生物柴油制备新工艺的研究进展

综述了生物柴油的特性及其生产方法,介绍了酯交换法制备生物柴油的反应机理及其近年来出现的各种新生产工艺,包括超临界法、生物催化法、超声波法、离子液体法等,指出了生物柴油技术发展面临的问题及研究方向。     

利用超临界技术制备生物柴油的研究现状

分析了超临界技术制备生物柴油的反应机理,重点阐述了温度、醇油比、压力、水、游离酸对超临界法制备生物柴油的影响.研究表明:超临界技术制备生物柴油在反应时间、对原料要求和产物回收等方面均具有传统碱催化法无法比拟的优势.展望了超临界技术制备生物柴油的工业应用前景,并对超临界技术制备生物柴油的研究提出了建议.     

正交试验探讨脂肪酸超临界酯化制备生物柴油

探讨脂肪酸在超临界甲醇中酯化反应的规律及最佳条件。以橡胶籽油脂肪酸为原料,在间歇式高温高压反应釜中通过酯化反应制备生物柴油,分别考察了酯化反应条件如反应温度、反应时间、甲醇与脂肪酸的体积比对酯化率的影响。应用正交试验方法得出酯化反应的较适宜条件为：反应温度290℃,反应时间30min,甲醇与脂肪酸的体积比为4：1。在此反应条件下转化率可达99．2％。橡胶籽油生物柴油成分主要有亚油酸甲酯、油酸甲酯、亚麻酸甲酯,还有少量的硬脂酸甲酯、棕榈酸甲酯。     

麻疯果油预处理及酯交换制备生物柴油的试验研究

以热榨麻疯果油为原料,采用液体碱酯交换法制备生物柴油,研究了最佳的脱胶、脱酸及酯交换反应条件.试验结果表明,最佳脱胶工艺条件:温度为80℃、磷酸用量为原料油质量的0.2%、反应时间为30min、加水量为磷脂质量的3倍:最佳脱酸工艺条件:温度为85℃、超碱量为原料油质量的0.2%、搅拌速度为70r/min、反应时间为30min;最佳酯交换反应条件:甲醇:油=6:1(物质的量比)、催化剂(甲醇钠)用量为原料油质量的1.2%、反应温度为65℃、反应时间为20min,甲酯转化率可达94%以上,甲酯产品各项性能指标达到GB/T20828-2007要求.     

棕榈油生物柴油低温流动性的改进及其对氧化稳定性的影响

文章对棕榈油生物柴油的低温流动性和氧化稳定性进行了分析,发现棕榈油生物柴油具有较好的氧化稳定性,但是低温流动性较差。通过不同的方法(与-10#柴油、油酸甲酯、菜籽油生物柴油按照不同体积比混合)对棕榈油生物柴油的低温流动性进行了改进,并利用流变仪和Rancimat法分析了改进方法对棕榈油生物柴油低温流动性及氧化稳定性的影响。研究结果表明:与油酸甲酯混合可以降低棕榈油生物柴油的胶凝点,但其氧化稳定性随之变差;当棕榈油生物柴油的体积含量为5%~20%时,与-10#柴油的混合使得油样的胶凝点低于-10℃,氧化诱导期大于20 h;当棕榈油生物柴油的体积含量低于40%时,与菜籽油生物柴油的混合使得油样的胶凝点低于0℃,氧化诱导期大于6 h。     

超声波制备生物柴油技术的研究进展

超声波技术作为一门新兴的技术已受到普遍关注.文章综述了近年来国内外超声波技术在生物柴油制备中应用的研究现状、制备原理和优缺点,指出了该技术在生物柴油制备中须要解决的问题,在此基础上提出超声波制备生物柴油技术的发展方向,认为开发更优良的的制备工艺是今后超声波制备生物柴油技术研究领域的主要任务.     

