Microwave assisted transesterification of rapeseed oil

Rapeseed is one of the important vegetable oil sources for biodiesel production due to its high oil content (around 40%). In this study rapeseed oil was converted to biodiesel by transesterification using microwave heating. Experiments were carried out in the presence of two different alkali catalysts which are sodium hydroxide and potassium hydroxide. Effects of various reaction parameters such as catalyst ratio, reaction temperature and time were investigated. Mono-, di- and triglyceride content of biodiesel were determined by gas chromatography analysis. Yield and purity (ester content) percentages of biodiesel were specified in weight, which are 88.3–93.7% and 87.1–99.4%, respectively. The results indicated that microwave heating has effectively increased the biodiesel yield and decreased the reaction time.     

Hydroprocessed rapeseed oil as a source of hydrocarbon-based biodiesel

This paper deals with the hydroprocessing of rapeseed oil representing a perspective technological way for production of biocomponents in diesel fuel range. Rapeseed oil was hydroprocessed at various temperatures (260-340 °C) under a pressure of 7 MPa in a laboratory flow reactor. Three Ni-Mo/alumina hydrorefining catalysts were used. Reaction products were analyzed using several gas-chromatographic methods. Reaction products contained water, hydrogen-rich gas and organic liquid product (OLP). The main components of OLP were identified as C₁₇ and C₁₈n-alkanes and i-alkanes. At a low reaction temperature, OLP contained also free fatty acids and triglycerides. At reaction temperatures higher than 310 °C, OLP contained only hydrocarbons of the same nature as hydrocarbons present in diesel fuel. Influence of reaction temperature and catalyst on the composition of reaction products is discussed.     

棉籽油酯交换法合成生物柴油的工艺研究

介绍了利用复合碱性催化棉籽油酯交换合成生物柴油的工艺过程,正交实验得出的适宜工艺条件为:醇油摩尔比为5.5∶1,反应时间50 min,反应温度35℃,催化剂用量1.0%,产率可达96%。并比较了生物柴油与0#柴油的性能。     

Transesterification of rapeseed oil in the presence of basic zeolites and related solid catalysts

The transesterification of rapeseed oil with methanol was performed by reflux of methanol over cesium-exchanged NaX faujasites, mixed magnesium-aluminum oxides, magnesium oxide, and barium hydroxide for different methanol-to-oil ratios. Over cesium-exchanged NaX faujasites and mixed magnesium-aluminum oxides, a long reaction time and a high methanol-to-oil ratio are required to achieve both high oil conversion and high yields in methyl esters. However, over a 300 m²/g magnesium oxide, methanol-to-oil ratios and reaction times are significantly reduced to obtain both high oil conversion and high yield in the methyl esters, particularly when the hydroxide precursor is calcined at 823 K. Finally, preliminary results with other basic solids such as barium hydroxide have shown a very high activity and a very high yield in esters. This catalyst is particularly effective since, for a methanol-to-oil ratio of 6, at reflux of methanol and after a reaction time of only 1 h, the oil conversion is about 80% with a nearly quantitative ester molar fraction. Part of this work was presented at the 91st AOCS Annual Meeting, San Diego, California, April 2000.     

预酯化-酯交换法利用餐饮废油脂制备生物柴油

以高酸值餐饮废油脂和乙醇为原料,采用预酯化-酯交换法制备生物柴油。第一步为预酯化反应,控制反应温度为70℃,最佳条件为:催化剂加入量为4%,反应时间为90min,带水剂加入量为10%,乙醇加入量控制在醇酸摩尔比为6∶1,可使油脂酸值降至4mg KOH·g-1以下,满足酯交换反应要求。第二步为酯交换反应,最佳条件是:醇油摩尔比为8∶1,碱性催化剂加入量为0.8%,反应温度为70℃,反应时间为30min。本方法具有反应时间短、转化率高,反应条件温和,清洁环保等优点。     

