid ethyl esters from soybean oil using CaO-based heterogeneous catalysts. Three different catalytic promoters were evaluated: Magnesium, zinc, and potassium. The reaction has evaluated the promoter content (promoter to calcium molar ratio), catalyst load, alcohol to oil molar ratio, and temperature. Response surface methodology (RSM) was used to evaluate the influence of each variable on the yield of biodiesel. The addition of K₂O or MgO in the catalyst has enhanced the yield in fatty acid ethyl esters, while the use of ZnO as a promoter was not successful.     

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.     

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.     

Clam shell catalyst for continuous production of biodiesel

Continuous flow transesterification of waste frying oil (WFO) with methanol for the biodiesel production was tested in a laboratory scale jacketed reactive distillation (RD) unit packed with clam shell based CaO as solid catalyst. The physiochemical properties of the clam shell catalysts were characterized by X-ray Diffraction (XRD), Brunauer–Emmett–Teller (BET), Scanning Electron Microscopy (SEM), and Energy Dispersive Atomic X-ray Spectrometry (EDAX). The effects of the reactant flow rate, methanol-to-oil ratio, and catalyst bed height were studied to obtain the maximum methyl ester conversion. Reboiler temperature of 65°C was maintained throughout the process for product purification and the system reached the steady state at 7 hr. The experimental results revealed that the jacketed RD system packed with clam shell based CaO showed high catalytic activity for continuous production of biodiesel and a maximum methyl ester conversion of 94.41% was obtained at a reactant flow rate of 0.2 mL/min, methanol/oil ratio of 6:1, and catalyst bed height of 180 mm.     

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.     

Production,engine performance,combustion, emission characteristics and economic feasibility of biodiesel from waste cooking oil: A review

The depletion of fossil fuel reserves and increasing demands for diesel are considered to be important triggers for many of the initiatives that have been taken to search for possible sources for the production of biodiesel from materials available within the country. It is possible to produce biodiesel from waste/used cooking oils (WCO) that is comparable in quality to that of fresh vegetable oil. Not only does reuse of WCO, which can otherwise harm human health, reduce the burden on the government of treating oily wastewater, disposing of the waste, and maintaining public sewers, it also significantly lowers the production cost of biodiesel. In the process of frying, oil undergoes many reactions, leading to the formation of a number of undesirable compounds, such as polymers, free fatty acids, and many other chemicals. This poses challenges in the transesterification of WCO. This article covers different techniques in the production of biodiesel from WCO. It also compares combustion, emissions, and engine performance characteristics of biodiesel from WCO as well as factors affecting biodiesel production from WCO and its economic feasibility.     

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.