生物柴油对增压柴油机排气温度和排放的影响

将菜籽油甲酯生物柴油和0号柴油在一台配有直喷系统和废气再循环系统的V6双涡轮增压柴油机上进行对比试验.试验结果表明,用菜籽油甲酯生物柴油比0号柴油产生较少的HC、CO和较高的NOx,同时有较低的排气温度.研究认为,较低的排气温度改善了废气再循环温度,而当进气温度相同时,排气温度有明显的变化.在不改变发动机参数的条件下,菜籽油甲酯生物柴油具有良好的推广应用前景.     

水力空化强化高芥酸菜籽油联产生物柴油和芥酸甲酯

水力空化条件下,以高芥酸菜籽油为原料,研究了醇-油不相溶体系的酯交换反应.结果表明:水力空化技术能大大缩短酯交换反应达到平衡的时间;与机械搅拌反应体系相比,在反应温度60℃、醇油摩尔比6∶1、催化剂用量1.0％ KOH的条件下,反应平衡时间可从60min缩短至30min,油酯的转化率从94％提高到99％,水力空化技术可强化醇油互不相溶体系酯交换反应传质过程,是一种高效的生物柴油制备方法.同时通过实验以高芥酸菜籽油为原料制备出高品质的生物柴油和高附价值的芥酸甲酯,为我国发展菜籽油生物柴油降低生产成本提供新思路.     

生物柴油生产的现状及其技术进展

3、生物柴油的生产技术进展。新开发的生产生物柴油的反酯化方法可克服碱催化反酯化的缺点，如甘油回收和催化剂脱除困难，反应不完全，以及当油中含有游离脂肪酸和/或水时会生成皂化产物。传统的碱催化方法从三甘油酯和甲醇生产脂肪酸甲酯存在几个问题，包括在室温下反应速率太慢。     

棕榈油生物柴油的低温流动性能及其改善研究

采用碱催化酯交换法制备3种生物柴油并研究其低温流动性能,通过添加市售降凝剂PPD、聚甘油酯PGE、自制生物柴油降凝剂PA作为低温流动改进剂,其中重点考察改进剂对棕榈油生物柴油的低温性能影响。实验表明:生物柴油DSC放热峰的开始温度与其冷滤点非常接近;另外,冷滤点与饱和脂肪酸甲酯含量不呈单一的线性关系。PPD、PGE、PA单独使用时具有一定的降滤效果,但不同生物柴油对同一改进剂的感受性有很大差别;多元复配的降滤效果明显优于单一改进剂的使用,PPD/PA/PGE配方比例为3∶1∶1和2∶2∶1时降低棕榈油生物柴油冷滤点7℃。     

Improved biodiesel manufacture at low temperature and short reaction time

Biodiesel, which is derived from oil/fat by transesterification with alcohol, has attracted considerable attention over the past decades due to its ability to subsidise fossil fuel derived energy as a renewable and carbon neutral fuel. Several approaches for biodiesel fuel production have been developed, among which transesterification using a catalyst gives high yields of methyl ester. This method has therefore been widely utilized for biodiesel production in a number of countries. In this study, a Downflow Liquid Contactor Reactor (DLCR) has been used for the liquid–liquid transesterification reaction of sunflower oil with alcohol with extraordinary results. The reactor provides great potential for chemical reactions, which are normally limited by mass transfer and possesses a number of distinctive advantages over conventional multiphase reactors. Inside the reactor a high velocity liquid jet stream is produced which generates powerful shear and energy, causing vigorous agitation in the upper part of the reactor. The high mixing intensity in the DLCR enabled the manufacture of biodiesel to European Standard EN14214 (ester content 96.5%) in 2.5 min at 40 °C with 0.43 wt.% alkali catalyst and alcohol to oil molar ratio of 4.5 to 1.0. The separation of FAME from glycerol is done by gravity settling only without water washing. The effect of the alcohol type (methanol, ethanol) on biodiesel yield was also investigated. The process offers the advantage of continuous large scale production with limited reactor volume.     

