Biodiesel fuels from palm oil via the non-catalytic transesterification in a bubble column reactor at atmospheric pressure: A kinetic study

Biodiesel has become more attractive recently because of its environmental benefits and the fact that it is made from renewable resources. Transesterification of vegetable oils with short-chain alcohol has long been a preferred method for producing biodiesel fuel. A new reactor was developed to produce fatty acid methyl esters (FAME) by blowing bubbles of superheated methanol vapor continuously into vegetable oil without using any catalysts. A kinetic study on the non-catalytic transesterification of palm oil was made in a reactor without stirring at atmospheric pressure. The effects of reaction temperatures (523, 543, and 563 K) on the rate constant, conversion, yield of methyl esters (ME) and composition of the reaction product under semi-batch mode operation are investigated. The activation energy and the frequency factor values of the transesterification reaction obtained in this experiment are 31 kJ/mol and 4.2, respectively. The optimum reaction temperature which gives the highest ME content (95.17% w/w) in the reaction product is 523 K, while the rate constant of the total system increased with reaction temperature.     

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.     

Effect of reaction parameters on the catalytic transesterification of cottonseed oil using silica sulfuric acid

Transesterification of refined cottonseed oil was studied in the presence of silica sulfuric acid as a new heterogeneous solid acid catalyst to overcome the drawbacks of homogeneous alkali and acid catalysts. The effect of various reaction parameters, such as oil to methanol ratio, reaction temperature, reaction time, and catalyst amount, was investigated. The highest methyl ester conversion was obtained at 373 K using 5% catalyst amount and 1:20 methanol ratio within 8 h. Silica sulfuric acid was found to be a promising catalyst for cleaner biodiesel production without tedious post treatments for the product purification.     

A novel one-pot synthesis of tetragonal sulfated zirconia catalyst with high activity for biodiesel production from the transesterification of soybean oil

A sulfated zirconia catalyst has been prepared by a novel one-pot vapor-controlled synthesis route using ammonium persulphate as sulfate agent. A possible formation mechanism of the catalyst is proposed. The effect of calcination temperature and S/Zr molar ratio on the structural, textural and catalytic properties of the prepared catalyst were investigated in detail using X-ray diffraction (XRD), N₂ adsorption–desorption, ammonia temperature programmed desorption (NH₃-TPD), Fourier transform infrared spectroscopy (FTIR) and a scanning electron microscope (SEM) which was equipped with an energy dispersive spectroscope (EDS). The results indicated that the samples calcined at 500 °C possessed zirconia of pure tetragonal structure, more content of sulfur and better distribution of acid sites on the surface of zirconia compared with the samples calcined at 600  °C at fixed S/Zr molar ratio. Moreover, they showed excellent catalytic activity with 100% yields of biodiesel for the transesterification of soybean oil with methanol.     

Alkaline catalyzed biodiesel production from moringa oleifera oil with optimized production parameters

The utilization of non-edible feedstock such as moringa oleifera for biodiesel production attracts much attention owing to the issue with regards to avoiding a threat to food supplies. In this study, the optimization of biodiesel production parameters for moringa oleifera oil was carried out. The free fatty acid value of moringa oil was found to be 0.6%, rendering the one step alkaline transesterification method for converting moringa fatty acids to their methyl esters possible. The optimum production parameters: catalyst amount, alcohol amount, temperature, agitation speed and reaction time were determined experimentally and found to be: 1.0 wt% catalyst amount, 30 wt% methanol amount, 60 °C reaction temperature, 400 rpm agitation rate and 60 min reaction time. With these optimal conditions the conversion efficiency was 82%. The properties of the moringa biodiesel that was produced were observed to fall within the recommended international biodiesel standards. However, moringa biodiesel showed high values of cloud and pour points of 10 °C and 3 °C respectively, which present a problem as regards use in cold temperatures.     

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.     

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.     

