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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Renewable biofuel production from hydrocracking of soybean biodiesel with a commercial petroleum Ni-W catalyst

As a potential hydrocarbon production method, the hydrocracking of soybean biodiesel, using a commercial petroleum hydrocracking catalyst, was studied. Experiments were carried out in a 1,000 mL, high-pressure autoclave for 2–4 hr over the temperature range of 200–280°C under an initial hydrogen pressure of 10 MPa. Hydrocracking of soybean biodiesel produced n-paraffins in the C₈–C₁₇ boiling range, which includes both green gasoline and diesel. Both pressure and temperature play important roles in the transformation of soybean biodiesel. Hydrocarbons can be formed above 220°C with a liquid yield of 81.76%. The n-alkanes content of the liquid product reached 32.29% at 280°C, with 88.32% C₁₁–C₁₄ selectivity. In addition, hydrocracking results in many changes of catalyst such as physical properties, morphology, etc. For the used catalyst, the concentrations of Ni and C increased, and the pore channels were significantly reduced.     

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.     

Possibility of converting indigenous Salvadora persica L. seed oil into biodiesel in Pakistan

In this research study, biodiesel has been successfully produced from vegetable seed oil of an indigenous plant Salvadora persica L. that meets the international biodiesel standard (ASTM D6751). The biodiesel yield was 1.57 g/5 g (31.4% by weight) and the in-situ transesterification ester content conversion was 97.7%. The produced biodiesel density was 0.894 g/mL, its kinematic viscosity 5.51 mm²/s, HHV 35.26 MJ/kg, flash point 210°C, cetane no. 61, and sulfur content 0.0844%. Thermal analysis of the biodiesel showed that 97% weight loss was achieved at 595°C with total oxidation of the biodiesel. The production energy efficiency was 0.46% with a lab scale setup, assuming the volume fraction ratio (volume of the sample/total volume of the equipment used). The results revealed that single-step in-situ transesterification method is suitable for the production of biodiesel from S. persica seed oil.     

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.     

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     

Production of chicken fat ethyl esters via optomized protocols with dry washing by silica gel

The chicken fat ethyl ester (CFEE) was developed through alkali-catalyzed transesterification with ethanol using potassium hydroxide (KOH) as a catalyst. Parameters affecting the process of transesterification such as the catalyst concentration, ethanol to oil molar ratio, reaction temperature, and reaction duration are investigated. As a result, maximum CFEEs of 90% (~96.21 ester content% w/w) was obtained under optimal conditions of 1.0 wt.% KOH, 8:1 ethanol to fat molar ratio, a reaction temperature of 70°C, and a duration of 90 min. Dry washing method using (3.0% w/w) of silica gel was used to purify the crude ethyl ester from the residual catalyst, glycerol, and other impurities. Properties of the produced ethyl esters were determined and found in accordance with specifications prescribed by the ASTM standards. Moreover, blends of CFEEs and petrodiesel were prepared and evaluated according to ASTM test methods.     

Scleropyrum pentandrum (Dennst.) mabb—oil as a feedstock for biodiesel production—engine performance and emission studies

A feasibility study on utilization of non edible oil of Scleropyrum pentandrum was carried out to see its potential as a new source for biodiesel production. Nonedible oil seeds of Scleropyrum pentandrum have oil content of 55–60%. Transesterification of freshly extracted oil in the presence of anhydrous sodium hydroxide at a concentration 1% (w/v oil) and methanol-oil ratio of 40% (v/v oil) yields 90.8% methyl esters under conventional heating. Month old oil requires sulfuric acid pretreatment (esterification) before transesterification. The transesterified oil has a density 889–893 kg/m³; kinematic viscosity of 4.21–5.7 mm²/s; cetane index 46.03; pour point of ?15°C and gross calorific value of 40.135 MJ/kg and oxidative stability of 2.35 hours. The properties are well within the Indian, European and American standard limits recommended for biodiesel except the oxidation stability, which can be improved by adding antioxidant additives. The engine performance studies of B10 and B20 blends of Scleropyrum pentandrum biodiesel (SP biodiesel) with statistical inference confirmed that it can be used as a fuel in CI engines without any engine modifications. The engine exhaust emission analysis showed that the emission of hydrocarbons can be minimized by at least 15–20%, CO emission by 15%, smoke opacity by 10–12% and moderately lesser CO₂ and NOx emissions.     