Biodiesel production by transesterification of duck tallow with methanol on alkali catalysts

Duck tallow was employed as a feedstock for the production of biodiesel by transesterification with methanol. The content of fatty acid methyl ester (FAME) was evaluated on various alkali catalysts during transesterification. The composition and chemical properties of the FAME were investigated in the raw duck tallow and the biodiesel products. The major constituent in the biodiesel product was oleic acid. The FAME content was 97% on KOH catalyst in the reaction. It was acceptable for the limit of European biodiesel qualities for BD100. Acid value, density, and kinematic viscosity of the biodiesel products also came up to the biodiesel qualities.     

The utilization of waste egg and cockle shell as catalysts for biodiesel production from food processing waste oil using stirring and ultrasonic agitation

The use of calcined egg and cockle shell as heterogeneous solid catalysts for a transesterification reaction to produce biodiesel from food processing waste has been investigated in this work. The CaO catalysts were obtained from the calcination of egg and cockle shell and were characterized by surface analysis, X-ray diffractometry (XRD), and scanning electron microscopy (SEM). The experiments employed stirring and ultrasonic agitation, which proved to be a time-efficient approach for biodiesel production from food processing waste oil. A response surface methodology (RSM) was used to evaluate the effects of the process variables methanol to oil molar ratio, catalyst concentration, and reaction time on biodiesel production. The optimal % fatty acid methyl ester values obtained when using egg and cockle shells as catalysts were found to be 94.7% and 94.4% when the methanol to oil molar ratios were 9.3:1 and 8.5:1, egg and cockle shell catalyst mass fraction percentages were 3.8% and 3.5%, and reaction times were 47 and 44 min, respectively. The study has shown that ultrasonic agitation might be employed in a practical pilot reactor for biodiesel production.     

Biodiesel production from olive–pomace oil of steam-treated alperujo

Recently interest has been revived in the use of plant-derived waste oils as renewable replacements for fossil diesel fuel. Olive–pomace oil (OPO) extracted from alperujo (by-product of processed olives for olive oil extraction), and produced it in considerable quantities throughout the Mediterranean countries, can be used for biodiesel production. A steam treatment of alperujo is being implemented in OPO extraction industry. This steam treatment improves the solid–liquid separation by centrifugation and facilitates the drying for further extraction of OPO. It has been verified that the steam treatment of this by-product also increases the concentration of OPO in the resulting treated solid, a key factor from an economic point of view. In the present work, crude OPO from steam-treated alperujo was found to be good source for producing biodiesel. Oil enrichment, acidity, biodiesel yield and fatty acid methyl ester composition were evaluated and compared with the results of the untreated samples. Yields and some general physicochemical properties of the quality of biodiesel were also compared to those obtained with other oils commonly used in biodiesel production. As for biodiesel yield no differences were observed. A transesterification process which included two steps was used (acid esterification followed by alkali transesterification). The maximum biodiesel yield was obtained using molar ratio methanol/triglycerides 6:1 in presence of sodium hydroxide at a concentration of 1% (w/w), reaction temperature 60 °C and reaction time 80 min. Under these conditions the process gave yields of about 95%, of the same order as other feedstock using similar production conditions.     

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 bronsted basic ionic liquid as an efficient and environmentally benign catalyst for biodiesel synthesis from soybean oil and methanol

Morpholine basic ionic liquid was synthesized with N-methyl morpholine, N-butyl bromide, and KOH by two-step method and was used to catalyze the transesterification of soybean oil with methanol to biodiesel. The structure of the catalyst were examined by ¹H nuclear magnetic resonance. The effects of the molar ratio of methanol to oil, reaction temperature, and amount of catalyst on the biodiesel yield were investigated. Optimized biodiesel yield of 94.5% was achieved with catalyst amount of 3.0 wt%, and methanol to soybean oil molar ratio of 14:1 at reaction temperature of 60 °C for 6 h. The catalyst has maintained sustained activity after being employed to six cycles. The prepared biodiesel component was analyzed by gas chromatography-mass spectrometry (GC-MS) and the results showed that the biodiesel comprised of hexadecanoic acid methyl ester, 10, 13-octadecadienoic acid methyl ester, 9-octadecenoic acid methyl ester, and octadecanoic acid methyl ester, illustrating that fatty acids of soybean oil were converted completely.     

