Transesterification of canola oil as biodiesel over Na/Zr-SBA-15 catalysts: Effect of zirconium content

A series of mesoporous Zr-SBA-15-supported Na catalysts was prepared and applied to the heterogeneous catalysis of canola oil transesterification. The effects of Si/Zr ratio, reaction time, and percentage of Na loading on the conversion to fatty acid methyl esters (FAME) were studied. The dependence of the textural structure and chemical properties of Zr-SBA-15 supports on Zr content was investigated using small-angle X-ray diffraction, Brunauer–Emmett–Teller analysis, transmission electron microscopy (TEM), and Fourier transform infrared (FTIR) spectroscopy. The results obtained from FTIR and TEM indicate that the incorporation of Zr atoms into the SBA-15 structure facilitated the formation of Brönsted acid sites and decreased the particle size of Na species. Catalysts with a higher Zr content enhanced the FAME yield. The optimum conditions determined were as follows: reaction temperature of 70 °C, 15 wt.% Na, reaction time of 6 h, and 12% catalyst content (wt.% oil) with a methanol/oil molar ratio of 6:1. The optimum conditions resulted in a FAME yield of up to 99%.     

Biodiesel production from refined sunflower vegetable oil over KOH/ZSM5 catalysts

ZSM5 zeolite was impregnated with different KOH loadings (15 wt.%, 25 wt.% and 35 wt.%) to prepare a series of KOH/ZSM5 catalysts. The catalysts were calcined at 500 °C for 3 h and then characterized by N₂ adsorption–desorption and X-ray diffraction (XRD) techniques. The catalysts were tested in the transesterification reaction in a batch reactor at 60 °C and under atmospheric pressure. It was found that KOH/ZSM5 with 35 wt.% loading showed the best catalytic performance. The best reaction conditions in the presence of KOH/ZSM5 (35 wt.%) were determined while modifying the catalyst to oil ratio and the reaction time. The highest methyl ester yield (>95%) was obtained for a reaction time of 24 h, a catalyst to oil ratio of 18 wt.%, and a methanol to oil molar ratio of 12:1. The properties of produced biodiesel complied with the ASTM specifications. The catalytic stability test showed that 35KOH/ZSM5 was stable for 3 consecutive runs. Characterization of the spent catalyst indicated that a slight deactivation might be due to the leaching of potassium oxides active sites.     

Performance evaluation of a vegetable oil fuelled compression ignition engine

Fuel crisis because of dramatic increase in vehicular population and environmental concerns have renewed interest of scientific community to look for alternative fuels of bio-origin such as vegetable oils. Vegetable oils can be produced from forests, vegetable oil crops, and oil bearing biomass materials. Non-edible vegetable oils such as linseed oil, mahua oil, rice bran oil, etc. are potentially effective diesel substitute. Vegetable oils have high-energy content. This study was carried out to investigate the performance and emission characteristics of linseed oil, mahua oil, rice bran oil and linseed oil methyl ester (LOME), in a stationary single cylinder, four-stroke diesel engine and compare it with mineral diesel. The linseed oil, mahua oil, rice bran oil and LOME were blended with diesel in different proportions. Baseline data for diesel fuel was collected. Engine tests were performed using all these blends of linseed, mahua, rice bran, and LOME. Straight vegetable oils posed operational and durability problems when subjected to long-term usage in CI engine. These problems are attributed to high viscosity, low volatility and polyunsaturated character of vegetable oils. However, these problems were not observed for LOME blends. Hence, process of transesterification is found to be an effective method of reducing vegetable oil viscosity and eliminating operational and durability problems. Economic analysis was also done in this study and it is found that use of vegetable oil and its derivative as diesel fuel substitutes has almost similar cost as that of mineral diesel.     

Biodiesel production from mixed soybean oil and rapeseed oil

The biodiesel (fatty acid methyl esters, FAME) was prepared by transesterification of the mixed oil (soybean oil and rapeseed oil) with sodium hydroxide (NaOH) as catalyst. The effects of mole ratio of methanol to oil, reaction temperature, catalyst amount and reaction time on the yield were studied. In order to decrease the operational temperature, a co-solvent (hexane) was added into the reactants and the conversion efficiency of the reaction was improved. The optimal reaction conditions were obtained by this experiment: methanol/oil mole ratio 5.0:1, reaction temperature 55 °C, catalyst amount 0.8 wt.% and reaction time 2.0 h. Under the optimum conditions, a 94% yield of methyl esters was reached ∼94%. The structure of the biodiesel was characterized by FT-IR spectroscopy. The sulfur content of biodiesel was determined by Inductively Coupled Plasma emission spectrometer (ICP), and the satisfied result was obtained. The properties of obtained biodiesel from mixed oil are close to commercial diesel fuel and is rated as a realistic fuel as an alternative to diesel. Production of biodiesel has positive impact on the utilization of agricultural and forestry products.     

