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 production from palm oil via heterogeneous transesterification

This paper presents the study of the transesterification of palm oil via heterogeneous process using montmorillonite KSF as heterogeneous catalyst. This study was carried out using a design of experiment (DOE), specifically response surface methodology (RSM) based on four-variable central composite design (CCD) with α (alpha) = 2. The transesterification process variables were reaction temperature, x₁ (50–190 °C), reaction period, x₂ (60–300 min), methanol/oil ratio, x₃ (4–12 mol mol^?1) and amount of catalyst, x₄ (1–5 wt%). It was found that the yield of palm oil fatty acid methyl esters (FAME) could reach up to 79.6% using the following reaction conditions: reaction temperature of 190 °C, reaction period at 180 min, ratio of methanol/oil at 8:1 mol mol^?1 and amount of catalyst at 3%.     

Biodiesel from corn germ oil catalytic and non-catalytic supercritical methanol transesterification

Transesterifications of grain of corn oil samples in KOH catalytic and in supercritical methanol were studied without using any catalyst. Biodiesel, an alternative biodegradable diesel fuel, is derived from triglycerides by transesterification with methanol and ethanol. The transesterification reaction is affected by the molar ratio of glycerides to alcohol, catalysts, reaction temperature, reaction time and free fatty acids and water content of oils or fats. It was observed that increasing the reaction temperature, especially to supercritical temperatures, had a favorable influence on methyl ester (biodiesel) conversion. The molar ratio of methanol to corn germ oil is also one of the most important variables affecting the yield of methyl esters. Higher molar ratios result in greater ester production in a shorter time. In the transesterification, free fatty acids and water always produce negative effects, since the presence of free fatty acids and water causes soap formation, consumes catalysts, and reduces catalyst effectiveness, all of which result in a low conversion.     

Biodiesel production by ultrasound-assisted transesterification: State of the art and the perspectives

In the present paper state-of-the art and perspectives of ultrasound-assisted (UA) biodiesel production from different oil-bearing materials using acid, base and enzyme catalysts are critically discussed. The ultrasound action in biodiesel production is primarily based on the emulsification of the immiscible liquid reactants by microturbulence generated by radial motion of cavitation bubbles and the physical changes on the surface texture of the solid catalysts generating new active surface area. The importance of ultrasound characteristics and other process variables for the biodiesel yield and the reaction rate is focused on. UA transesterification is compared with other techniques for biodiesel production. Several different developing methods reducing the biodiesel production costs such as the optimization of process factors, the development of the process kinetic models, the use of phase transfer catalysts, the application of the continuous process, the design of novel types of ultrasonic reactors and the in situ ultrasound application in transesterification of oily feedstocks are also discussed.     

Biodiesel production using enzymatic transesterification - Current state and perspectives

Biodiesel has attracted considerable interest in recent years as an alternative, biodegradable and nonpolluting transportation fuel. Conventional alkaline process for biodiesel production are energy-consuming and generate undesirable by-products such as soaps, that make difficult the separation and purification of biodiesel.Particular attention has been dedicated to the use of lipases as biocatalysts for biodiesel production due to their favorable conversion rate obtained in gentle conditions and relatively simple downstream processing steps for the purification of biodiesel and by-products. However, comparatively to conventional chemical processes, the major obstacles for enzymatic production of biodiesel remain the cost of lipases, the relatively slower reaction rate and lipases inactivation caused by methanol and glycerol.This review evaluates the current status and perspectives for enzymatic biodiesel production and indicates the key operational variables that influence lipase activity and stability together with the technological solutions for industrial implementation of enzymatic process.     

Biodiesel production through transesterification of triolein with various alcohols in an ultrasonic field

The biodiesel production through transesterification of triolein with various alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol and decanol was investigated at molar ratio 6:1 (alcohol:triolein) and 25 °C in the presence of base catalysts (NaOH and KOH) under ultrasonic irradiation (40 kHz) and mechanical stirring (1800 rot/min) conditions. It was found that the rate of the alkyl ester formation under the ultrasonic irradiation condition was higher than that under the stirring condition. In addition, it was confirmed that the rate depended upon the kind of alcohols; as the number of carbon in alcohol increased, the rate of the ester formation tended to decrease. On the other hand, the secondary alcohols such as 2-propanol, 2-butanol, 2-hexanol, and 2-octanol showed little ester conversion, suggesting that the steric hindrance strongly affected the transesterification of triolein.     