Optimization of the transesterification reaction in biodiesel production

In this paper response surface methodology (RSM) was used to study the transesterification reaction of rapeseed oil for biodiesel production. The three main factors that drive the conversion of triglycerides into fatty acid methyl esters (FAME) were studied according to a full factorial design at two levels. These factors were catalyst concentration (KOH), temperature and reaction time. The range investigated for each factor was selected taking into account the process of Fox Petroli S.p.A. Analysis of variance (ANOVA) was used to determine the significance of the factors and their interactions which primarily affect the first of the two transesterification stages. This analysis evidenced the best operating conditions of the first transesterification reaction performed at Fox’s plant: KOH concentration 0.6% w/w, temperature 50 °C and reaction time 90 min with a CH₃OH to KOH ratio equal to 60. Three empirical models were derived to correlate the experimental results, suitable to predict the behavior of triglyceride, diglyceride and monoglyceride concentration. These models showed a good agreement with the experimental results, demonstrating that this methodology may be useful for industrial process optimization.     

Lipase-catalyzed transesterification of rapeseed oil and 2-ethyl-1-hexanol

Lipase-catalyzed transesterification (alcoholysis) of lowerucic acid rapeseed oil and 2-ethyl-1-hexanol without an additional organic solvent was studied in stirred batch reactors. Of a number of commercially available enzymes investigated, the best results were obtained with aCandida rugosa lipase. The optimal transesterification conditions were an oil/alcohol molar ratio of 1∶2.8, a minimum of 1.0% (w/w) added water, and with a temperature of 37–55°C. Under the optimal conditions, a nearly complete conversion was obtained in one hour with 14.6% (w/w) lipase, whereas 0.3% (w/w) lipase required 10 h for similar results. The enzyme was inactivated at 60°C.     

Ignition delay in a palm oil and rapeseed oil biodiesel fuelled engine and predictive correlations for the ignition delay period

This paper presents the results of engine tests of biodiesels obtained by transesterification of palm oil and rapeseed oil and with fossil diesel fuel as a reference. The analysis is focused on the determination of the ignition delay and on obtaining a predictive correlation for it. The experiments show no significant difference in in-cylinder pressures at injection timing for each fuel. With biodiesel slightly lower peak cylinder pressures were observed for most engine conditions. Palm oil and rapeseed oil biodiesel gave shorter ignition delay than fossil diesel fuel due to the higher cetane number for the biodiesels. The ignition delay data were correlated as a function of the equivalence ratio, the mean cylinder pressure and mean temperature over the ignition delay interval. A comparison is made with other available correlations. The ignition delay values estimated by the new correlations are in good agreement with the experiments.     

Fuel properties of hydroprocessed rapeseed oil

This paper deals with the hydroprocessing of rapeseed oil as a source of hydrocarbon-based biodiesel. Rapeseed oil was hydroprocessed in a laboratory flow reactor under four combinations of reaction conditions at temperatures 310 and 360 °C and under hydrogen pressure of 7 and 15 MPa. A commercial hydrotreating Ni-Mo/alumina catalyst was used. Reaction products contained mostly n-heptadecane and n-octadecane accompanied by low concentrations of other n-alkanes and i-alkanes. Reaction product obtained at 360 °C and 7 MPa was blended into mineral diesel fuel in several concentration levels ranging from 5 to 30 wt.%. It was found, that most of the standard parameters were similar to or better than those of pure mineral diesel. On the other hand, low-temperature properties were worse, even after addition of high concentrations of flow improvers.     