Synthesis and characterisation of rubber seed oil trans-esterified biodiesel using cement clinker catalysts

The synthesis of biodiesel using rubber seed oil by a transesterification reaction using cement clinker catalysts was studied. The mineral composition and morphology of both the catalysts were analysed using X-ray diffraction and scanning electron microscopy. The gas chromatography–mass spectrometry, Fourier transform infrared spectroscopy and nuclear magnetic resonance studies were used to find the Fatty acid methyl ester content and various compounds of esters in the synthesised biodiesel, which showed an efficient conversion of rubber seed oil to biodiesel. The highest yield of 80% was obtained from calcium oxide catalyst (1.5?g) activated at 50°C with a methanol-to-oil ratio of 6:1. The highest yield of 70% biodiesel was obtained using a cement clinker catalyst (0.5?g) activated at 50°C with a methanol-to-oil ratio of 6:1. The significant physical properties of biodiesel flash point, acid value and saponification value were found, and the results are within the American standard test method (ASTM D6751) limits.     

Synthesis of biodiesel from vegetable oil with methanol catalyzed by Li-doped magnesium oxide catalysts

The preparation of a Li-doped MgO for biodiesel synthesis has been investigated by optimizing the catalyst composition and calcination temperatures. The results show that the formation of strong base sites is particularly promoted by the addition of Li, thus resulting in an increase of the biodiesel synthesis. The catalyst with the Li/Mg molar ratio of 0.08 and calcination temperature of 823 K exhibits the best performance. The biodiesel conversion decreases with further increasing Li/Mg molar ratio above 0.08, which is most likely attributed to the separated lithium hydroxide formed by excess Li ions and a concomitant decrease of BET values. In addition, the effects of methanol/oil molar ratio, reaction time, catalyst amount, and catalyst stability were also investigated for the optimized Li-doped MgO. The metal leaching from the Li-doped MgO catalysts was detected, indicating more studies are needed to stabilize the catalysts for its application in the large-scale biodiesel production facilities.     

Castor oil transesterification reaction: A kinetic study and optimization of parameters

In this paper, parameters affecting castor oil transesterification reaction were investigated. Applying four basic catalysts including NaOCH₃, NaOH, KOCH₃ and KOH the best one with maximum biodiesel yield was identified. Using Taguchi method consisting four parameters and three levels, the best experimental conditions were determined. Reaction temperature (25, 65 and 80 °C), mixing intensity (250, 400 and 600 rpm), alcohol/oil ratio (4:1, 6:1 and 8:1) and catalyst concentration (0.25, 0.35 and 0.5%) were selected as experimental parameters. It was concluded that reaction temperature and mixing intensity can be optimized. Using the optimum results, we proposed a kinetic model which resulted in establishing an equation for the beginning rate of transesterification reaction. Furthermore, applying ASTM D 976 correlation, minimum cetane number of produced biodiesel was determined as 37.1.     

Manufacturing of zeolite based catalyst from zeolite tuft for biodiesel production from waste sunflower oil

In the present work, zeolite based catalyst was prepared from zeolite tuft by impregnation methods. The zeolite tuft was initially treated with hydrochloric acid (16%) and then several KOH/zeolite catalysts were prepared by impregnation in KOH solutions. Various solutions of KOH with different molarities (1–6 M) were used. Further modification for the catalyst was performed by a 2nd step impregnation treatment by heating and stirring the KOH/zeolite to 80 °C for 4 h. The zeolite tuft and the prepared catalysts were characterized by several analytical techniques in order to explore their physicochemical properties. These tests include: X-Ray Fluorescence (XRF), Scanning Electron Microscopy (SEM), Zero point of Charge (PHzpc), Fourier Transform Infrared (FT-IR), Energy-dispersive X-Ray analysis (EDX) and X-Ray Diffraction (XRD). The catalysts were then used for transesterification of waste sunflower vegetable oil in order to produce biodiesel. Among the different catalysts prepared, the 1–4M KOH/TZT catalyst provided the maximum biodiesel yield of 96.7% at 50 °C reaction temperature, methanol to oil molar ratio of 11.5:1, agitation speed of 800 rpm, 335 μm catalyst particle size and 2 h reaction time. The physicochemical properties of the produced biodiesel comply with the EN and ASTM standard specifications.     