亚临界甲醇中固体催化剂催化酯交换反应的活性比较

对几种固体催化剂用于亚临界甲醇与大豆油的酯交换反应制备生物柴油的催化活性进行了研究。考察在不同催化剂作用下酯交换反应产物中脂肪酸甲酯（FAMEs）含量随反应时间的变化规律。结果表明。在醇油摩尔比为40，反应温度为180℃，反应压力为2～3MPa，催化剂用量为3g及反应时间为10min的条件下，K2O／γ-Al2O3催化酯交换反应的产物中FAMEs含量达90％。     

Biodiesel production from waste cooking oil over sulfonated catalysts

Biodiesel production from waste cooking oil with methanol was carried out in the presence of poly(vinyl alcohol) with sulfonic acid groups (PVA-SO₃H) and polystyrene with sulfonic acid groups (PS-SO₃H), at 60°C. The PVA-SO₃H catalyst showed higher catalytic activity than the PS-SO₃H one. In order to optimize the reaction conditions, different parameters were studied. An increase of waste cooking oil conversion into fatty acid methyl esters with the amount of PVA-SO₃H was observed. When the transesterification and esterification of WCO was carried out with ethanol over PVA-SO₃H, at 60°C, a decrease of biodiesel production was also observed. The WCO conversion into fatty acid ethyl ester increased when the temperature was increased from 60 to 80°C. When different amounts of free fatty acids were added to the reaction mixture, a slight increase on the conversion was observed. The PVA-SO₃H catalyst was reused and recycled with negligible loss in the activity.     

Comparison of biodiesel production from crude Jatropha oil and Krating oil by supercritical methanol transesterification

This work compared the production of biodiesel from two different non-edible oils with relatively high acid values (Jatropha oil and Krating oil). Using non-catalytic supercritical methanol transesterification, high methyl ester yield (85–90%) can be obtained in a very short time (5–10 min). However, the dependence of fatty acid methyl ester yield on reaction conditions (i.e., temperature and pressure) and the optimum conditions were different by the source of oils and were correlated to the amount of free fatty acids (FFAs) and unsaturated fatty acid content in oils. Krating oil, which has higher FFAs and unsaturated fatty acid content, gave higher fatty acid methyl ester yield of 90.4% at 260 °C, 16 MPa, and 10 min whereas biodiesel from Jatropha oil gave fatty acid methyl ester yield of 84.6% at 320 °C, 15 MPa and 5 min using the same molar ratio of methanol to oil 40:1. The product quality from crude Krating oil met the biodiesel standard. Pre-processing steps such as degumming or oil purification are not necessary.     

Application of response surface methodology for optimizing transesterification of Moringa oleifera oil: Biodiesel production

Response surface methodology (RSM), with central composite rotatable design (CCRD), was used to explore optimum conditions for the transesterification of Moringa oleifera oil. Effects of four variables, reaction temperature (25–65 °C), reaction time (20–90 min), methanol/oil molar ratio (3:1–12:1) and catalyst concentration (0.25–1.25 wt.% KOH) were appraised. The quadratic term of methanol/oil molar ratio, catalyst concentration and reaction time while the interaction terms of methanol/oil molar ratio with reaction temperature and catalyst concentration, reaction time with catalyst concentration exhibited significant effects on the yield of Moringa oil methyl esters (MOMEs)/biodiesel, p < 0.0001 and p < 0.05, respectively. Transesterification under the optimum conditions ascertained presently by RSM: 6.4:1 methanol/oil molar ratio, 0.80% catalyst concentration, 55 °C reaction temperature and 71.08 min reaction time offered 94.30% MOMEs yield. The observed and predicted values of MOMEs yield showed a linear relationship. GLC analysis of MOMEs revealed oleic acid methyl ester, with contribution of 73.22%, as the principal component. Other methyl esters detected were of palmitic, stearic, behenic and arachidic acids. Thermal stability of MOMEs produced was evaluated by thermogravimetric curve. The fuel properties such as density, kinematic viscosity, lubricity, oxidative stability, higher heating value, cetane number and cloud point etc., of MOMEs were found to be within the ASTM D6751 and EN 14214 biodiesel standards.     

Recent developments on heterogeneous catalysts for biodiesel production by oil esterification and transesterification reactions: A review

Heterogeneous catalysis is widely applied in industry due to important advantages it offers to chemical processes such as improved selectivity and easy catalyst separation from reaction mixture, reducing process stages and wastes. This is the reason why nowadays heterogeneous catalysts are being developed to produce biodiesel. Several catalytic materials have been showed in bibliography: acid solids capable to carry out free fatty acids esterification reaction, base solids which are able to carry out triglycerides transesterification reaction and bifunctional solids (acid–base character) which show ability to simultaneously catalyze esterification and transesterification reaction. This review discusses the latest advances in research and development related with heterogeneous catalysts used to produce biodiesel.     