油脂酯交换反应催化剂的研究进展

综述了均相碱性催化剂和多相碱性催化剂,尤其是碱土金属氧化物、阴离子型层柱化合物和新型分子筛材料在油脂酯交换反应中的应用;针对高酸值油脂的特点,对“两步酯交换法”和固体酸催化法进行了讨论,并对应用性能较好的带磺酸根的稠环化合物型和介孔材料催化剂的结构与催化性能的关系进行了分析;评述了生物酶催化具有反应条件温和、污染物排放少以及超临界酯交换反应具有体系不怕水、反应速率快等优点。     

用棉籽油制备生物柴油

采用棉籽油为原料连续化生产生物柴油,研究了工艺及设备的设计。由棉籽油与甲醇在催化剂NaOH存在下由酯交换反应制得生物柴油。在优化条件下反应50 min,转化率达到99%。生产的生物柴油,各项指标与天然柴油相似。其各项燃烧指标优于或与普通柴油相仿,满足欧洲Ⅱ排放标准。     

Production of biodiesel from palm oil (Elaeis guineensis) using heterogeneous catalyst: An optimized process

Response surface methodology (RSM) based on central composite design (CCD) was used to optimize the three important reaction variables — methanol/oil molar ratio (x₁), reaction time (x₂) and amount of catalyst (x₃) for production of biodiesel from palm oil using KF/ZnO catalyst. Based on the CCD, a quadratic model was developed to correlate the reaction variables to the biodiesel yield. From the analysis of variance (ANOVA), the most influential factor on the experimental design response was identified. The predicted yield after process optimization was found to agree satisfactory with the experimental value. The optimum conditions for biodiesel production were found as follows: methanol/oil ratio of 11.43, reaction time of 9.72 h and catalyst amount of 5.52 wt%. The optimum biodiesel yield was 89.23%.     

Mg-Al类水滑石催化大豆油酯交换制备生物柴油

采用共沉淀法制备了不同n(Mg)/n(Al)比的Mg-Al类水滑石,在不同温度下焙烧得到复合氧化物,作为大豆油与甲醇反应制备生物柴油的催化剂。结果表明,未焙烧Mg-Al类水滑石的催化活性较差,而n(Mg)/n(Al)=3的类水滑石在450℃焙烧时具有极高的催化活性。在反应温度65℃,醇/油15,催化剂用量为大豆油质量的2%,反应3 h,生物柴油产率可达97.4%。催化剂回收再用性能良好,重复使用3次,生物柴油收率仍在90%左右。     

Optimization of ultrasonic-assisted heterogeneous biodiesel production from palm oil: A response surface methodology approach

The use of ultrasonic processor in the heterogeneous transesterification of palm oil for biodiesel production has been investigated. Response surface methodology was employed to statistically evaluate and optimize the biodiesel production process catalyzed by two alkaline earth metal oxide catalysts i.e. BaO and SrO. SEM, surface analysis, AAS analysis and the Hammett indicator methods were used for characterization of the catalysts. Four different variables including reaction time (10-60 min), alcohol to oil molar ratio (3:1-15:1), catalyst loading (0.5-3.0 wt.%) and ultrasonic amplitude (25-100%) were optimized. Mathematical models were developed and used to predict the behavior of the process. The models were able to accurately predict the biodiesel yield with less than 5% error for both catalysts. The basic strength of the catalysts was the main reason of their high activities. This study confirmed that the ultrasonic significantly improved the process by reducing the reaction time to less than 50 min and the catalyst loading to 2.8 wt.% to achieve biodiesel yields of above 95%. The optimum alcohol to oil ratio was found to be at 9:1 while the best amplitudes were ∼ 70 and ∼ 80% for the BaO and SrO catalysts, respectively.     

