Synthesis of biodiesel from waste vegetable oil with large amounts of free fatty acids using a carbon-based solid acid catalyst

A carbon-based solid acid catalyst was prepared by the sulfonation of carbonized vegetable oil asphalt. This catalyst was employed to simultaneously catalyze esterification and transesterification to synthesis biodiesel when a waste vegetable oil with large amounts of free fatty acids (FFAs) was used as feedstock. The physical and chemical properties of this catalyst were characterized by a variety of techniques. The maximum conversion of triglyceride and FFA reached 80.5 wt.% and 94.8 wt.% after 4.5 h at 220 °C, when using a 16.8 M ratio of methanol to oil and 0.2 wt.% of catalyst to oil. The high catalytic activity and stability of this catalyst was related to its high acid site density (–OH, Brönsted acid sites), hydrophobicity that prevented the hydration of –OH species, hydrophilic functional groups (–SO₃H) that gave improved accessibility of methanol to the triglyceride and FFAs, and large pores that provided more acid sites for the reactants.     

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.     

以棉籽油皂脚为原料制备生物柴油

文章探讨了在酸性催化剂作用下以酸化的棉籽油皂脚为原料制备生物柴油的工艺,为棉籽油生产过程中产生的废料--棉籽油皂脚的回收利用开辟了一条新的途径.试验考察了催化剂用量、反应时间、投料比等因素对反应收率的影响,并通过正交试验优化得到了最佳工艺条件:催化剂(浓硫酸)用量4%(以脂肪物质量计),反应时间10 h,脂肪物与甲醇物质的量比为1:10.在上述最优条件下产品收率可达83%.     

Optimization of a batch CaO-catalyzed transesterification of used domestic waste oil with methanol and elucidation of a mathematical correlation between biodiesel yield and percent conversion

ABSTRACT

The major drawback of the wide applicability of biodiesel is its price compared to the conventional petro-diesel. The feedstock and the applied catalyst in the transesterification reaction are the main contributor for the overall cost of the biodiesel production. Thus, this study summarizes the optimization of a batch transesterification reaction of used domestic waste oil (UDWO) with methanol using CaO, which can be easily prepared from different cheap and readily available natural sources. Quadratic model equations were elucidated describing the effect of methanol:oil molar ratio, CaO concentration wt.%, reaction temperature °C, reaction time h, and mixing rate rpm on biodiesel yield and conversion percentage. The optimum operating conditions were found to be competitive with those of the high-cost immobilized enzyme Novozym435. An overall acceptable agreement was achieved between the produced biodiesel, its blends with petro-diesel and the available commercial petro-diesel, and the international fuel standards. A precise and reliable logarithmic mathematical model was predicted correlating the production of pure high-quality biodiesel yield with the conversion percentage which were measured based on the fatty acid methylester content and decrease in viscosity, respectively.     

Biocatalytic production of biodiesel from cottonseed oil: Standardization of process parameters and comparison of fuel characteristics

The enzymatic production of biodiesel by transesterification of cottonseed oil was studied using low cost crude pancreatic lipase as catalyst in a batch system. The effects of the critical process parameters including water percentage, methanol:oil ratio, enzyme concentration, buffer pH and reaction temperature were determined. Maximum conversion of 75–80% was achieved after 4 h at 37 °C, pH 7.0 and with 1:15 M ratio of oil to methanol, 0.5% (wt of oil) enzyme and water concentration of 5% (wt of oil). Various organic solvents were tested among which a partially polar solvent (t-butanol) was found to be suitable for the reaction. The major fuel characteristics like specific gravity, kinematic viscosity, flash point and calorific value of the 20:80 blends (B20) of the fatty acid methyl esters with petroleum diesel conformed very closely to those of American Society for Testing Materials (ASTM) standards.     

Optimized alkali-catalyzed transesterification of wild mustard (Brassica juncea L.) seed oil

Biodiesel was developed from a non-edible oil source, i.e., wild mustard (Brassica juncea L) oil through optimized alkali-catalyzed transesterification with methanol using potassium hydroxide as a catalyst. Biodiesel yield of (95.54 % with 96.72 % w/w ester content) was obtained under optimal conditions of 0.75 % KOH w/w of oil, 6:1 methanol to oil molar ratio, 60°C temperature, and a duration of 45 min. Properties of wild mustard (Brassica juncea L) oil biodiesel were determined and found to be within the limits of ASTM D6751 specifications. As a result, wild mustard (Brassica juncea L), as an agricultural crop, might be a reasonable feedstock for biodiesel production.     

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 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.     

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.     

NaOH impregnated sepiolite based heterogeneous catalyst and its utilization for the production of biodiesel from canola oil

NaOH/sepiolite nanocomposite heterogenous base catalyst (NaOH/sep.) was prepared via impregnation process and tested in a three-neck flask equipped with thermometer and reflux condenser for the production of biodiesel from transesterification of canola oil in an excess amount of methanol. The ratio of NaOH and sepiolite was selected as 1:4. The influence of various operational parameters was examined such as methanol to oil molar ratio, catalyst dosage, and reaction temperature. Untreated sepiolite and NaOH loaded sepiolite were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Scanning electron microscopy and Energy dispersive spectroscopy analysis. Overall NaOH/sep. based biodiesel production yield was examined by the help of Gas chromatography-mass spectrometry analysis. The yield was calculated from the peak areas as 80.93% which is better than that of expensive catalysis system using studies.     

