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.     

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.     

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。     

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.     

麻疯果油制备生物柴油及其经济效益

选用了非食用油麻疯果油为原料,以氢氧化钠、氢氧化钾、甲醇钠为催化荆,通过酯交换法制取生物柴油,研究表明最适宜工艺条件为:醇油比6:1,反应温度60℃,反应时间80min,搅拌强度为600 r/min,催化剂用量为1.2%,转化率达到97%以上,且生物柴油各项理化指标均符合美国和德国测试标准.且从麻疯果的种植到生物柴油的生产整个产业链出发,其原料成本更低,经济效益更大,体现了不与粮争地的优势.     

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.     

用于生物柴油制备的KF/Al2O3固体碱催化剂的研究

采用浸渍法制备了KF/Al₂O₃固体碱催化剂，并将其应用于大豆油与甲醇酯交换制备生物柴油的反应。通过酯交换反应的转化率对催化剂制备工艺进行了优化，得出最佳制备条件：KF理论负载质量分数为Al₂O₃的45%，浸渍时间6 h，焙烧温度500 ℃，优化条件下制备的催化剂在大豆油与甲醇物质的量比为12∶1、催化剂用量为油质量的2%、反应时间3 h和反应温度(60～65) ℃条件下,酯交换转化率可达97.15%。     

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。     

碳酸根型镁铝复合氢氧化物的合成和表征及其催化性能

以恒定pH值共沉淀法合成碳酸根型镁铝水滑石,用XRD、IR、TG-DTA和SEM等手段进行表征。XRD衍射表明，Mg与Al物质的量比为1∶1、3∶1、4∶1和6∶1的合成物均有水滑石结构。热重-差热分析(TG-DTA)显示，水滑石有两个吸热峰值:第一吸收峰值在200～250 ℃, 第二吸热峰值在400～450 ℃,最大损失重量在2780%～33.41%。SEM分析可知，样品呈层状、棒状、针状和蜂窝状等结构。并对镁铝复合氢氧化物作为催化剂用于生物柴油制备作了研究。结果表明，Mg与Al物质的量比为3∶1的水滑石可使甲酯收率达到90%左右，且可重复使用。产品达到德国生物柴油质量标准。     

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。     

氧化锌催化菜籽油制生物柴油

氧化锌被用于菜籽油甲醇酯交换反应催化剂并制备生物柴油,从不同的锌盐得到的氧化锌在170～220 ℃都具有很好的活性。对氧化锌催化剂进行了活性评价和反应条件研究。结果表明,氧化锌催化剂具有很好的抗酸和抗水性能,在水质量分数高达20%和游离脂肪酸高达15%时,仍保持较高的反应转化率,可大幅度简化原料油的预处理和产品的分离纯化过程。     

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%.     

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.     

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。