【作者】 刘欢；

【导师】 杨运泉； 王威燕；

【作者基本信息】 湘潭大学 ， 化学工程与技术， 2014， 硕士

【摘要】 随着全球经济的快速发展，能源短缺和环境问题的日益凸显，开发可再生资源已成为一个被广泛关注的研究课题。生物油是将生物质高温裂解转化而成的液体燃料，与化石能源相比，生物质燃油含氮、硫化合物少，它燃烧时不会给环境带来污染，被认为是最有可能替代化石能源的可再生能源。但是生物油中含有大量的酸、醛、酮、酚、呋喃等含氧化合物，高含氧量显著降低油品的品质，使得生物油的燃烧热低、稳定性差、粘度高，而且有腐蚀性，严重阻碍了其作为碳氢燃料的广泛使用，无法直接作为高品位能源，需进一步加氢脱氧精制。因此，我们必须对生物质油进行加氢脱氧提质改性，使其达到使用标准，开发出高效的加氢脱氧催化剂，并将催化剂应用到对生物质油的加氢脱氧反应中去，对生物油催化加氢脱氧(HDO)制备新型石油替代能源具有重要意义。目前国外广泛开发应用的贵金属催化剂基本上是由铂、钯、铑等贵金属组成的。该催化剂具有活性高、寿命长等优点，被广泛应用于生物油的催化加氢脱氧反应中。载体对负载型催化剂的催化性能有着重要的影响，它可有效地分散活性组分，提高催化剂的活性和降低催化剂成本，并且常与活性组分共同对催化反应产生作用。载体主要用于支持活性组分，使催化剂具有特定的物理性状。当前，国内外研究较多的催化剂载体有：二氧化硅，氧化铝，活性炭等。在载体选取时，必须对效率、催化活性、催化剂负载的牢固性、使用寿命、价格等作综合考虑。负载型贵金属催化剂主要用单一载体，如Al2O3，活性炭等，而以CeO2-Al2O3复合载体负载Pt用于加氢脱氧反应的研究报道还极少。在共沉淀法制备载体的基础上，本实验采用超声波辅助共沉淀法制备了具有高比表面积、大孔容与孔径的CeO2-Al2O3复合载体，并以此制备出一系列负载型Pt/CeO2-Al2O3催化剂，用BET，TEM，XRD等方法对复合载体和催化剂进行表征分析，以对甲基苯酚为模型化合物，研究了Pt/CeO2-Al2O3催化剂的加氢脱氧性能，并考察了载体中Ce-Al比对其催化对甲基苯酚加氢脱氧反应性能的影响。结果表明，Pt负载型催化剂在反应中表现出了较好的加氢活性和脱氧选择性，在573K温度和4.0MPa的氢气压力下，当Ce/Al=1时，催化剂显示较高的加氢脱氧活性，转化率达到94.8%，甲基环己烷的选择性达96.4%，脱氧率高达98.5%，催化效果最好。更多还原

【Abstract】 With the rapid development of global economy, the growing energy shortages andenvironmental problems has been turned up, effective use of the existing fossil resourcesand the development of renewable resources has become a widely concerned researchtopic.Bio-oil is the high temperature cracking conversion of biomass liquidfuels.Compared with the fossil energy, it will not cause environmental pollution duringburning and biomass fuel less nitrogen and sulfur compounds, so is thought to be mostlikely part of the renewable energy to replace fossil energy.But because of the bio-oil wasproduced by biomass thermal cracking, therefore it contains a lot of acid, aldehyde, ketone,phenol,furan and other oxygen containing compounds.High oxygen content significantlyreduced the quality of the product and makes the oil of low heat of combustion, poorstability, high viscosity, low volatile and corrosive and serious hindered the widespreaduse of it as a hydrocarbon fuel, not directly as the high grade energy.So we need furtherhydrogenation deoxidization refined.Therefore, the development of oil hydrogenationdeoxidization modification research is of great significance for the preparation of new oilalternative energy.The current extensive development and application of the preciousmetal catalyst is basically composed of platinum, palladium, rhodium and other preciousmetals.The catalyst has the advantages of high activity, long service life and widely usedin biological oil catalytic HDO.Supporter on the catalytic performance of load typecatalyst has an important influence, it can effectively load and dispersed active component,and improve the efficiency of the catalyst and reduce costs, and often with the activecomponent of catalytic reaction, so choose the appropriate supporter is very important.In this paper, the precious metal Pt catalysts was used in catalytic bio-oil HDOrefined, and achieved significant results.Currently, the main metal load type catalyst with asingle supporter, such as Al2O3, activated carbon, etc., and CeO2-Al2O3compositesupporter load used in the study of the hydrogenation deoxidization reaction is rarelyreported.CeO2-Al2O3composite supporter may than single CeO2and Al2O3supporter has abetter performance.This experiment using the ultrasonic coprecipitation preparation has high specificsurface area, large entrance and nanometer CeO2-Al2O3composite supporter ofaperture.The products were characterized by means of BET、TEM and XRD. With4-Methylphenol as the model compounds, the Pt/CeO2-Al2O3catalyst hydrogenation deoxidization performance, and examines the supporter in the Ce-Al than the4-Methylphenol catalyzed hydrogenation deoxidization reaction.The results show that theload of catalyst in the reaction after showed good hydrogenation activity anddeoxidization selective;In573k temperature and hydrogen partial pressure of4.0MPa,when the Ce/Al=1, catalyst showed higher activity of hydrogenation deoxidization,conversion rate reached94.8%and the selectivity of methyl cyclohexane was96.4%, andthe deoxidation rate is as high as100%.This is the best catalytic effect.更多还原