超临界甲醇与黑松香制备生物柴油的反应研究

STUDY OF ESTERIFCATION OF BLACK ROSIN WITH SUPERCRITICAL METHANOL FOR BIODISESEL PRODUCTION

以重质松节油为溶剂，在无催化剂条件下进行超临界甲醇与黑松香的反应研究。考察反应时间、温度、压力和黑松香／甲醇质量比对反应的影响；检测黑松香基生物柴油的理化性能；拟合反应动力学模型。结果表明，较优反应条件为反应时间3h，反应温度613K，反应压力10—12MPa，黑松香／甲醇质量比1：0.8，反应酯化率为94．02％；黑松香基生物柴油B5的各项理化性能指标基本达到生物柴油调和燃料（B5）国家标准GB／T25199-2010；采用积分法并结合Hooke-Jeeves模式搜索对反应动力学进行分析，黑松香与超临界甲醇的反应级数为1．42～1．62，平均反应级数为1．51，表观活化能为81．36kJ／mol，动力学模型计算值与实验数据吻合良好。

Without any catalyst and using heavy turpentine as solvent, the preparation of biodiesel by esterification with black rosin as raw material under supercritical methanol conditions was studied. The effect of reaction time, reaction temperatures, reaction pressure and quality ratio of black rosin to methanol on the rate of esterification were investigated. The physico-chemical properties of biodiesel were also tested. Lastly, reaction kinetics analysis was studied by integral method and Hooke-Jeeves pattern search method. The results show that the optimal reaction conditions are as follows： reaction time of 3 h, reaction temperature of 613 K, reaction pressure of 10-12 MPa, and the mass ratio of black rosin to methanol 1：0.8, the rate of esterification of black rosin reaches 94.02%. The various physico-chemical properties of biodiesel B5 meet basically the requirements of diesel national （B5） standards GB/T 25199-2010. The reaction orders of esterification reaction of black rosin in supercritical methanol are 1.42-1.62, the average order is 1.51 and the activation energy is 81.36 kJ/mol. The experimental results are in good agreement with the kinetics model.