Producing biodiesel from waste animal oil by modified ZnO

Biodiesel produced by transesterification of waste animal oil is a promising green fuel in the future. ZnO-Al₂O₃ and ZnO/Zn₂Al composition oxides were prepared by co-precipitation method and impregnation method, respectively. The above catalysts were characterized by X-ray diffraction (XRD), Brunauer--Emmett--Teller (BET) and CO₂ adsorption and temperature-programmed desorption (CO₂-TPD) and show that the high activity for the catalyst is attributed to its high alkalinity. The reaction parameters were optimized and the results show that the transesterification ratio of waste animal oil can reach 98.7% with 10% ZnO/Zn₂Al catalyst after 2 h. Moreover, 10%ZnO/Zn₂Al compound oxides can be active for the successive cycles. The glycerol as a predominant by-product after transesterification is of high purity with high use value.     

Assessment of biomass and lipid productivity and biodiesel quality of an indigenous microalga Chlorella sorokiniana MIC-G5

Generation of biodiesel from microalgae has been extensively investigated; however, its quality is often not suitable for use as fuel. Our investigation involved the evaluation of biodiesel quality using a native isolate Chlorella sorokiniana MIC-G5, as specified by American Society for Testing and Materials (ASTM), after transesterification of lipids with methanol, in the presence of sodium methoxide. Total quantity of lipids extracted from dry biomass, of approximately 410–450 mg g^?1 was characterized using FTIR and ¹H NMR. After transesterification, the total saturated and unsaturated fatty acid methyl esters (FAMEs) were 43% and 57%, respectively. The major FAMEs present in the biodiesel were methyl palmitate (C16:0), methyl oleate (C18:1), and methyl linoleate (C18:2), and the ¹H NMR spectra matched with criteria prescribed for high-quality biodiesel. The biodiesel exhibited a density of 0.873 g cm^–3, viscosity of 3.418 mm² s^?1, cetane number (CN) of 57.85, high heating value (HHV) of 40.25, iodine value of 71.823 g I₂ 100 g^?1, degree of unsaturation (DU) of 58%, and a cold filter plugging point (CFPP) of –5.22°C. Critical fuel parameters, including oxidation stability, CN, HHV, iodine value, flash point, cloud point, pour point, density, and viscosity were in accordance with the methyl ester composition and structural configuration. Hence, C. sorokiniana can be a promising feedstock for biodiesel generation.     

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.     

Super effective Zn-Fe-doped TiO2 nanofibers as photocatalyst for ammonia borane hydrolysis

In this study, the photocatalytic activity of TiO₂ nanofibers toward ammonia borane hydrolysis has been strongly modified by doping the nanostructure by ZnO and Fe₂O₃ oxides. Due to the differences in the work function and band gap energy among the three semiconductors (TiO₂, ZnO and Fe₂O₃), illumination of TiO₂ leads to accumulate the electrons and holes on the conduction and valance bands of Fe₂O₃ and ZnO, respectively. Accordingly, the experimental results indicated that the surface of the obtained nanofibers is very active which results in an instant hydrolysis of ammonia borane molecules reaching the active zone surrounding the nanofibers. Moreover, negative activation energy was determined as increasing the temperature led to decrease the photocatalytic performance. Furthermore, kinetic studies indicated that the heterogeneous catalytic reaction describing the ammonia borane hydrolysis process is zero order which additionally supports the super activity of the introduced nanofibers. It was also observed that Fe₂O₃ content in the introduced nanofibers has distinct influence as the best performance was obtained at 1 wt%. The modified TiO₂ nanofibers were prepared by calcination of electrospun nanofibers composed of titanium isopropoxide, zinc acetate and iron acetate in air at 700 °C for 1 h. Overall, the present study opens a new avenue to overcome the fast electrons/holes recombination dilemma facing TiO₂-based nanostructures.