【作者】 李浩南；

【导师】 钟耕；

【作者基本信息】 西南大学 ， 农产品加工及贮藏工程， 2007， 硕士

【摘要】 由于石化燃料资源的日益耗竭和环保的迫切需要，清洁能源的开发越来越受到人们的重视。世界各国的能源研究人员从环境保护和资源战略的角度出发，积极探索发展替代燃料以及可再生能源，生物柴油就是其中一种。而制约生物柴油发展的关键因素就是原料的价格问题，寻找一种廉价的原料并将其转化也是研究的主要方向。废弃油脂以其价廉、来源广泛而满足合成生物柴油的需要。将废弃油脂合成生物柴油，不仅可以解决废弃油脂对食品安全和环境保护的冲击，而且可以解决合成生物柴油的原料成本过高的问题。本文选用废弃油脂为原料，通过降酸与酯化相结合的工艺将其转化成生物柴油，具体结论如下：1通过过滤、脱水和脱色等方式，使废弃油脂中的杂质、水分得到了很好的控制，脱色率达35.27％；结合树脂的特性，采用摇瓶装置，通过单因素试验比较脱酸效果，B型树脂的脱酸效果最好，脱酸工艺为：温度60℃，时间3h，16％的树脂(废弃油脂的质量)，醇油摩尔比为9:1；树脂的再生方式为先用5％的NaCl浸泡5h，再用5％的HCl浸泡5h，最后用5％的NaOH浸泡5h，树脂可再生12次以上，其活性仍保持稳定。但脱酸过程的时间比较长，在树脂的再生分离过程中也会有树脂损失，操作过程相对复杂。2在单因素实验的基础上，使用连续化反应体系，采用二次正交旋转组合设计，通过响应面法分析反应温度、醇油摩尔比、树脂的高度和进样流速对废弃油脂脱酸率的影响。结果发现：(1)四个因素对脱酸率都有显著或极显著的影响，影响由大到小依次为：温度＞醇油摩尔比＞树脂高度＞进样流速，反应温度与进样流速的交互作用对脱酸率有极显著的负影响。(2)在反应温度53.49～56.71℃，醇油摩尔比12.05:1～13.29:1，树脂的高度26.79cm～30.15cm，进样流速0.298mL／s～0.305mL／s的优化参数条件下，废弃油脂的脱酸率达96.29％(酸值小于1mgKOH／g)有95％以上的可能性。3以产物中甲酯含量和得率为指标，通过单因素试验确定了使产物中甲酯含量达98.0％的碱法合成生物柴油工艺为：反应温度60℃，反应时间40min，醇油摩尔比为12:1，1.0％的氢氧化钠(废弃油脂的质量)，控制油脂的水分≤0.3％，反应过程进行中速搅拌。4确定了废弃油脂合成生物柴油的整体工艺；通过气象色谱法检测，废弃油脂合成的生物柴油的主要成分是肉豆寇酸甲酯C14:0，软脂酸甲酯C16:0，棕榈油酸甲酯C16:1，硬脂酸甲酯C18:0，油酸甲酯C18:1，亚油酸甲酯C18:2，花生酸甲酯C20:0，亚麻酸甲酯C18:3，芥酸甲酯C22:1，甲酯总含量达98.11％；生物柴油的性能指标达到了欧洲Ⅱ~#标准。更多还原

【Abstract】 Cleansing energy sources is gaining more and more attention as an attractive fuel due to the depleting of fossil fuel resources and environmental protection.The expert actively explores and develops replacing fuel and regenerative energy from the start of environmental protection and resource strategy, biodiesel is one kinds of among them. The cost problem of material is the key factor that restricts the development of biodiesel line. So seeking one kind of cheap material is one of the direction to study, too. Waste oils and fats will meet the need to synthesize biodiesel because of its sleazy price and broad source. Waste oils and fats used to synthesize biodiesel, are not only able to resolve the problem that the impact of waste oils and fats to safety of food, but also to the problem of exorbitant cost of material. The waste oils and fats are selected and used to produce biodiesel by combining deacid value and esterification technology. The conclusions are as follows:1 The impurity and moisture content in waste oils and fats get very good controlling by filtration, dehydration and decoloring, decolor rate is up to 35.27%. The effect on deacid value was investigated by single factor experimentation base on the characteristic of resin, the B type resin exhibited the best effect on acid value. The parameters of deacid value technology were: reaction temperature 60℃, reaction time 3h, 16% resin(resin weight/ waste oils and fats weight), methanol-to-oil molar ratio 9:1. The regeneration method of resin by the following three steps: (1) diping the resin into distilled water containing 5% NaCl for 5h, (2) then diping it into distilled water containing 5% HC1 for 5h, (3) regenerating with distilled water containing 5% NaOH for 5h, resin exhibited stabilization catalytic activities after 12 time regeneration. The reaction time is comparatively long in the shaking-up flask, resin will be loss in the process of the resin regeneration and separation, operation process is relatively complicated.2 Based on the factor experiment, using continuous reaction system, a quadratic rotation-orthogonal combination design and response surface method was used to study and analyse the effects of reaction temperature, methanol-to-oil molar ratio, height of resin and velocity of sample flow on rate of deacid value. The results were as follow:(1) All the four factors significantly affected the rate of deacid value, and the sequence was reaction temperature > methanol-to-oil molar ratio > height of resin > velocity of sample flow. The interaction of reaction temperature and velocity of sample flow had negative effects on the rate of deacid value.(2)On the optimized conditions, namely reaction temperature 53.49～56.71℃, methanol-to-oil molar ratio 12.05:1～13.29:1, height of resin26.79 cm～30.15cm and velocity of sample flow0.298 mL/s～0.305 mL/s, the percent of rate of deacid value was more than 96.29% on the possibility of 95% and above.3 The single factor experimentation was used to obtain the biodiesel synthesis technique which put the contents of methyl ester and rate of yield as the target. And the parameters to producing biodiesel containing 98.0% methyl ester were: reaction temperature 60℃, reaction time 40min, methanol-to-oil molar ratio 12:1, 1.0% NaOH (resin weight/ waste oils and fats weight)., less than 0.3 % moisture content, middle blending speed was used in the reaction process.4 The whole technology was established for the synthesizing of biodiesel with waste oils and fats. By means of gas chromatography, main components of biodiesel were methyl myristate (C14:0), methyl palmitate (C16:0), methyl palmitoleate(C16:1), methyl stearate(C18:0), methyl oleate(C18:1), methyl linoleate(C18:2), methyl arachidonate(C20:0), methyl linolenate(C18:3), methyl erucate (C22:1). The total contents of methyl ester reach 98.11 %.The performance index of biodiesel reached EN II standard.更多还原