Zinc oxide nanorods based catalysts for hydrogen production by steam reforming of methanol

Zinc oxide (ZnO) nanorods were epitaxially grown on porous cordierite support by a hydrothermal process and utilized for catalyzing methanol steam reforming (MSR) reaction. Catalytic activity of ZnO nanorods for MSR process was correlated to the terminated surfaces of ZnO crystallites. Copper (Cu), palladium (Pd) and gold (Au) nanoparticles infused ZnO nanorods were prepared by in-situ precipitation of the metals on the nanorods. 28% hydrogen selectivity was observed with Cu/ZnO nanorods (Cu/10Zn), while Pd/ZnO nanorods and (Pd/10Zn) showed slightly lower activity. Higher catalytic activity of copper and palladium impregnated ZnO nanorods can be attributed to the synergistic combination of bimetallic oxides. In contrast, Au/ZnO nanorods (Au/10Zn) showed very high activity for methanol dehydrogenation and higher than 97% methanol conversion was achieved for operating temperatures as low as 200 °C.     

Biodiesel production by microalgal biotechnology

Biodiesel has received much attention in recent years. Although numerous reports are available on the production of biodiesel from vegetable oils of terraneous oil-plants, such as soybean, sunflower and palm oils, the production of biodiesel from microalgae is a newly emerging field. Microalgal biotechnology appears to possess high potential for biodiesel production because a significant increase in lipid content of microalgae is now possible through heterotrophic cultivation and genetic engineering approaches. This paper provides an overview of the technologies in the production of biodiesel from microalgae, including the various modes of cultivation for the production of oil-rich microalgal biomass, as well as the subsequent downstream processing for biodiesel production. The advances and prospects of using microalgal biotechnology for biodiesel production are discussed.     

Calculation and analysis of sub/supercritical methanol preheating tube for continuous production of biodiesel via supercritical methanol transesterification

Biodiesel is an important renewable energy. Supercritical methanol transesterification for biodiesel has recently been concerned because of its obvious advantages. The tubular reactor is an ideal reactor for continuous preparation of biodiesel via supercritical methanol transesterification. A methanol preheating tube is necessary for the tubular reaction system because the reaction temperature for supercritical methanol transesterification is usually 520–600 K. Therefore, in the range of 298–600 K, changes of the density, isobaric capacity, viscosity and thermal conductivity of sub/supercritical methanol with temperature are first discussed. Then on the basis of these thermophysical properties, an integration method is adopted for the design of sub/supercritical methanol preheating tube when methanol is preheated from 298 K to 600 K at 16 MPa and the influencing factors on the length of the preheating tube are also studied. The computational results show that the Reynolds number Re and the local convection heat-transfer coefficient α of sub/supercritical methanol flowing in Φ6× 1.5 mm preheating tube change drastically with temperature. For the local overall heat transfer coefficient K and the average overall heat transfer coefficient K _m, temperature also has an important influence on them when the inlet velocity of methanol is lower than 0.5 m/s. But when the inlet velocity of methanol is higher than 0.5 m/s, K and K _m almost keep invariable with temperature. Additionally, both the outlet temperature and the inlet velocity of methanol are the key affecting factors for the length of the preheating tube, especially when the outlet temperature is over the critical temperature of methanol. At the same time, the increase of tin bath’s temperature can shorten the required length of the preheating tube. At the inlet flow rate of 0.5 m/s, the required length of the preheating tube is 2.0m when methanol is preheated from 298 K to 590 K at 16 MPa with keeping the tin bath’s temperature 620 K, which is in good agreement with the experimental results.     

Calculation and analysis of sub/supercritical methanol preheating tube for continuous production of biodiesel via supercritical methanol transesterification

Biodiesel is an important renewable energy. Supercritical methanol transesterification for biodiesel has recently been concerned because of its obvious advantages. The tubular reactor is an ideal reactor for continuous preparation of biodiesel via supercritical methanol transesterification. A methanol preheating tube is necessary for the tubular reaction system because the reaction temperature for supercritical methanol transesterification is usually 520―600K. Therefore, in the range of 298―600K, changes of the density, isobaric capacity, viscosity and thermal conductivity of sub/supercritical methanol with temperature are first discussed. Then on the basis of these thermophysical properties, an integration method is adopted for the design of sub/supercritical methanol preheating tube when methanol is preheated from 298K to 600K at 16MPa and the influencing factors on the length of the preheating tube are also studied. The computational results show that the Reynolds number Re and the local convection heat-transfer coefficient α of sub/supercritical methanol flowing in ф6mm×1.5mm preheating tube change drastically with temperature. For the local overall heat transfer coefficient K and the average overall heat transfer coefficient K_m, temperature also has an important influence on them when the inlet velocity of methanol is lower than 0.5m/s. But when the inlet velocity of methanol is higher than 0.5m/s, K and K_m almost keep invariable with temperature. Additionally, both the outlet temperature and the inlet velocity of methanol are the key affecting factors for the length of the preheating tube, especially when the outlet temperature is over the critical temperature of methanol. At the same time, the increase of tin bath’s temperature can shorten the required length of the preheating tube. At the inlet flow rate of 0.5m/s, the required length of the preheating tube is 2.0m when methanol is preheated from 298K to 590K at 16MPa with keeping the tin bath’s temperature 620K, which is in good agreement with the experimental results.     