Transesterification of jojoba oil,sunflower oil,neem oil,rocket seed oil and linseed oil by tin catalysts

The methanolysis of jojoba oil has been studied in the presence of tin powder, dibutyltin diacetate (C₄H₉)₂Sn(OOCCH₃)₂, dioctyltin diacetate (C₈H₁₇)₂Sn(OOCCH₃)₂, dibutyltin oxide (C₄H₉)₂SnO, dioctyltin oxide (C₈H₁₇)₂SnO, diphenyltin oxide (C₆H₅)₂SnO, dibutyltin chloride dihydroxide (C₄H₉)₂Sn(OH)₂Cl, butyltinhydroxide hydrate (C₄H₉)Sn(=O)OH.xH₂O, Ni nanoparticles and Pd nanoparticles act as catalysts. Among these, 1 weight % of dibutyltin diacetate shows the maximum conversion. Then, methanolysis of sunflower oil, neem oil, rocket seed oil and linseed oil into methyl esters studied in the presence of 1% dibutyltin diacetate as a catalyst and was compared their percentage conversions. The experimental yield for the conversion of jojoba oil, sunflower oil, neem oil, rocket seed oil and linseed oil into biodiesel was found to be 71%, 51%, 50.78%, 40.90% and 39.66%, respectively. The experimental yield of the conversion of jojoba oil into methyl esters was found to be increased up to 96% by increasing reaction time, without emulsion formation. The synthesis of jojoba seed oil biodiesel (JSOB), soybean oil biodiesel (SOB), neem oil biodiesel (NOB), rocket seed oil biodiesel (RSOB) and linseed oil biodiesel (LSOB) was confirmed by NMR (¹H & ¹³C) and FT-IR analyses of biodiesel.     

Performance and emission analysis of compression ignition engine using biodiesels from Acid oil,Mahua oil,and Castor oil

Research on and use of biodiesels for engines is growing continuously in the present era. Compression ignition (CI) engine performance for biodiesels of blends B20 from Acid oil, Mahua oil, and Castor oil is experimentally investigated. The engine performance analysis in the form of brake‐specific fuel consumption, brake‐specific energy consumption, brake thermal efficiency (BTE), exhaust gas temperature (EGT), and air fuel ratio are compared with diesel as base fuel. Emission characteristics like CO, CO₂, NOx, and opacity are comparatively studied in detail for the considered biodiesels. The entire study is compared with the performance of engine when pure diesel is chosen as fuel. From the complete analysis it was observed that the BTE was higher for Acid oil and Mahua oil among the biodiesels used. And regarding CO emissions, Mahua oil showed lower effect than other biodiesels. Upto 6% increase in EGT of Mahua oil was obtained at no load and for other loads the percent reduced. For all the biodiesels the % enhancement in Co, CO₂, and NOx was more than 60% at highest load compared with diesel.     

Biodiesel production from castor oil in Brazil: A difficult reality

The Brazilian National Program for Production and Use of Biodiesel (PNPB in Portuguese) has created a huge demand for biodiesel in Brazil. The PNPB is strongly based on social development through the inclusion of family farmers in projects integrated with biodiesel power plants. Among the various oilseeds, castor bean (Ricinus communis L.) was identified as the ideal one to promote social development in the semi-arid region. However, although promising, the mechanisms of the federal program are still insufficient to promote the effective participation of family farmers. This research shows that companies are facing huge problems in implementing contracts with family farmers. It describes and analyzes the functioning dynamics of this agro-production chain. This paper addresses the identification and the discussion of these obstacles, in order to increase the competitiveness of the biodiesel agribusiness chain, based on castor oil social projects in Brazil.     

