摘要
经典禅语近年来，车用柴油中硫含量的控制越来越严格，然而，柴油深度加氢脱硫的同时，也造成柴油润滑性能的降低，这将严重影响发动机油泵、气缸的性能。油酸甘油酯作为一种绿色柴油润滑性改进剂，具有低毒，易降解，润滑性好等优点，该类酯中尤以三油酸甘油酯效果最佳，对柴油的适用性更广。黄河三角洲京博化工研究院有限公司也开发了该酯类产品，但合成工艺存在很大的不足，如设备腐蚀严重、三废产生量大、产品质量不稳定等。通过分析考察发现，产生的主要原因是：（1）油酸原料中饱和脂肪酸含量过高，导致产品的浊点高；（2）酯化反应工艺采用的催化剂对后期产品精制存在影响，导致产品不稳定，最终影响到柴油质量。因此研发一种更经济、绿色环保的酯化工艺显得尤为重要。
本文首先对三种浊点和饱和脂肪酸含量均偏高（10%左右）的植物油酸进行提纯。选用孔径25μm的滤布，在0.25~0.4MPa的压力下，进行三级恒温冷冻压滤，经压滤后不饱和脂肪酸纯度达到99%以上，凝点由-1℃降至-19℃、浊点由3℃降至-11℃，产率均在80%以上，各项指标优于进口妥尔油酸。通过对比分析各油酸中不饱和脂肪酸的含量、浊点及原料价格，最终选择精制后的棉籽油酸作为合成酯型润滑性改进剂的原料。
其次，对酯化反应工艺进行研究，确定最佳工艺条件。主要工作包括：（1）催化剂筛选，确定对甲苯磺酸效果优于分子筛催化剂；（2）对筛选出的对甲苯磺酸催化剂进行优化，制备出一种活性氧化铝负载对
甲苯磺酸催化剂，具有较高的催化活性，并且，污染小，不腐蚀设备，后处理简单，是一种创新型催化剂；（3）对酯化反应操作条件（催化剂的用量、反应温度、反应时间、酸醇摩尔比）进行优化，确定了最佳工艺条件：酸醇摩尔比2.85:1，反应温度150℃，催化剂用量为5%，反应时间3h，转化率可高达98.5%。
最后，选择精制后的棉籽油酸作为原料，按照上述的最佳反应条件完成中试放大。将合成产品按照200mg/kg添加量加入到低硫柴油中，加剂后柴油磨斑直径达到国家标准，且对柴油的低温流动性，氧化安定性，十六烷值等指标不会产生副作用。
关键词：低硫柴油，润滑性能，酯类添加剂，油酸甘油酯
Synthesis and Application of Glycerol Trioleate
Hou Xiaofeng（Mechatronic Engineering）
Directed by Prof. Hou Yingfei
Abstract
The control index of sulfur content in automotive diel becomes increasingly strict. With the deep hy
drogenation of diel, the lubricating property of the diel decreas, which has bad influences on the engine oil pump and cylinder. Oleic acid glycerides are a kind of green lubricity improvers for diel, becau they are low toxicity, easy degradation and good lubricity. Especially, glycerol trioleate is the best, which has a wider applicability for diel. Chambroad Chemical Industry Rearch Institute has also developed an ester product of this kind, but the preparation method has some drawbacks, such as equipment corrosion, waste materials, and the unsteady of product quantity. Two reasons have be found according to investigation. The first is that the content of saturated fatty acids in materials is too high. The other is that the catalyst ud in the esterification reaction has negative effects on the refinement of the final products. Therefore, it is particularly important to develop a more economical and green esterification process.
Firstly, in this paper, three kinds of plant oleic acid, who cloud point and saturated fatty acid content（about 10%）are high, were purified by three-grade-filtration at a constant low temperature. After purification, the purity of unsaturated fatty acids reached more than 99%, the freezing point decread from -1℃to -19℃, and the cloud point decread from 3℃to -11℃. The product yield of the three plant oleic acids were all over 80%. The indicators were better than the import tall oleic acid. By comparing unsaturated fatty acids’ purity, cloud point and material price, the refined cottons
eed oleic acid was lected as the best raw material for the synthesis of ester lubricity improvers.
