超临界乙醇体系中苯酚催化加氢的降解规律  

Degradation behavior of phenol though catalytic hydrogenation in supercritical ethanol

作　　者：孙梅娟[1] 黄晓典[1] 关清卿[1] 张春云[2] 柴欣生[2] 田森林[1] 宁平[1] 谷俊杰[1] 

机构地区：[1]昆明理工大学环境科学与工程学院,云南昆明650093 [2]华南理工大学制浆造纸工程国家重点实验室,广东广州510640

出　　处：《化工进展》2014年第7期1902-1907,共6页Chemical Industry and Engineering Progress

基　　金：国家自然基金(21307049);云南省高端科技人才引进计划(2010CI110);云南重大科技专项(2012ZB002);云南应用基础研究(2013FZ032);昆明理工大学校人培基金(14118583)项目

摘　　要：目前,液化的生物油与石油粗油成分接近,通常环类化合物含量高,如煤焦油中酚及其衍生物含量占40%以上,急需加氢升级技术。超临界乙醇（243.1℃,6.38MPa）温度、压力条件低,具有良好的传质性能,且为绿色、可再生溶剂。在超临界乙醇体系下的催化加氢是一种油升级有效方式。本文以苯酚为生物油中环类化合物典型模型,在300～400℃、Pt/C催化剂下,探讨超临界乙醇体系下苯酚催化加氢过程。研究分析了超临界乙醇中温度、氢气压力和反应时间对苯酚催化加氢降解规律的影响,并建立了能很好地描述过程中苯酚转化率的动力学模型（R2=0.989）。实验表明：该体系下的苯酚催化加氢降解反应的级数为二级,反应的活化能为51.7kJ/mol;尽管升高温度和氢气压力均能提高苯酚的转化率,但温度对转化率的影响更为显著。本研究将为更好地控制反应过程和提高超临界乙醇体系中苯酚的转化率提供参考。Supercritical ethanol（243.1℃,6.38MPa）has lower temperature and pressure conditions and has good mass transfer performance,so it can serve as a green,renewable solvent in hydrogenation technology. Catalytic hydrogenation under supercritical ethanol system is an effective way to upgrade oil. In this paper,the hydrogenation process of phenol,a typical model compounds in bio-oil,was explored under supercritical ethanol system at 300—400℃ with Pt/C catalyst. This paper investigated the effects such as temperature,hydrogen pressure and reaction time on the degradation of phenol by catalytic hydrogenation in supercritical ethanol. The results showed that higher temperature and hydrogen pressure increased phenol conversion rate,and the effects of temperature was more remarkable. A kinetic model was established based on the results. The model could accurately predict the conversion rate of phenol at different process conditions（R2 = 0.989）. The results of kinetic investigation indicated that the reaction order of the catalytic hydrogenation of phenol in supercritical ethanol was two,and the activation energy was 51.7kJ/mol.

关 键 词：超临界乙醇 苯酚 催化加氢 动力学模型 

分 类 号：TQ03-3[化学工程] TQ517.4