碱性离子液体催化菜籽油制备生物柴油的试验研究
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摘要
能源是人类社会赖以生存和发展的重要物质基础。随着环境和能源双重压力的不断加大,发展可再生、环保的化石燃料的替代品已经成为世界各国的共识。生物柴油以其良好的性能而展现出来的巨大的潜力和广阔的市场前景逐渐成为人们关注的焦点。
生物柴油的制备方法有直接混合法、微乳液法、高温热裂解法、酯交换法。而酯交换中的碱催化法因其反应条件温和,催化剂成本低,反应速度快,转化率高,是目前工业生产中使用较为广泛的一种方法。
离子液体是指在室温或接近室温(<150℃)的条件下呈现液态的、完全由阴阳离子构成的物质。作为一种新型的环境友好溶剂和液体酸碱催化剂,具有其它溶剂和传统催化剂不具备的优点。由于其独特而优良的性能,它被认为是21世纪最有希望的绿色溶剂和催化剂之一,现已应用于催化反应、有机合成、分离科学以及电化学等诸多领域。
本论文以实验室自制的碱性离子液体氢氧化—丁基三甲基咪唑([Bmim]OH)为催化剂,进行了菜籽油的酯交换反应、超声波辅助下的菜籽油酯交换反应,以及菜籽油的原料特性、菜籽油脂肪酸和菜籽油生物柴油的成份分析等相关试验研究。
对于[Bmim]OH催化菜籽油的酯交换反应,通过单因素和正交试验的手段,详细研究了醇油摩尔比、反应温度、反应时间和离子液体用量对酯交换反应的影响及离子液体的稳定性。结果表明,在n(甲醇)：n(菜籽油)=16：1、反应温度150℃、反应时间4h和催化剂用量为菜籽油质量6%的条件下,生物柴油收率可达96.2%,并且该离子液体的稳定性良好,循环使用五次催化性能没有明显降低。反应动力学的研究显示,该反应的反应级数为0.7075,活化能为43.94kJ/mol,指前因子为96056.32。该反应的动力学模型为-(dcA)/(dt)=96056.32e-(43.93)/(RT)C A0.7075。
对于超声波辅助下的碱性离子液体[Bmim]OH催化菜籽油制备生物柴油,超声波频率59KHz时得到的最优反应条件是：超声波功率200W、反应温度90℃、反应时间1h、n(甲醇)：n(菜籽油)=16：1和催化剂用量为菜籽油质量6%。该条件下,酯交换反应脂肪酸甲酯收率达到90.8%。
超高效液相色谱测得的菜籽油生物柴油的主要成分为亚麻酸甲酯、亚油酸甲酯、油酸甲酯、芥酸甲酯。菜籽油生物柴油的主要成分是含有18个C的脂肪酸甲酯,其分子结构满足理想的柴油替代品的要求,是合格的燃料替代品。
Energy is an important material base of human society to exist and develop.With the dual increasing pressures of environment and energy, the development of renewable, environmente-friendly fuels to replace fossil fuels has become a world consensus. Biodiesel,for its good performance bring the huge potential and broad market prospects, becomes gradually the focus of attention.
There are many methods for preparation of biodiesel, direct mixing method, micro-emulsion method, high-temperature thermal cracking method and transesterification. currently,The base catalyzed transesterification,for its mild reaction conditions, low cost of catalyst, fast reaction rate, and high conversion ratio, is one of more widely used methods in industrial.
Ionic liquid is liquid under the room temperature or near room temperature (<150℃) and entirely composed of the anion and cation. As a new type of environment-friendly solvent and liquid catalyst, Ionic liquid has many unique advantages. Because of unique and excellent performance, it is considered to be one of the most promising green solvent and catalyst in the 21st century.It has been used in catalytic reaction, organic synthesis, separation science and electrochemical and other areas.
In this paper, using a laboratory-made alkaline ionic liquid [Bmim] OH as catalyst for transesterification of rapeseed oil and ultrasound-assisted transesterification of rapeseed oil.The raw material characteristics of rapeseed oil,and rapeseed oil fatty acids and rapeseed biodiesel component analysis and other related study.
Through a single factor and orthogonal tests, The author seriously study of many factors which are effect on transesterification, such as molar ratio between methanol to rapeseed oil, reaction temperature, reaction time and amount of ionic liquids, and the ionic liquid stability. The results showed that the optimum reaction conditions were:n(methanol):n(rapeseed oil)=16:1, reaction temperature150℃, reaction time 4h, dosage of catalyst 6% of rapeseed oil weight. Yield of biodiesel was 96.2%. The ionic liquid is stable and without decreasing,which repeatedly used for 5 times.Reaction kinetics studies have shown that the reaction order was 0.7075, the activation energy was 43.94 kJ/mol, preexponential factor was 96,056.32. The reaction kinetic model was.-(dcA)/(dt)=96056.32e-(43.93)/(RT)C A0.7075.
Rapeseed biodiesel preparation under the ultrasound-assisted alkaline ionic liquid [Bmim] OH, we get the optimal reaction conditions were:ultrasonic frequency 59KHz, ultrasonic power 200W, reaction temperature 90℃, reaction time 1h, n (methanol):n (rapeseed oil)=16:1 and the amount of catalyst for the quality of rapeseed oil 6%. Under these conditions, biodiesel yield was 90.8%.