Effect of injection parameters on the combustion and emission characteristics in a common-rail direct injection diesel engine fueled with waste cooking oil biodiesel

The objective of this paper was to study the effects of the injection pressure and injection timing on the combustion and emission characteristics in a single-cylinder common-rail direct injection (CRDI) diesel engine fueled with waste cooking oil (WCO) biodiesel and commercial diesel fuel. The fuel property including fatty acid composition for the biodiesel were measured and compared with those of the conventional diesel fuel. The engine tests were conducted at two injection pressures (80 and 160 MPa) and different injection timings from −25 to 0 crank angle degree (CAD) after top dead center (aTDC) under two different engine loads. The results showed that the indicated specific fuel consumption (ISFC) with respect to the injection timings of the biodiesel was higher than that of the diesel fuel under all experimental conditions. The peak cylinder pressure and the peak heat release rate of the biodiesel were slightly lower, while the ignition delay was slightly longer under all operating conditions. In terms of emissions, the biodiesel had benefits in reduction of smoke, carbon monoxide (CO), hydrocarbon (HC) emissions especially with high fuel injection pressure. The nitrogen oxide (NO_x) emissions of the biodiesel were relatively higher than those of the diesel under all experimental conditions.     

大豆酸化油制备生物柴油的研究

试验研究了大豆酸化油在复合酸催化剂的作用下与甲醇发生转酯化和酯化反应生成脂肪酸甲酯(生物柴油)的最佳反应条件.试验结果表明,该酯化及转酯化反应的最佳操作条件:复合酸催化剂的用量为大豆油质量的5%、油醇摩尔比为1:6、反应时间为6h、反应温度为65℃.     

Effect of feedstocks and chain length of alcohols on whole-cell-catalyzed generation of alkyl esters

The dried biomass of a whole-cell catalyst was used for the generation of alkyl esters from cottonseed oil and acid oil with different alcohols (methanol to decanol) as acyl acceptors. The conversion of alkyl esters increased from methanol (12%) to pentanol (96%), followed by decreased from hexanol (86%) to decanol (64%) in case of acid oil. The extent of transesterification was significantly higher (P < 0.01) in case of acid oil, with most of the acyl acceptors as compared to cottonseed oil. The study demonstrates the use of dried biomass of fungus as catalyst and an effective feedstock such as acid oil, for the generation of various industrially important alkyl esters.     

固体酸催化剂在生物柴油合成实验中的研究

针对生物柴油催化合成技术中，采用一般催化剂所存在的问题，自制了4种固体酸催化剂，测试了它们在以大豆酸化油为原料制备生物柴油反应中的催化活性及重复使用性，确定了合成生物柴油的工艺条件。     

Production of biodiesel from castor oil using iron (II) doped zinc oxide nanocatalyst

The depletion of fossil fuels has caused the price of petroleum to rise remarkably and created need for alternative energy such as biodiesel. In the present study, the biodiesel was produced from castor oil using ferromagnetic zinc oxide nanocomposite as heterogeneous catalyst for transesterification reaction. Single phase of nanocatalyst were confirmed by X-Ray Diffraction analysis. The spherical shape of the aggregated nanocatalyst was observed in Scanning Electron Microscopy. Magnetic properties were analysed using vibrating sample magnetometer. Atomic Force Microscopic analysis revealed the larger surface area and roughness of nanocatalyst. The biodiesel yield of 91% (w/w) was obtained in 50 min at 55 °C with 14 wt % catalyst loading and 12:1 methanol/oil ratio and was confirmed by Gas chromatograph with Mass Spectrometer. The result showed that the iron (II) doped ZnO nanocatalyst is a promising catalyst for the production of biodiesel via heterogeneous catalytic transesterification under milder reaction conditions.     

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.     

Fuel properties of blend and biodiesel generated from acid oil using whole cell biocatalyst

Biodiesel was generated through whole cell catalyzed transesterification of acid oil, to the extent of up to 92%. The fuel properties of biodiesel (B100) and its blend (B20) were determined and compared with standard biodiesel as per American Society for Testing and Materials (ASTM) standard (ASTM D6751). B100 and B20 showed good pour point of ?26°C and ?29°C, respectively, indicating their operation viability in colder environment. Other properties of biodiesel are quite similar to petroleum diesel and ASTM standard. The results of this study reveal the potential use of acid oil as feedstock for generation of fuel grade biodiesel through biocatalyzed transesterification.     

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.     

Optimization of biodiesel production from waste cooking oil using waste bone as a catalyst

This work determined the association between several parameters of biodiesel production from waste cooking oil (WCO) using waste bovine bone (WBB) as catalyst to achieve a high conversion to fatty acid methyl ester (%FAME). The effect of three independent variables was used as the optimum condition using response surface methodology (RSM) for maximizing the %FAME. The RSM analysis showed that the ratio of MeOH to oil (mol/mol), catalyst amount (%wt), and time of reaction have the maximum effects on the transform to FAME. Moreover, the coefficient of determination (R²) for regression equations was 99.19%. Probability value (P < 0.05) demonstrated a very good significance for the regression model. The optimal values of variables were MeOH/WCO ratio of 15.49:1 mol/mol, weight of catalyst as 6.42 wt%, and reaction time of 128.67 min. Under the optimum conditions, %FAME reached 97.59%. RSM was confirmed to sufficiently describe the range of the transesterification parameters studied and provide a statistically accurate estimate of the best transform to FAME using WBB as the catalyst.     

菜籽油超声波法制备生物柴油的研究

以菜籽油和甲醇为反应原料,以KNO3/Al2O3为催化剂,采用超声波法制备生物柴油,考察了超声波频率、醇油物质的量比、催化剂用量等条件对反应的影响。试验结果表明,该反应的最佳条件:超声波频率为30kHz,醇油物质的量比为7∶1,催化剂用量为菜籽油质量的2.0%。在此条件下,生物柴油产率为94%。所得生物柴油的主要性能指标均符合德国的生物柴油标准。