Biodiesel production from vegetable oils via catalytic and non-catalytic supercritical methanol transesterification methods

This paper reviews the production and characterization of biodiesel (BD or B) as well as the experimental work carried out by many researchers in this field. BD fuel is a renewable substitute fuel for petroleum diesel or petrodiesel (PD) fuel made from vegetable or animal fats. BD fuel can be used in any mixture with PD fuel as it has very similar characteristics but it has lower exhaust emissions. BD fuel has better properties than that of PD fuel such as renewable, biodegradable, non-toxic, and essentially free of sulfur and aromatics. There are more than 350 oil bearing crops identified, among which only sunflower, safflower, soybean, cottonseed, rapeseed and peanut oils are considered as potential alternative fuels for diesel engines. The major problem associated with the use of pure vegetable oils as fuels, for Diesel engines are caused by high fuel viscosity in compression ignition. Dilution, micro-emulsification, pyrolysis and transesterification are the four techniques applied to solve the problems encountered with the high fuel viscosity. Dilution of oils with solvents and microemulsions of vegetable oils lowers the viscosity, some engine performance problems still exist. The viscosity values of vegetable oils vary between 27.2 and 53.6 mm²/s whereas those of vegetable oil methyl esters between 3.59 and 4.63 mm²/s. The viscosity values of vegetable oil methyl esters highly decreases after transesterification process. Compared to no. 2 diesel fuel, all of the vegetable oil methyl esters were slightly viscous. The flash point values of vegetable oil methyl esters are highly lower than those of vegetable oils. An increase in density from 860 to 885 kg/m³ for vegetable oil methyl esters or biodiesels increases the viscosity from 3.59 to 4.63 mm²/s and the increases are highly regular. The purpose of the transesterification process is to lower the viscosity of the oil. The transesterfication of triglycerides by methanol, ethanol, propanol and butanol, has proved to be the most promising process. Methanol is the commonly used alcohol in this process, due in part to its low cost. Methyl esters of vegetable oils have several outstanding advantages among other new-renewable and clean engine fuel alternatives. The most important variables affecting the methyl ester yield during the transesterification reaction are molar ratio of alcohol to vegetable oil and reaction temperature. Biodiesel has become more attractive recently because of its environmental benefits. Biodiesel is an environmentally friendly fuel that can be used in any diesel engine without modification.     

Biodiesel from Milo (Thespesia populnea L.) seed oil

There is a need to seek non-conventional seed oil sources for biodiesel production due to issues such as supply and availability as well as food versus fuel. In this context, Milo (Thespesia populnea L.) seed oil was investigated for the first time as a potential non-conventional feedstock for preparation of biodiesel. This is also the first report of a biodiesel fuel produced from a feedstock containing cyclic fatty acids as T. populnea contains 8,9-methylene-8-heptadecenoic (malvalic) and smaller amounts of two cyclopropane fatty acids besides greater amounts of linoleic, oleic and palmitic acids. The crude oil extracted from T. populnea seed was transesterified under standard conditions with sodium methoxide as catalyst. Biodiesel derived from T. populnea seed oil exhibited fuel properties of density 880 kg m⁻³, kinematic viscosity 4.25 mm²/s; cetane number 59.8; flash point 176 °C; cloud point 9 °C; pour point 8 °C; cold filter plugging point 9 °C; sulfur content 11 mg kg⁻¹; water content 150 mg kg⁻¹; ash content 15 mg kg⁻¹; and acid value as KOH 250 mg kg⁻¹. The oxidative stability of 2.91 h would require the use of antioxidants to meet specifications in standards. Generally, most results compared well with ASTM D6751 and EN 14214 specifications.     

Catalytic production of biodiesel from soy-bean oil, used frying oil and tallow

Three fatty materials, soy-bean oil, used frying oil and tallow, were transformed into two different types of biodiesel, by transesterification and amidation reactions with methanol and diethylamine respectively. The ignition properties of these types of biodiesel were evaluated calculating the cetane index of the transesterification products, and the blending cetane number of the amide biodiesel blended with conventional diesel. Amide biodiesel enhances the ignition properties of the petrochemical diesel fuel, and it could account for the 5% market share that should be secured to biofuels by 2005.     

Viscosity correlations for jojoba oil blends with biodiesel and petroleum diesel

In this study, the effect of temperature and mixture composition on viscosity of Jojoba oil-Biodiesel (JO-BD) and Jojoba oil-Diesel (JO-PD) blends are investigated. Moreover, the relationship between the viscosity and the specific gravity of the blends is studied. Experimental viscosity data for the temperature range between 20°C and 80°C are used. The results show that the viscosity–temperature dependency can be well correlated by Vogel model for the viscosity–temperature relation. Also, a method that could estimate the blends viscosity from the specific gravity data is established.     

