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.     

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.     

Biodiesel from different oil using fixed-bed and plug-flow reactors

In this study, a pilot scale of 100 t/year biodiesel production system, mainly consisting of a fixed-bed and a down-stream plug-flow reactors, was setup to test different feedstock oils, especially a kind of high-acidified oil, trap grease, for their feasibility as biodiesel feedstock in China. The tested oils include three kinds of typical oil from Guangdong Province, China: rapeseed oil, Chinese wood oil, and trap grease. At the same time the optimum residence time for a plug-flow reactor to perform transesterification reaction was investigated in this study. At the temperature of 65 °C, methanol/oil molar ratio of 6:1 and KOH load of 1.2 wt% of oil, the optimum residence time was found to be 19 min. A type of ion-exchange resin was used to fill in the fixed-bed reactor and used as the esterification catalyst for pretreating on the high-acidified oil. For the fresh catalyst, the acid value of trap grease could be reduced from 114 mg KOH/g to about 2 mg KOH/g after 13 h at temperature 75 °C, catalyst load of 15 wt% of oil, methanol addition of 20 wt% of oil. The lifetime test for the catalyst indicated that its life is over 30 days. The quality of biodiesel derived from three feedstock oils is compared with newly published China BD100 standard of GB/T20828-2007. A comparison of the results reveals that the biodiesel generated through this system could satisfactorily meet China BD100 standard. It indicates that the designed process in this system has a good adaptability for different kinds of oil.     

Biodiesel production from soybean and Jatropha oils using cesium impregnated sodium zirconate as a heterogeneous base catalyst

Cesium modified sodium zirconate (Cs-Na₂ZrO₃) was prepared by ionic exchange from sodium zirconate (Na₂ZrO₃), which was synthesized via a solid state reaction. Both ceramics, i.e., pristine Na₂ZrO₃ and the Cs-Na₂ZrO₃, were used as basic heterogeneous catalysts in biodiesel production. Soybean and Jatropha oils were used as triglyceride sources for transesterification reactions. Parameters, such as catalyst concentration (between 0.5 and 3 wt%), reaction time, different methanol/vegetable oil molar ratios, and temperature of the reaction, were evaluated. The cesium cation influence was evaluated from the basic transesterification reactivity. The results showed that the introduction of cesium significantly modified the catalytic activity in biodiesel production. Cs enhanced the reaction kinetics in obtaining biodiesel and reduced the reaction time in comparison with pristine Na₂ZrO₃. The results showed that Cs-Na₂ZrO₃ as a basic heterogeneous catalyst exhibited the best fatty acid methyl esters (FAME) conversion for soybean oil (98.8%) at 1 wt%, 30:1 methanol/oil ratio, 65 °C, and 15 min. The best conditions for Jatropha oil (90.8%) were 3 wt%, 15:1 methanol/oil ratio, 65 °C, and 1 h. The impregnation of Na₂ZrO₃ with cesium represents a very exciting alternative heterogeneous base catalyst for biodiesel production.     

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.     

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.     

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 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.     

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.     

Preparation, characterization and application of heterogeneous solid base catalyst for biodiesel production from soybean oil

A solid base catalyst was prepared by neodymium oxide loaded with potassium hydroxide and investigated for transesterification of soybean oil with methanol to biodiesel. After loading KOH of 30 wt.% on neodymium oxide followed by calcination at 600 °C, the catalyst gave the highest basicity and the best catalytic activity for this reaction. The obtained catalyst was characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), Thermogravimetric analysis (TGA), N₂ adsorption-desorption measurements and the Hammett indicator method. The catalyst has longer lifetime and maintained sustained activity after being used for five times, and were noncorrosive and environmentally benign. The separate effects of the molar ratio of methanol to oil, reaction temperature, mass ratio of catalyst to oil and reaction time were investigated. The experimental results showed that a 14:1 M ratio of methanol to oil, addition of 6.0% catalyst, 60 °C reaction temperature and 1.5 h reaction time gave the best results and the biodiesel yield of 92.41% was achieved. The properties of obtained biodiesel are close to commercial diesel fuel and is rated as a realistic fuel as an alternative to diesel.     

Effect of incompletely converted soybean oil on biodiesel quality

Presence of fully converted monoalkyl esters is the major requirement in quality biodiesel. Due to high associated costs with testing and widespread production of biodiesel not only in commercial scale but also in small scale, there is a high propensity of substandard biodiesel entering the market and being used in compression ignition engines. Due to this reason, it is important to understand how low grade biodiesel with a lower methyl ester conversion affects the parameters of quality standards and as a result, engine performance and durability. In this paper, the performance of fatty acid methyl esters with different proportions of unconverted triglycerides has been evaluated. The study has comprehensively evaluated the effect of unconverted triglycerides on flash point, water and sediment, kinematic viscosity, sulfur content, sulfated ash, copper strip corrosion, cetane number, cloud point, carbon residue, acid number, free glycerin, total glycerin, phosphorus content and distillation temperature.     

Optimization of conversion of waste rapeseed oil with high FFA to biodiesel using response surface methodology

In the present study, waste rapeseed oil with high free fatty acids (FFA) was used as feedstock for producing biodiesel. In the pretreatment step, FFA was reduced by distillation refining method. Then, biodiesel was produced by alkaline-catalyzed transesterification process, which was designed according to the 2⁴ full-factorial central composite design. The response surface methodology (RSM) was used to optimize the conditions for the maximum conversion to biodiesel and understand the significance and interaction of the factors affecting the biodiesel production. The results showed that catalyst concentration and reaction time were the limiting conditions and little variation in their value would alter the conversion. At the same time, there was a significant mutual interaction between catalyst concentration and reaction time.The biodiesel produced in the present experiment was analyzed by gas chromatography/mass spectrometry (GC/MS), which showed that it mainly contained six fatty acid methyl esters. In addition, the diesel indexes analysis showed that most of the fuel properties were in reasonable agreement with the 0# diesel standard of China (GB252-2000) and the biodiesel standard of America (ASTM D6751).     

