魏光涛 杨艳娟 王艺志 李仲民 莫润淋 张琳叶

摘   要：采用硫化型NiMo/活性白土为催化剂，以非粮植物油麻疯树油为原料制备第二代生物柴油. 利用等体积浸渍和CS2原位活化结合的方法制备出硫化型NiMo/活性白土催化剂，并通过XRD、BET、Py-FTIR和NH3-TPD等技术对其结构和性能进行表征. 考察了不同反应温度、催化剂用量、反应初始氢压、反应时间下麻疯树油的转化率及生成C15-C18烃类的选择性. 实验结果表明，最优的反应条件为：反应温度300 ℃、催化剂质量分数为7.5%、反应初始氢压3.5 MPa和反应时间60 min，在该反应条件下，麻疯树油的转化率达到95.19%，生成C15-C18烃类的选择性为84.53%. 对最优油品的组分进行了分析，在硫化型NiMo/活性白土催化剂作用下，麻疯树油经加氢饱和、加氢脱氧、脱羰及裂化等反应生成含C15-C18链烃，即第二代生物柴油.

关键词：麻疯树油;甘油三甘酯;加氢;第二代生物柴油;硫化型NiMo/活性白土催化剂;加氢机理;生物燃料

中图分类号：TQ426.64;TD985              文献标志码：A

Preparation of Second Generation Biodiesel Via

Hydrodeoxygenation of Jatropha Oil

WEI Guangtao1，YANG Yanjuan1，WANG Yizhi1，LI Zhongmin1，MO Runlin1，ZHANG Linye1，2?

（1. School of Chemistry and Chemical Engineering，Guangxi University，Nanning 530004，China;

2. Guangxi Key Laboratory of Bio-refinery，Nanning 530007，China）

Abstract：Non-edible jatropha oil was catalyzed by the sulfurated NiMo/activated clay catalyst to produce the second generation biodiesel. By the method of isovolumetric impregnation plus in-situ activation by CS2，a sulfurated NiMo/activated clay catalyst was prepared， and the structure and performance of the catalyst were studied by XRD， BET， Py-FTIR and NH3-TPD techniques. The effects of different reaction conditions such as reaction temperature， catalyst dosage， hydrogen pressure， reaction time on the reaction were investigated. The experimental results show that the optimal reaction conditions are as follows： the reaction temperature is 300 ℃，the catalyst mass fraction is 7.5%， the initial hydrogen pressure of the reaction is 3.5 MPa， and the reaction time is 60 min. Under these conditions，the conversion ratio of jatropha oil and the selectivity to C15-C18 reached 84.53% and 95.19%，respectively. The main components of optimal product were analyzed. With the sulfurated NiMo/activated clay， the second generation biodiesel with the main components of C15-C18 alkenes was obtained via the reactions of hydrogenation saturation， hydrodeoxygenation， hydrodecarbonylation and cracking.

Key words：jatropha oil;triglycerides;hydrogenation;second generation biodiesel;sulfurated NiMo/activated clay catalyst;hydrogenation mechanism;biofuel

生物柴油是一种可降解、可再生、绿色环保的新型生物燃料[1-2]，可作为传统化石燃料的替代品. 通过酯化、酯交换反应制备的第一代生物柴油因具有流动性差、与石化柴油兼容性差、氧含量高、热值低等缺点而限制了其广泛应用[3-4].  与第一代生物柴油相比，以动植物油脂为原料经加氢催化裂解制备的第二代生物柴油因低温流动性优异，与石化柴油兼容性好和较高的十六烷值而成为研究热点[5-6].  在制备第二代生物柴油过程中，原料选择非常重要，因为……