Study on the viscosity of jojoba oil blends with biodiesel or petroleum diesel

In this study, generalized equations for predicting temperature-dependent viscosities of jojoba oil/biodiesel (JO-BD) and jojoba oil/diesel blends are given and a Buddenbrerg–Wilke mixing equation for predicting the viscosities of the blends is used. For JO-BD blends, the maximum overall absolute average deviation obtained using the proposed models is 1.85% and it is comparable with that obtained using Tat and Van Gerpen (1.96%) model and at the same time lower than those obtained using Walther model (4.61%) and Wang–Briggs model (4.68%). The results obtained using Buddenbrerg–Wilke mixing equation are in agreement with those obtained using Arrhenius and Cragoe mixing models.     

Biodiesel production from crude rice bran oil and properties as fuel

This research reported on the successfully production of biodiesel by transesterification of crude rice bran oil (RBO). The process included three-steps. Firstly, the acid value of RBO was reduced to below 1 mg KOH/g by two-steps pretreatment process in the presence of sulfuric acid catalyst. Secondly, the product prepared from the first process was carried out esterification with an alkaline catalyst. The influence of four variables on conversion efficiency to methyl ester, i.e., methanol/RBO molar ratio, catalyst amount, reaction temperature and reaction time, was studied at this stage. The content of methyl ester was analyzed by chromatographic analysis. Through orthogonal analysis of parameters in a four-factor and three-level test, the optimum reaction conditions for the transesterification were obtained: methanol/RBO molar ratio 6:1, usage amount of KOH 0.9% w/w, reaction temperature 60 °C and reaction time 60 min. In the third step, methyl ester prepared from the second processing step was refined to become biodiesel. Fuel properties of RBO biodiesel were studied and compared according to ASTM D6751-02 and DIN V51606 standards for biodiesel. Most fuel properties complied with the limits prescribed in the aforementioned standards. The consequent engine test showed a similar power output compared with regular diesel but consumption rate was slightly higher. Emission tests showed a marked decrease in CO, HC and PM, however, with a slight increase in NO_X.     

Optimization of biodiesel production from camelina oil using orthogonal experiment

Camelina oil is a low-cost feedstock for biodiesel production that has received a great deal of attention in recent years. This paper describes an optimization study on the production of biodiesel from camelina seed oil using alkaline transesterification. The optimization was based on sixteen well-planned orthogonal experiments (OA₁₆ matrix). Four main process conditions in the transesterification reaction for obtaining the maximum biodiesel production yield (i.e. methanol quantity, reaction time, reaction temperature and catalyst concentration) were investigated. It was found that the order of significant factors for biodiesel production is catalyst concentration > reaction time > reaction temperature > methanol to oil ratio. Based on the results of the range analysis and analysis of variance (ANOVA), the maximum biodiesel yield was found at a molar ratio of methanol to oil of 8:1, a reaction time of 70 min, a reaction temperature of 50 °C, and a catalyst concentration of 1 wt.%. The product and FAME yields of biodiesel under optimal conditions reached 95.8% and 98.4%, respectively. The properties of the optimized biodiesel, including density, kinematic viscosity, acid value, etc., were determined and compared with those produced from other oil feedstocks. The optimized biodiesel from camelina oil meets the relevant ASTM D6571 and EN 14214 biodiesel standards and can be used as a qualified fuel for diesel engines.     

Using of cotton oil soapstock biodiesel–diesel fuel blends as an alternative diesel fuel

In this study, usability of cotton oil soapstock biodiesel–diesel fuel blends as an alternative fuel for diesel engines were studied. Biodiesel was produced by reacting cotton oil soapstock with methyl alcohol at determined optimum condition. The cotton oil biodiesel–diesel fuel blends were tested in a single cylinder direct injection diesel engine. Engine performances and smoke value were measured at full load condition. Torque and power output of the engine with cotton oil soapstock biodiesel–diesel fuel blends decreased by 5.8% and 6.2%, respectively. Specific fuel consumption of engine with cotton oil soapstock–diesel fuel blends increased up to 10.5%. At maximum torque speeds, smoke level of engine with blend fuels decreased up to 46.6%, depending on the amount of biodiesel. These results were compared with diesel fuel values.     