Evaluation of biodiesel obtained from cottonseed oil

Esters from vegetable oils have attracted a great deal of interest as substitutes for petrodiesel to reduce dependence on imported petroleum and provide a fuel with more benign environmental properties. In this work biodiesel was prepared from cottonseed oil by transesterification with methanol, using sodium hydroxide, potassium hydroxide, sodium methoxide and potassium methoxide as catalysts. A series of experiments were conducted in order to evaluate the effects of reaction variables such as methanol/oil molar ratio (3:1–15:1), catalyst concentration (0.25–1.50%), temperature (25–65 °C), and stirring intensity (180–600 rpm) to achieve the maximum yield and quality. The optimized variables of 6:1 methanol/oil molar ratio (mol/mol), 0.75% sodium methoxide concentration (wt.%), 65 °C reaction temperature, 600 rpm agitation speed and 90 min reaction time offered the maximum methyl ester yield (96.9%). The obtained fatty acid methyl esters (FAME) were analyzed by gas chromatography (GC) and ¹H NMR spectroscopy. The fuel properties of cottonseed oil methyl esters (COME), cetane number, kinematic viscosity, oxidative stability, lubricity, cloud point, pour point, cold filter plugging point, flash point, ash content, sulfur content, acid value, copper strip corrosion value, density, higher heating value, methanol content, free and bound glycerol were determined and are discussed in the light of biodiesel standards such as ASTM D6751 and EN 14214.     

Conventional and in situ transesterification of castor seed oil for biodiesel production

In the present study, biodiesel production from Ricinus communis L. red and BRS-149 nordestina varieties seed oil is reported. Reactions were made through conventional and in situ processes using ethanol and evaluating the addition of n-hexane as co-solvent. The content of ethyl esters was quantified by ¹H NMR. The highest conversions were obtained from crude oil (conventional reaction) after pre-esterification, using ethanol and a molar ratio of alcohol to oil of 60; furthermore, the addition of n-hexane was not significant on yield. Under these conditions, best conversion was around 95% for both varieties.     

酯交换法在生物柴油制备中的研究进展

介绍了国内外生物柴油制备方法的研究进展,主要阐述了非均相催化、均相催化、生物催化和超临界催化技术等酯交换法的研究进展。阐明了各种催化法的优缺点,指出了目前酯交换法研究的热点和未来发展的方向。     

Application of response surface methodology for optimization of biodiesel production by transesterification of soybean oil with ethanol

In this paper, the transesterification of soybean oil with ethanol is studied. The transesterification process can be affected by differing parameters. The biodiesel production process was optimized by the application of factorial design 2⁴ and response surface methodology. The combined effects of temperature, catalyst concentration, reaction time and molar ratio of alcohol in relation to oil were investigated and optimized using response surface methodology. Optimum conditions for the production of ethyl esters were the following: mild temperature at 56.7 °C, reaction time in 80 min, molar ratio at 9:1 and catalyst concentration of 1.3 M.     

棕榈油酯交换制备生物柴油的反应动力学

在甲醇与棕榈油的摩尔比为6∶1和催化剂KOH用量为棕榈油质量1.0%的条件下,研究不同温度下棕榈油制备生物柴油的酯交换反应动力学,采用Origin软件拟合曲线方程,建立棕榈油酯交换反应的宏观动力学模型。研究结果表明:棕榈油制备生物柴油的酯交换反应遵循1.40级动力学方程,反应速率随温度的升高而加快,二者符合Arrhenius方程,该反应的活化能为27.23 kJ/mol,频率因子为1.4×103。文中研究建立的反应动力学模型将对扩大试验研究提供理论依据和基础数据支持。     

Hydrocracking of petroleum vacuum distillate containing rapeseed oil: Evaluation of diesel fuel

Hydrocracking of pure petroleum vacuum distillate and the same fraction containing 5 wt.% of rapeseed oil was carried out at 400 and 420 °C and under a hydrogen pressure of 18 MPa over commercial Ni-Mo catalyst. Reaction products were separated by distillation into kerosene, gas oil and the residue. Fuel properties of fractions suitable for diesel production were evaluated (gas oils and remixed blends of kerosene and gas oil). Gas oils obtained from co-processing showed very good fuel properties as the remixed distillates did. Gas oil obtained from co-processing at 420 °C showed also reasonable key low-temperature properties (cloud point: −23 °C, CFPP: −24 °C) similar to those of gas oil obtained from pure petroleum raw material processing.