Optimization of transesterification conditions for the production of fatty acid methyl ester (FAME) from Chinese tallow kernel oil with surfactant-coated lipase

Surfactant-coated lipase was used as a catalyst in preparing fatty acid methyl ester (FAME) from Chinese tallow kernel oil from Sapium sebiferum (L.) Roxb. syn. Triadica sebifera (L.) small. FAME transesterification was analyzed using response surface methodology to find out the effect of the process variables on the esterification rate and to establish prediction models. Reaction temperature and time were found to be the main factors affecting the esterification rate with the presence of surfactant-coated lipase. Developed prediction models satisfactorily described the esterification rate as a function of reaction temperature, time, dosage of surfactant-coated lipase, ratio of methanol to oil, and water content. The FAME mainly contained fatty acid esters of C16:0, C18:0, C18:1, C18:2, and C18:3, determined by a gas chromatograph. The optimal esterification rate was 93.86%. The optimal conditions for the above esterification ratio were found to be a reaction time of 9.2 h, a reaction temperature of 49 °C, dosage of surfactant-coated lipase of 18.5%, a ratio of methanol to oil of 3:1, and water content of 15.6%. Thus, by using the central composite design, it is possible to determine accurate values of the transesterification parameters where maximum production of FAME occurs using the surfactant-coated lipase as a transesterification catalyst.     

Production of FAME by palm oil transesterification via supercritical methanol technology

The present study employed non-catalytic supercritical methanol technology to produce biodiesel from palm oil. The research was carried out in a batch-type tube reactor and heated beyond supercritical temperature and pressure of methanol, which are at 239 °C and 8.1 MPa respectively. The effects of temperature, reaction time and molar ratio of methanol to palm oil on the yield of fatty acid methyl esters (FAME) or biodiesel were investigated. The results obtained showed that non-catalytic supercritical methanol technology only required a mere 20 min reaction time to produce more than 70% yield of FAME. Compared to conventional catalytic methods, which required at least 1 h reaction time to obtain similar yield, supercritical methanol technology has been shown to be superior in terms of time and energy consumption. Apart from the shorter reaction time, it was found that separation and purification of the products were simpler since no catalyst is involved in the process. Hence, formation of side products such as soap in catalytic reactions does not occur in the supercritical methanol method.     

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.     

A facile noncatalytic methyl ester production from waste chicken tallow using single step subcritical methanol: Optimization study

In this modern era, an increase in urbanization causes the escalating trend of fuel demand as well as environmental pollution problems. Various biofuels research with the respect of climate change and emission reduction recently intensifies, particularly in biodiesel. In Indonesia, diesel oil currently in use contains 20% of biodiesel. Utilizing waste‐based resources such as rendered chicken tallow as the feedstock could be the solution to both energy and environmental challenges. However, chicken tallow contains a significant amount of free fatty acid (FFA) which will obstruct the production yield of biodiesel. In this study, catalyst‐free subcritical methanol has been employed to convert waste chicken tallow (WCT) with high FFA into biodiesel. Design of experiment was conducted to study the effect of temperature, time, and the molar ratio of methanol to fats on the purity and recovery of fatty acid methyl esters (FAMEs). Based on the optimization study performed by response surface methodology (RSM), all three independent variables gave a significant effect on the recovery of FAME. From the experimental results, the maximum FAME yield obtained was 98.43 ± 0.22% with the optimum condition as follows: 167°C, 36.8 minutes, and 42.7:1 (methanol/WCT, mol/mol), while the predicted FAME yield obtained using RSM was 97.76%. The methyl ester composition of WCT‐based biodiesel ranges from C13 to C24.     

Fast biodiesel production from beef tallow with radio frequency heating

Efficient biodiesel production from beef tallow was achieved with radio frequency (RF) heating. A conversion rate of 96.3 ± 0.5% was obtained with a NaOH concentration of 0.6% (based on tallow), an RF heating for 5 min, and a methanol/tallow molar ratio of 9:1. Response surface methodology was employed to evaluate the influence of NaOH dose, RF heating time, and methanol/tallow ratio. The alkaline concentration showed the largest positive impact on the conversion rate. Similar fast conversion from canola oil to biodiesel was achieved in our previous work, indicating that RF heating, as an accelerating technique for biodiesel production, had a large applying area. Viscosities of biodiesel products from beef tallow and canola oil were measured as 5.23 ± 0.01 and 4.86 ± 0.01 mm² s^?1, respectively, both meeting the specification in ASTM D6751 (1.9–6.0 mm² s^?1).