The main component of rapeseed oil biodiesel is grease containing C18, its molecular structure meets the requirements of diesel substitute, is an ideal substitute for diesel oil. After measuring rapeseed oil biodiesel with UPLC, its main components were flax acid methyl ester, linoleic acid methyl ester, oil acid methyl ester, and mustard methyl.
生物柴油的制备方法有直接混合法、微乳液法、高温热裂解法、酯交换法。而酯交换中的碱催化法因其反应条件温和,催化剂成本低,反应速度快,转化率高,是目前工业生产中使用较为广泛的一种方法。
离子液体是指在室温或接近室温(<150℃)的条件下呈现液态的、完全由阴阳离子构成的物质。作为一种新型的环境友好溶剂和液体酸碱催化剂,具有其它溶剂和传统催化剂不具备的优点。由于其独特而优良的性能,它被认为是21世纪最有希望的绿色溶剂和催化剂之一,现已应用于催化反应、有机合成、分离科学以及电化学等诸多领域。
本论文以实验室自制的碱性离子液体氢氧化—丁基三甲基咪唑([Bmim]OH)为催化剂,进行了菜籽油的酯交换反应、超声波辅助下的菜籽油酯交换反应,以及菜籽油的原料特性、菜籽油脂肪酸和菜籽油生物柴油的成份分析等相关试验研究。
对于[Bmim]OH催化菜籽油的酯交换反应,通过单因素和正交试验的手段,详细研究了醇油摩尔比、反应温度、反应时间和离子液体用量对酯交换反应的影响及离子液体的稳定性。结果表明,在n(甲醇)：n(菜籽油)=16：1、反应温度150℃、反应时间4h和催化剂用量为菜籽油质量6%的条件下,生物柴油收率可达96.2%,并且该离子液体的稳定性良好,循环使用五次催化性能没有明显降低。反应动力学的研究显示,该反应的反应级数为0.7075,活化能为43.94kJ/mol,指前因子为96056.32。该反应的动力学模型为-(dcA)/(dt)=96056.32e-(43.93)/(RT)C A0.7075。
对于超声波辅助下的碱性离子液体[Bmim]OH催化菜籽油制备生物柴油,超声波频率59KHz时得到的最优反应条件是：超声波功率200W、反应温度90℃、反应时间1h、n(甲醇)：n(菜籽油)=16：1和催化剂用量为菜籽油质量6%。该条件下,酯交换反应脂肪酸甲酯收率达到90.8%。
超高效液相色谱测得的菜籽油生物柴油的主要成分为亚麻酸甲酯、亚油酸甲酯、油酸甲酯、芥酸甲酯。菜籽油生物柴油的主要成分是含有18个C的脂肪酸甲酯,其分子结构满足理想的柴油替代品的要求,是合格的燃料替代品。
Energy is an important material base of human society to exist and develop.With the dual increasing pressures of environment and energy, the development of renewable, environmente-friendly fuels to replace fossil fuels has become a world consensus. Biodiesel,for its good performance bring the huge potential and broad market prospects, becomes gradually the focus of attention.
There are many methods for preparation of biodiesel, direct mixing method, micro-emulsion method, high-temperature thermal cracking method and transesterification. currently,The base catalyzed transesterification,for its mild reaction conditions, low cost of catalyst, fast reaction rate, and high conversion ratio, is one of more widely used methods in industrial.
Ionic liquid is liquid under the room temperature or near room temperature (<150℃) and entirely composed of the anion and cation. As a new type of environment-friendly solvent and liquid catalyst, Ionic liquid has many unique advantages. Because of unique and excellent performance, it is considered to be one of the most promising green solvent and catalyst in the 21st century.It has been used in catalytic reaction, organic synthesis, separation science and electrochemical and other areas.
In this paper, using a laboratory-made alkaline ionic liquid [Bmim] OH as catalyst for transesterification of rapeseed oil and ultrasound-assisted transesterification of rapeseed oil.The raw material characteristics of rapeseed oil,and rapeseed oil fatty acids and rapeseed biodiesel component analysis and other related study.
Through a single factor and orthogonal tests, The author seriously study of many factors which are effect on transesterification, such as molar ratio between methanol to rapeseed oil, reaction temperature, reaction time and amount of ionic liquids, and the ionic liquid stability. The results showed that the optimum reaction conditions were:n(methanol):n(rapeseed oil)=16:1, reaction temperature150℃, reaction time 4h, dosage of catalyst 6% of rapeseed oil weight. Yield of biodiesel was 96.2%. The ionic liquid is stable and without decreasing,which repeatedly used for 5 times.Reaction kinetics studies have shown that the reaction order was 0.7075, the activation energy was 43.94 kJ/mol, preexponential factor was 96,056.32. The reaction kinetic model was.-(dcA)/(dt)=96056.32e-(43.93)/(RT)C A0.7075.
Rapeseed biodiesel preparation under the ultrasound-assisted alkaline ionic liquid [Bmim] OH, we get the optimal reaction conditions were:ultrasonic frequency 59KHz, ultrasonic power 200W, reaction temperature 90℃, reaction time 1h, n (methanol):n (rapeseed oil)=16:1 and the amount of catalyst for the quality of rapeseed oil 6%. Under these conditions, biodiesel yield was 90.8%.
The main component of rapeseed oil biodiesel is grease containing C18, its molecular structure meets the requirements of diesel substitute, is an ideal substitute for diesel oil. After measuring rapeseed oil biodiesel with UPLC, its main components were flax acid methyl ester, linoleic acid methyl ester, oil acid methyl ester, and mustard methyl.
引文
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