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1、分类号 TQ339 学校编号 10490 UDC 密级 武汉工程大学硕士学位论文题目: 生物柴油的连续化制备学科专业： 化学工艺研究方向： 生物质能源研 究 生： 马家玉指导教师： 王存文 教授 王为国 副教授二 0 0 八 年 四 月独 创 性 声 明 本人声明所呈交的学位论文是我个人在导师指导下进行的研究工作及取得的研究成果。尽我所知，除文中已经标明引用的内容外，本论文不包含任何其他个人或集体已经发表或撰写过的研究成果。对本文的研究做出贡献的个人和集体，均已在文中以明确方式标明。本人完全意识到本声明的法律结果由本人承担。 学位论文作者签名： 年 月 日学位论文版权使用授权书 本学位论文作者
2、完全了解我校有关保留、使用学位论文的规定，即：我校有权保留并向国家有关部门或机构送交论文的复印件和电子版，允许论文被查阅。本人授权武汉工程大学研究生处可以将本学位论文的全部或部分内容编入有关数据库进行检索，可以采用影印、缩印或扫描等复制手段保存和汇编本学位论文。 保 密 ， 在 年解密后适用本授权书。本论文属于 不保密。 （请在以上方框内打“”）学位论文作者签名： 指导教师签名： 年 月 日 年 月 日A Thesis Submitted in Fulfillment of the Requirementsfor the Degree of Master of EngineeringConti
3、nuous Preparation of Biodiesel Major : Chemical TechnologyCandidate : Ma JiayuSupervisor : Professor Wang cunwen Associate Professor Wang weiguoWuhan Institute of TechnologyWuhan, 430074, Hubei, ChinaApril, 2008摘 要摘 要生物柴油是一种新的生物质可再生能源，具有深远的经济效益与社会效益。目前国内外生产生物柴油主要采用间歇搅拌釜式反应器，并形成了一套较为成熟的工艺,但单位体积反应器内生产
4、效率低。本论文采用管式反应器和逆流塔式反应器替代搅拌釜式反应器，以达到降低成本的目的。本文的研究内容和结论为：（1）甲醇与植物油的混合状况对生物柴油的制备有重大影响，研究了填料对甲醇植物油混合状况的影响，实验结果表明：填料的加入，促进了甲醇植物油的混合。（2）以KOH为催化剂，用食用大豆油为原料，在管式反应器中进行了生物柴油的连续化制备，研究了在不同的反应温度及停留时间下，填料对生物柴油收率的影响。实验表明：填料的加入，极大地提高了生物柴油的收率。（3）自行设计了用于生物柴油连续化制备的塔式反应器，实现了油相与醇相在反应器内逆流接触。并以浓H2SO4为催化剂，棉籽油毛油为原料 ，在逆流塔式反应
5、器中进行了生物柴油的连续化制备，考察了实验装置的稳定性和反应温度、停留时间、醇油摩尔比、催化剂的用量、塔板数对生物柴油收率的影响，得出了适宜的反应条件。结果表明：反应初始物料醇油摩尔比越低，停留时间越短,越容易达到稳态；塔板数越多，生物柴油收率越高；醇油摩尔比6:1，温度70，催化剂的用量为油品质量的7%，停留时间6h是酸催化的适宜反应条件，此时生物柴油的收率为93.7%。在同一实验条件下，对逆流塔式反应器与间歇搅拌釜式反应器进行了对比，实验结果显示了逆流塔式反应器的优越性。（4）以NaOH为催化剂，在自制的塔式反应器中进行了生物柴油的连续化制备，考察了反应温度、停留时间、醇油摩尔比、催化剂的
6、用量、甲醇含水量对生物柴油收率的影响，得出了适宜的反应条件。实验结果表明：工业甲醇经简单预处理后，与分析甲醇反应效果相近；醇油摩尔比7:1，温度65，催化剂的用量为油品质量的1.2%，停留时间3h是碱催化的适宜反应条件，在该条件下，生物柴油的收率为88.4%。本文首次在酯交换反应体系中采用逆流塔式反应器，取得很好的效果，值得进一步研究和推广应用。关键词：生物柴油；填料；混合状况；逆流塔式反应器；连续化操作；酯交换反应IAbstractAbstractBiodiesel is a novel renewable biomass energy, which can bring great econ
7、omic and social benefits. Although the present technique of biodiesel production using batch reactors is mature, but its efficiency is low. The tubular reactor and countercurrent tower reactor, which can reduce the manufacturing cost, are adopted to substitute BSTR. The present work is summarized as
8、 follows:(1) The mixing state of methanol to vegetable oil has great influence on preparation of the biodiesel. In this dissertation, an experimental research on effects of packing on the mixing process of methanol to vegetable oil was conducted. The experimental results showed that the joining of t
9、he packing dramatically promoted two-phase mixing.(2) A study was made of the reaction of trans-esterification of edible soybean oil by means of methanol, using KOH as catalysts in a tubular reactor. The effects of reaction temperature, resident time and packing on the yield of biodiesel were studie
10、d. The experimental results showed that the joining of the packing greatly promoted the yield of biodiesel.(3) A countercurrent tower reactor in order to realize continuous preparation of biodiesel was designed, and the countercurrent contact between methanol phase and vegetable oil phase in the cou
11、ntercurrent tower reactor was realized. And biodiesel was prepared by transesterification from vulgar cottonseed oil and methanol, using H2SO4 as catalysts. The stability of experiment plant and the effect of methanol to oil molar ratio, temperature, column plates, resident time and catalyst dosage
12、upon the yield of biodiesel were studied systematically. It was found that when methanol to oil molar ratio was lower and the resident time was short, the steady state could be established more quickly. More column plates could promote the yield of biodiesel. The highest yield was 93.7% achieved at
13、70 and resident time 6h and 7% H2SO4 (w%) of oil and methanol to oil molar ratio at 6:1. In addition, a comparison between the countercurrent tower reactor and the batch reactor was carried out under the same condition and the results revealed the superiority of countercurrent tower reactor.(4) A st
14、udy was made of the reaction of transesterification of vulgar cottonseed oil by means of methanol, using NaOH as catalysts in a self-made reactor. The effects of methanol to oil molar ratio, temperature, industrial grade methanol, resident time and catalyst dosage upon the yield of biodiesel were studied systematically. The results showed that the effect of the simple pretreatment of industrial methanol was close with analysing methanol. The highest yield was 88.4% at 65, resident time of 3h and 1.2% NaOH (w%) of oil and metha