Optimization of transesterification process parameters of castor oil ethanolysis using response surface methodology-based genetic algorithm

Castor oil is unusual oil that is predominantly composed of ricinoleic acid. In the present study, castor oil biodiesel was produced from castor oil with bio-alcohol (ethanol) via a transesterification process. Also, this study investigates the influence of transesterification process parameters, i.e., reaction temperature, catalyst (sodium ethoxide) concentration, and ethanol:castor oil molar ratio on the yield of castor oil ethyl ester. The experiments are carried our as per a central composite design. A second-order response surface model was developed to predict the yield of castor oil ethyl ester as a function of transesterification process parameters. The developed models indicated that the predicted values are well in agreement with the experimental results. Finally, optimization of transesterification process parameters was carried out using a response surface methodology-based genetic algorithm. The optimization results indicated a reaction temperature of 41°C, catalyst concentration of 1.25% w/w of oil, and ethanol to oil molar ratio of 18.42 for achieving a higher yield of castor oil ethyl ester of 93.9%.     

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.     

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.     

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.     

Alkaline-catalyzed transesterification of Silurus triostegus Heckel fish oil: Optimization of transesterification parameters

The present work reports the production of biodiesel from Silurus triostegus Heckel fish oil (STFO) through alkaline-catalyzed transesterification by using potassium hydroxide (KOH) as an alkaline catalyst with methanol. Chemical and physical properties of the extracted oil were determined. It was found that STFO has a low acid value (1.90 mg KOH/g oil); hence no pre-treatment such as acid esterification is required to produce the biodiesel. The influence of the experimental parameters such as KOH concentration (0.25–1.0% w/w of oil), methanol to oil molar ratio (3:1, 6:1, 9:1 and 12:1), reaction temperature (32, 45 and 60 °C), reaction duration (30, 60, 90 and 120 min), type of the catalyst (potassium or sodium hydroxide) and step multiplicity (single- and two-step transesterification) on the yield of the biodiesel were investigated. The maximum biodiesel yield (96%) was obtained under the optimized parameters of the transesterification (KOH 0.50% w/w, 6:1 methanol to oil, at 32 °C for 60 min). The properties of the produced biodiesel were found to conform with the ASTM standard, indicating its suitability for internal combustion engines. Blending of the produced biodiesel with petro diesel with various volume percentages was investigated as well.     

Evaluation and optimization of two stage sequential in situ transesterification process for fatty acid methyl ester quantification from microalgae

This study demonstrates a direct transesterification (DT) method for reliable quantification of microalgal lipid. Primary screening of various transesterification methods and the types of biomass (wet, oven dried and lyophilized) were performed with heterotrophically grown Chlorella sp. FC2 IITG which revealed two stage DT with lyophilized biomass using NaOH in first stage and H₂SO₄ in second stage as the best combination with fatty acid methyl ester (FAME) yield of 39.17% (w/w, dry cell weight). Further optimization of transesterification parameters for selected method using response surface methodology, predicted the optimum values for catalyst to biomass ratio 0.67 (w/w) and 2.07 (v/w), methanol to biomass ratio 49.51 (v/w) and 61.07 (v/w) and reaction time 19.33 (min) and 10 (min) for first and second stages respectively. The optimum conditions showed 462.6% and 445.4% increment in FAME yield when compared with Bligh and Dyer method for Chlorella sp. FC2 IITG and Chlorella sorokiniana FC6 IITG respectively with highest transesterification efficiency of 98.96%. Improved transesterification efficiency of two stage DT was attributed to efficient destabilization of cell wall as confirmed by scanning electron microscopic imaging. FAME produced via DT of Chlorella sp. FC2 IITG satisfied most of the biodiesel properties as per ASTM D6751 and hence, could be an alternative to petro-diesel.     

Tetramethylguanidine as an efficient catalyst for transesterification of waste frying oils

New catalysts and environmentally benign processes may lead to methyl ester production with improved properties at competitive costs. In this study, transesterification of waste frying oil to biodiesel using tetramethylguanidine as a strong base catalyst was conducted. The influence of catalyst concentration and of certain physicochemical properties of waste frying oil was investigated. Experiments were also performed on a semi-refined cottonseed oil for comparison purposes. Experimental results showed that methyl ester conversion was dependent on the type of oil, catalyst concentration and reaction time.     

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 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.     

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.