Calcium-based mixed oxide catalysts for methanolysis of Jatropha curcas oil to biodiesel

Calcium-based mixed oxides catalysts (CaMgO and CaZnO) have been investigated for the transesterification of Jatropha curcas oil (JCO) with methanol, in order to evaluate their potential as heterogeneous catalysts for biodiesel production. Both CaMgO and CaZnO catalysts were prepared by coprecipitation method of the corresponding mixed metal nitrate solution in the presence of a soluble carbonate salt at ∼ pH 8-9. The catalysts were characterized by X-ray diffraction (XRD), temperature programmed desorption of CO₂ (CO₂-TPD), scanning electron microscopy (SEM) and N₂ adsorption (BET). The conversion of JCO by CaMgO and CaZnO were studied and compared with calcium oxide (CaO), magnesium oxide (MgO) and zinc oxide (ZnO) catalysts. Both CaMgO and CaZnO catalysts showed high activity as CaO and were easily separated from the product. CaMgO was found more active than CaZnO in the transesterification of JCO with methanol. Under the suitable transesterification conditions at 338 K (catalyst amount = 4 wt. %, methanol/oil molar ratio = 15, reaction time = 6 h), the JCO conversion of more than 80% can be achieved over CaMgO and CaZnO catalysts. Even though CaO gave the highest activity, the conversion of JCO decreased significantly after reused for forth run whereas the conversion was only slightly lowered for CaMgO and CaZnO after sixth run.     

A comparative study of vegetable oil methyl esters (biodiesels)

In the present study, rubber seed oil, coconut oil and palm kernel oil, which are locally available especially in Kerala (India), are chosen and their transesterification processes have been investigated. The various process variables like temperature, catalyst concentration, amount of methanol and reaction time were optimized. Biodiesel from rubber seed oil (with high free fatty acid) was produced by employing two-step pretreatment process (acid esterification) to reduce acid value from 48 to 1.72 mg KOH/g with 0.40 and 0.35 v/v methanol-oil ratio and 1.0% v/v H₂SO₄ as catalyst at a temperature of 63(±2) °C with 1 h reaction time followed by transesterification using methanol-oil ratio of 0.30 v/v, 0.5 w/v KOH as alkaline catalyst at 55(±2) °C with 40 min reaction time to yield 98-99% biodiesel. Coconut oil and palm oil, being edible oils, transesterification with 0.25 v/v methanol-oil ratio, 0.50% w/v KOH as at 58(±2) °C, 20 min reaction time for coconut oil and 0.25% v/v methanol-oil ratio, 0.50% w/v KOH as alkaline catalyst at 60(±2) °C for palm kernel oil will convert them to 98-99% biodiesel. The brake thermal efficiency of palm oil biodiesel was higher with lower brake specific fuel consumption, but rubber seed oil biodiesel(ROB) showed less emission (CO and NO_x) compared to other biodiesels.     

Performance and emission study of Mahua oil (madhuca indica oil) ethyl ester in a 4-stroke natural aspirated direct injection diesel engine

In this investigation, Mahua Oil Ethyl Ester was prepared by transesterification using sulfuric acid (H₂SO₄) as catalyst and tested in a 4-stroke direct injection natural aspirated diesel engine. Tests were carried out at constant speed of 1500 rev/min at different brake mean effective pressures. Results showed that brake thermal efficiency of Mahua Oil Ethyl Ester (MOEE) was comparable with diesel and it was observed that 26.36% for diesel whereas 26.42% for MOEE. Emissions of carbon monoxide, hydrocarbons, oxides of nitrogen and Bosch smoke number were reduced around 58, 63, 12 and 70%, respectively, in case of MOEE compared to diesel. Based on this study, MOEE can be used a substitute for diesel in diesel engine.     

Characterization and transesterification of Iranian bitter almond oil for biodiesel production

In the present work the production of biodiesel using bitter almond oil (BAO) in a potassium hydroxide catalyzed transesterification reaction was investigated. The BAO was obtained from resources available in Iran and its physical and chemical properties including iodine value, acid value, density, kinematic viscosity, fatty acid composition and mean molecular weight were specified. The low acid value of BAO (0.24 mg KOH/g) indicated that the pretreatment of raw oil with acid was not required. The fatty acid content analysis confirmed that the contribution of unsaturated fatty acids in the BAO is high (84.7 wt.%). Effect of different parameters including methanol to oil molar ratio (3–11 mol/mol), potassium hydroxide concentration (0.1–1.7% w/w) and reaction temperature (30–70 °C) on the production of biodiesel were investigated. The results indicated that these parameters were important factors affecting the tranesterification reaction. The fuel properties of biodiesel including iodine value, acid value, density, kinematic viscosity, saponification value, cetane number, flash point, cloud point, pour point and distillation characteristics were measured. The properties were compared with those of petroleum diesel, EN 14214 and ASTM 6751 biodiesel standards and an acceptable agreement was observed.