植物油作为发动机燃料及生物柴油制备的研究

本文详细介绍了植物油作为发动机燃料的4种应用方式。生物柴油是绿色可再生能源，由动植物油的酯交换反应获得。讨论了生物柴油制备过程中的反应动力学以及水份、游离脂肪酸、催化剂、醇油摩尔比、反应温度等对酯交换的影响。     

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.     

Biodiesel production from neem towards feedstock diversification: Indian perspective

In developing countries like India where 70% of country's petroleum needs are met by import, energy security assumes significance in view of uncertainty of supply and increasing price of petroleum fuels. Fuels of bio origin not only provide energy security, but also reduce emissions of harmful pollutants and greenhouse gases and ensure rural upliftment by increasing employment in agricultural sector. India cannot afford to produce biodiesel from edible oil seeds as it is done in the American and European countries. Extensive focus has been given on producing biodiesel from non-edible sources, specifically from Jatropha. Discrepancies between the expectation and realities regarding Jatropha as a feedstock necessitate efforts for diversification of the feedstocks. Scientific research should therefore be directed towards oilseeds like Karanja, Sal, Mahua, Neem, etc. that are widely available and sustainable to the diverse socio-economic and environmental conditions of rural India. Among them the evergreen neem with its wide availability and various useful uses may be a potential feedstock for biodiesel production. In this paper attempts have been made to overview the morphology of neem tree, various useful uses, physical and chemical characteristics of neem oil and optimized production process for biodiesel production from neem oil.     

Combustion and performance evaluation of a diesel engine fueled with biodiesel produced from soybean crude oil

In this study, the biodiesel produced from soybean crude oil was prepared by a method of alkaline-catalyzed transesterification. The important properties of biodiesel were compared with those of diesel. Diesel and biodiesel were used as fuels in the compression ignition engine, and its performance, emissions and combustion characteristics of the engine were analyzed. The results showed that biodiesel exhibited the similar combustion stages to that of diesel, however, biodiesel showed an earlier start of combustion. At lower engine loads, the peak cylinder pressure, the peak rate of pressure rise and the peak of heat release rate during premixed combustion phase were higher for biodiesel than for diesel. At higher engine loads, the peak cylinder pressure of biodiesel was almost similar to that of diesel, but the peak rate of pressure rise and the peak of heat release rate were lower for biodiesel. The power output of biodiesel was almost identical with that of diesel. The brake specific fuel consumption was higher for biodiesel due to its lower heating value. Biodiesel provided significant reduction in CO, HC, NO_x and smoke under speed characteristic at full engine load. Based on this study, biodiesel can be used as a substitute for diesel in diesel engine.     

Biodiesel production over copper vanadium phosphate

In the present study, copper vanadium phosphate (CuVOP) with three-dimensional network structure was synthesized by hydrothermal method, and was characterized by Infrared spectrum (IR), elemental analysis (EA), EDXRF (energy dispersive X ray fluorescence) etc. Moreover, soybean oil was used as feedstock for producing biodiesel, and biodiesel was produced by CuVOP-catalyzed transesterification process. Response surface methodology was employed to statistically evaluate and optimize the conditions for the maximum conversion to biodiesel, and the effects of amount of catalyst, ratio of methanol to oil, reaction time and reaction temperature were investigated by the 2⁴ full-factorial central composite design. The maximum conversion is obtained at amount of catalyst of 1.5%, methanol/oil molar ratio of 6.75, reaction temperature of 65 °C and reaction time of 5 h. Copper vanadium phosphate CuVOP resulted very active in the transesterification reaction for biodiesel production.     

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.     

Environmental effect of rapeseed oil ethyl ester

Exhaust emission tests were conducted on rapeseed oil methyl ester (RME), rapeseed oil ethyl ester (REE) and fossil diesel fuel as well as on their mixtures. Results showed that when considering emissions of nitrogen oxides (NO_x), carbon monoxide (CO) and smoke density, rapeseed oil ethyl ester had less negative effect on the environment in comparison with that of rapeseed oil methyl ester. When fuelled with rapeseed oil ethyl ester, the emissions of NO_x showed an increase of 8.3% over those of fossil diesel fuel. When operated on 25–50% bio-ester mixed with fossil diesel fuel, NO_x emissions marginally decreased. When fuelled with pure rapeseed oil ethyl ester, HC emissions decreased by 53%, CO emissions by 7.2% and smoke density 72.6% when compared with emissions when fossil diesel fuel was used. Carbon dioxide (CO₂) emissions, which cause greenhouse effect, decreased by 782.87 g/kWh when rapeseed oil ethyl ester was used and by 782.26 g/kWh when rapeseed oil methyl ester was used instead of fossil diesel fuel. Rapeseed oil ethyl ester was more rapidly biodegradable in aqua environment when compared with rapeseed oil methyl ester and especially with fossil diesel fuel. During a standard 21 day period, 97.7% of rapeseed oil methyl ester, 98% of rapeseed oil ethyl ester and only 61.3% of fossil diesel fuel were biologically decomposed.     

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.