Secondly, we studied the esterification process and determined the conditions of reaction. (1) P-toluenesulfonic acid was lected as a better kind of catalyst than molecular sieve. (2) To optimize the catalyst, we prepared an activated aluminium oxide supported p-toluene sulfonic acid catalyst, which has high catalytic activity, less pollution, no
corrosion equipment and simple post-processing. (3) We optimized the conditions of the esterification reaction, including the amount of catalyst, reaction temperature. The optimum process conditions were determined as follows: the reaction temperature, reaction time, addition of catalyst, and the molar ratio of acid to alcohol were 150oC, 3h, 5%, and 2.85:1. Under this conditions, the conversion could be as high as 98.5%.
Finally, the pilot test was successfully completed using the refined cottoned oleic acid under the above conditions. When the addition of production into the low sulfur diel oil was 200 mg/kg, the diel abrasion spot diameter could meet the request of national standard. It was also proved that the addition of this product into diel was safety for the low temperature fluidity, oxidation stability, cetane number, etc.
Key words：Low sulfur diel oil, Lubricating property, Ester additive, Glycerol oleat
目录
第1章绪论 (1)
1.1 我国柴油质量升级情况 (1)
1.1.1 我国柴油标准的发展 (1)
1.1.2 柴油低硫化对柴油质量的影响 (2)
1.2 柴油的组成和性质与其润滑性能的关系 (3)
1.2.1 芳烃对柴油润滑性的影响 (3)
1.2.2 柴油粘度对柴油润滑性的影响 (3)
1.2.3 氮化物对柴油润滑性的影响 (3)
1.2.4 含氧化合物与柴油润滑性的关系 (4)
1.2.5 硫化物与柴油润滑性的关系 (4)
1.3 柴油润滑性改进剂的研究进展 (4)
1.3.1 脂肪酸酯和生物柴油 (4)
1.3.2 羧酸类有机物 (5)
1.3.3 醇、醚类有机物 (5)
1.3.4 脂肪胺酰胺类有机物 (5)
1.4 本课题主要的研究内容 (6)
第2章油酸原料的精制 (8)
2.1 引言 (8)
2.2 实验仪器设备与试剂 (8)
2.2.1 实验试剂 (8)
九月十五
2.2.2 实验主要仪器（设备） (8)
2.3 产品评价 (9)
2.4 原料精制 (9)
2.4.1 植物油酸种类 (11)
幼儿教师观2.4.2 原料植物油酸的化学组成分析 (13)
2.5 原料精制制备工艺 (13)
2.5.1 分子精馏法 (13)
2.5.2 尿素络合法 (13)我要吃鱼翅
2.5.3 恒温冷冻压滤法 (14)
2.6 提纯条件的确定 (14)
2.6.1 恒温冷冻时间对提纯的影响 (14)
2.6.2 恒温冷冻温度和次数对提纯的影响 (15)
2.6.3 滤布孔径对提纯的影响 (16)
2.6.4 压滤机压力对提纯的影响 (16)
关于健康的文案2.7 产物的纯度检测 (17)
2.8 副产物纯度检测 (21)
2.9 提纯产物物性分析 (23)
2.10 本章小结 (26)
第3章柴油润滑性改进剂的合成及应用研究 (27)
3.1 引言 (27)
3.2 实验仪器及试剂 (27)
3.2.1 实验仪器 (27)
3.2.2 实验试剂 (27)
3.3 实验方案 (28)
3.3.1 新型润滑性改进剂反应机理 (28)
3.3.2 实验反应装置 (28)
工作通讯3.4 产品评价及分析方法 (29)
放松肌肉的方法3.4.1 红外光谱分析 (29)
3.4.2 运动粘度测定 (30)
3.4.3 闪点测定 (30)
3.4.4 抗磨性能评价 (31)
3.4.5 润滑性改进剂酸值的测定 (32)
3.4.6 原料反应转化率的计算 (32)
3.4.7 柴油性能的评定方法 (32)
3.4.8 柴油分水性能的评定方法 (33)
3.4.9 柴油堵塞性能的评定方法 (33)长线股票
3.5 合成工艺探究 (34)
3.5.1 酯化反应工艺催化剂筛选 (34)
3.5.2 酸醇摩尔比对酯化反应的影响 (43)
3.5.3 催化剂用量对酯化反应的影响 (44)
3.5.4 反应时间对酯化反应的影响 (45)