A rapid ultrasound-assisted production of biodiesel from a mixture of Karanj and soybean oil

Karanj oil having high free fatty acid was neutralized with a dilute alkali solution and then mixed with soybean oil in different ratios in order to reduce the free fatty acid content significantly. The mixture of the oils was then transesterified with methanol to produce fatty acid methyl ester. The transesterification was carried out using ultrasonication energy of 20 kHz in pulse mode. It was found that up to 60% Karanj oil in the blended mixture could produce good quality biodiesel that met the ASTM standards. However, the lesser content of Karanj oil in the mixture, the lesser the reaction parameters viz. alcohol to oil molar ratio, catalyst concentration, and reaction time. About 99% yield of methyl esters was obtained when the Karanj oil content in the mixture was 20% with a reaction time of 30 min, catalyst concentration 1 wt%, and a temperature of 55°C.     

Reaction conditions of ultrasound‐assisted production of biodiesel: A review

Ultrasound‐assisted biodiesel production is an emerging technology that features high energy density, high conversion efficiency, and environment friendliness. This review evaluates the influence of process parameters, including ultrasonic power, ultrasonic frequency, catalyst dosage, alcohol/oil ratio, reaction temperature, reaction time, and alcohol type, on the yield of ultrasonic‐assisted production of biodiesel. Limitations associated with ultrasonic‐assisted production of biodiesel are also analyzed. Further development of this technology is explored. Copyright © 2016 John Wiley & Sons, Ltd.     

Analysis and evaluation of operating variables for the yield of Karanja and neem oil-based biodiesel production

The aim of this research is to present the possibilities of the use of non-edible oils in biodiesel production, to consider the various methods for treatment of non-edible oils and to emphasise the influence of the operating and reaction conditions on the process rate and the ester yield. Because of biodegradability and non-toxicity biodiesel has become more attractive as alternative fuel. Biodiesel is produced mainly from vegetable oils by transesterification. For economic and social reasons, edible oils should be replaced by lower-cost and reliable feedstock for biodiesel production, such as non-edible plant oils. In this work biodiesel is produced from neem and Karanja by using butanol, propanol, ethanol and methanol as alcohols and KOH and NaOH as alkali catalysts by the transesterification process. The aim of this research is to analyse the different reaction parameters such as catalyst concentration, type of catalyst, types of alcohol, alcohol to oil molar ratio, reaction time and reaction temperature on the yield of biodiesel from non-edible oils. The maximum yield obtained was 95% with Karanja as oil with methanol and KOH as alkali catalyst at oil to alcohol molar ratio of 6:1 in 1 h at 60°C. Special attention is paid to the possibilities of producing biodiesel from non-edible oils.     

我国生物质能源现代化应用前景展望(三)——生物质能源转化技术经济评估

秸秆、动植物油脂、微藻等生物质原料可以生产液体运输燃料,生物燃料的化学成分包括醇、酯、烃三类。燃料乙醇主要替代汽油,受到各国重视,其中纤维素乙醇技术发展较快。脂肪酸甲酯是第一代生物柴油的主要成分,价格主要受油脂原料价格的影响,由于和柴油相容性差,低温流动性不好,将逐渐被加氢生产的第二代生物柴油取代。相比醇、酯等含氧燃料,烃类生物燃料在使用性能上有很多优势。有多条技术路线可以生产烃类燃料,其中油脂加氢制喷气燃料已接近商业应用,热解油加氢可将木质生物质原料中的"木质素"组分转化为生物油,大型快速热解工厂可以和热电联产装置组成联合系统,从而提高工厂综合热效率,降低生物燃料生产成本。因此,快速热解生产汽柴油将成为主要的生物燃料生产路线。生物质与煤共气化技术通过提高气化温度,不仅可以提高生物质气化效率,减少焦油的生成,还可以解决生物质供给的季节性问题,为生物质的高效利用提供了一条新的技术途径。微藻高压液化生产柴油是最具发展潜力的第三代生物燃料技术,我国需要加强微藻养殖及加工技术攻关。