高酸价原料生产生物柴油

GIEC OpenIR > 中国科学院广州能源研究所

	高酸价原料生产生物柴油
其他题名	Biodiesel Production from Feedstocks with High Acid Values
	王忠铭
导师	吴创之
	2008-03-20
学位授予单位	中国科学院广州能源研究所
学位授予地点	广州能源研究所
学位名称	博士
关键词	煎炸废油地沟油豆油皂脚麻疯树油生物柴油
摘要	保证能源安全和控制环境污染是我国实现可持续发展的前提，生物柴油作为环境友好的可再生能源已经成为重点研究开发的一种化石燃料的替代品。目前欧美普遍使用的大豆油和菜籽油在中国油料市场价格昂贵，原料成本过高是我国生物柴油商业化生产的瓶颈。本研究根据具有代表性的煎炸废油、地沟油、豆油皂脚和高酸价麻疯树油等低价位、高酸价生物柴油生产原料的各自特点，采取了不同工艺进行了生物柴油的合成研究。使用承压反应装置，在酸催化剂的作用下，完成了利用煎炸废油和地沟油一步法生产生物柴油的优化实验。通过旋转中心组成实验设计和结果分析，得到了两个二次多项式模型。结果证明在确定反应温度的条件下，甲醇加入量、催化剂用量和反应时间在反应过程决定了产物甲酯含量，这样为酸催化同步酯化和酯交换反应提供了广泛适用的理论依据。比较研究了硫酸和固体酸催化剂（Amberlyst-15）在煎炸废油、地沟油和高酸价麻疯树油预酯化过程的催化效果，总结出利用固体酸催化剂在60℃完成煎炸废油的预酯化，在90℃和95℃完成麻疯树油和地沟油的预酯化的两条绿色工艺路线。通过先用水稀释豆油皂脚，再控制硫酸加入速度和加入量的方式，在室温条件下分离出豆油皂脚内的游离脂肪酸和甘油酯（酸化油）。对于未发酵皂脚，分离率达97%；对于发酵皂脚，分离率为91~93%。通过全析因实验设计及实验结果分析，建立以过量甲醇内含水量和反应时间为自变量，以预酯化后麻疯树油的酸值为因变量的二次多项式模型。设定预酯化后麻疯树油的酸值，根据模型完成理论计算，得到重复使用过量甲醇和硫酸预酯化麻疯树油所需要的反应时间，并通过实际的20次实验验证了该模型的准确性和实用性。该预处理方法减少了硫酸加入总量，缩短了反应时间，对实际工业化生产具有应用价值。在小试实验数据的基础上设计完成年产200吨生物柴油的小型中间试验装置，并利用固体酸催化剂在该装置上进行了酸值为7.12mgKOH/g的桐油预酯化反应实验，及随后在活塞流反应器上的碱催化转酯化反应。商业化生产的技术分析表明，地沟油和生物柴油的价格变化对项目经济效益的影响表现很敏感。其它因素不变的情况下，地沟油价格增加10%或生物柴油降低10%都会出现亏损。从亏损额上分析，生物柴油的市场价格对盈利能力影响更大。甲醇和甘油的变化对盈利水平影响较小，主要是因为是它们在整个物料平衡过程中物质总量相对于地沟油和生物柴油小
其他摘要	Energy safety and environment protection play key role in the sustainable development of our country. As an environment friendly renewable energy, bodiesel is considered as a promising alternative of fossil diesel. Refined rapeseed and soybean oils in China are too expensive to make biodiesel competitive in the market. High price of feedstock becomes the bottleneck for biodiesel development. This research focus on the utilization of low cost feed stock, such as used frying oil, trap grease, soap stock and jatropha oil with high acid value. Comparison and optimization of the technologies related to different feedstocks have been conducted in this work. Biodiesel production from used frying oil and trap grease via acid catalysis was carried out in a pressurized reactor. Through central rotatable design, two quadric polynomial models were obtained. Methanol, sulfuric acid loading and the reaction time were the significant factors influenced the ester content of the biodiesel. This result provided reliable data for acid catalyzed both esterification and transesterification. Studies on the activity of solid acid (Amberlyst-15) concluded that used frying oil could be esterified at 60℃ and jatropha oil with about 5% free fatty acids, trap grease with 50% free fatty acids should be treated at 90℃, 95℃. A novel separation process of soapstock at room temperature was developed through dilution with water, pH control of the followed acidulation. Yield of acid oil can be achieved at 97% and 91~93% based on fresh soapstock and fermented soapstock respectively. Water content of excess methanol and reaction time were taken as two independent variables, the acid values of jatropha oil were taken as response surface, and a quadric polynomial model was established through a full factorial design. A high efficient method was developed by 20 verification experiments carried out based on this model. The total sulfuric acid and the average reaction time were decreased significantly, which is valueble for biodiesel commercialization using jatropha oil as feedstock. A small pilot plant with a capacity of 200tons/year was designed based on the results of the experiments in the laboratory. Tung oil with an acid value of 7.12mgKOH/g was esterified in the fixed reactor, and then it was transesterified in the plug flow reactor continuously. Economic analysis showed that the profitability of biodiesel production from trap grease was sensitive to the change of prices of trap grease and biodiesel. Budget deficit is expected if the price of trap grease increases 10% or the price of biodiesel decreases 10% while other factors are stable. The effect of biodiesel price is more significant than the price of trap grease. The change of methanol and glycerol price is less important because of the sum of them relative to the trap grease and biodiesel is small.
页数	140
语种	中文
文献类型	学位论文
条目标识符	http://ir.giec.ac.cn/handle/344007/4057
专题	中国科学院广州能源研究所
推荐引用方式 GB/T 7714	王忠铭. 高酸价原料生产生物柴油[D]. 广州能源研究所. 中国科学院广州能源研究所,2008.

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