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.     

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.     

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.     

Dry reforming of methane over oil palm shell activated carbon and ZSM-5 supported cobalt catalysts

In this study, cobalt supported oil palm shell activated carbon (Co/OPS-AC) and ZSM-5 zeolite (Co/ZSM-5) catalysts have been prepared for dry reforming of methane. Cobalt ratios of 6.0 and 14.0 wt% were deposited via wet impregnation method to the OPS-AC and ZSM-5 catalysts. The catalysts were characterized by XRD, N₂ adsorption--desorption isotherms, BET surface area, SEM, FESEM-EDX, TPR-H₂, and TPD-NH₃. The dry reforming of methane was performed using a micro reactor system under the condition of 10,000 ml/h.g-cat, 3 atm, CH₄/CO₂ ratio of 1.2:1.0 and temperature range from 923 K to 1023 K. The gaseous products were analyzed by gas chromatography (GC) with thermal conductivity detector (TCD) and further quantified to determine the conversions of CH₄ and CO₂, and the yields of CO and H₂. Experimental results revealed both catalysts exhibited lower conversions of CO₂ and CH₄ with the increase in temperature from 923 K to 1023 K. The reduced conversions may be due to the formation of carboneous substance on the catalyst known as coking. Comparatively, Co/OPS-AC gave higher conversions of CO₂ and CH₄ as well as higher yields of H₂ and CO as it has a higher surface area than Co/ZSM-5 which subsequently rendered higher activity for the reforming of methane. With the increasing cobalt loadings and reaction temperature, OPS-AC(14) catalyst exhibited improved activity and H₂/CO ratio. Based on these results, cobalt supported OPS activated carbon catalyst was suggested to be more effective for CO₂ and CH₄ conversions.     

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.     

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.     

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.     

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.     

Effects of alkali promoters on the textural and catalytic properties of mesoporous Fe–Al–Cu catalysts for water gas shift reaction

Mesoporous Fe₂O₃–Al₂O₃–CuO catalysts promoted with alkali oxides were synthesized and used in water gas shift reaction (WGSR) at high temperatures for hydrogen purification. These chromium-free catalysts were characterized using nitrogen adsorption/desorption, hydrogen temperature programmed reduction, X-ray diffraction (XRD), and transmission electron microscopy techniques. The synthesized catalysts with narrow single-modal pore size distribution in mesopore region possessed high specific surface area. The catalytic results revealed that except Cs, the addition of other alkali promoters declined the catalytic activity. However, all catalysts showed higher catalytic performance than the conventional commercial catalyst. The results showed an optimum content of Cs promoter (3 wt.%) for the promoted Fe–Al–Cu catalyst (3 wt.% Cs-FAC), which exhibited the highest activity in WGSR at high temperature.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Design and optimization of new La1−xCexNi1−yFeyO3 (x,y = 0–0.4) nano catalysts in dry reforming of methane

The paper reports the production of syngas from dry reforming of methane (DRM) over La_1?xCe_xNi_1?yFe_yO₃ (x, y = 0–0.4) perovskites. A series of La_1?xCe_xNi_1?yFe_yO₃ were designed by central composite design (CCD) and synthesized by a sol–gel auto combustion method. Artificial neural network (ANN) approach was used to determine the relationship between preparation and operational parameters on the performance of the catalysts in the DRM process. Nickel mole fraction, lanthanum mole fraction, calcination temperature, and reaction temperature were considered as input variables, and conversion of methane was considered as the output variable. An ANN model with nine neurons in the hidden layer was the suitable in predicting conversion of methane. The genetic algorithm (GA) was subsequently used to determine the optimal preparation condition for enhancing the conversion of methane. La_0.6Ce_0.4Ni_0.99Fe_0.01O₃ catalyst, calcined at 756°C was obtained to be the most active catalyst owing to the optimal composition of nickel and lanthanum in the catalyst formulation.     

CO2 recycling by reaction with renewably-generated hydrogen

A laboratory-scale reactor system was built and operated to demonstrate the feasibility of catalytically reacting carbon dioxide (CO₂) with renewably-generated hydrogen (H₂) to produce methane (CH₄) according to the Sabatier reaction: CO₂ + 4H₂ → CH₄ + 2H₂O. A cylindrical reaction vessel packed with a commercial methanation catalyst (Haldor Topsøe PK-7R) was used. Renewable H₂ produced by electrolysis of water (from solar- and wind-generated electricity) was fed into the reactor along with a custom blend of 2% CO₂ in N₂, meant to represent a synthetic exhaust mixture. Reaction conditions of temperature, flow rates, and gas mixing ratios were varied to determine optimum performance. The extent of reaction was monitored by real-time measurement of CO₂ and CH₄. Maximum conversion of CO₂ occurred at 300–350 °C. Approximately 60% conversion of CO₂ was realized at a space velocity of about 10,000 h^?1 with a molar ratio of H₂/CO₂ of 4/1. Somewhat higher total CO₂ conversion was possible by increasing the H₂/CO₂ ratio, but the most efficient use of available H₂ occurs at a lower H₂/CO₂ ratio.