【作者】 胡文斌；

【导师】 贾广信；

【作者基本信息】 中北大学 ， 化学工艺， 2012， 硕士

【摘要】 甲醇与汽油混合配制而成的甲醇汽油可以有效缓解我国的能源压力，降低我国对石油的依赖程度。然而其中应用最多的M15甲醇汽油挥发性强，使得饱和蒸汽压较高，容易造成汽车和加油设施的气阻问题。通过甲醇汽油蒸馏催化改性技术（即在催化剂作用下对蒸馏得到的甲醇汽油轻组分进行催化反应，经过催化反应转化减少其主要的易挥发组分），可以降低M15甲醇汽油的饱和蒸汽压，最终达到消除或改善气阻现象的目的。负载型磷钨酸对甲醇汽油催化改性中的醚化、烷基化等反应具有较高的催化活性，因此，本研究采用负载型磷钨酸对M15甲醇汽油轻组分进行催化改性，以达到降低饱和蒸汽压，改善气阻现象的目的。采用气相色谱分析和饱和蒸汽压测定的方法对催化改性效果进行分析评价，通过正交实验和单因素实验，确定了负载型磷钨酸催化剂对M15甲醇汽油轻组分催化改性的工艺条件为：反应温度85℃、空速1.0h^-1、压力1.25MPa。通过考察不同制备条件对M15甲醇汽油轻组分催化改性效果的影响，确定了负载型磷钨酸催化剂的最佳制备条件为：负载量30%，焙烧温度300℃。与活性炭和中性氧化铝相比，二氧化硅作为载体的负载型磷钨酸在M15甲醇汽油轻组分催化改性中具有更好的催化效果。采用锌、镧、锆、钴等助催化剂对载体进行改性，各改性负载型磷钨酸催化剂对M15甲醇汽油轻组分催化改性的效果不同，其中在负载量3%、改性载体焙烧温度550℃条件下制得的镧改性负载型磷钨酸催化剂催化效果最好。与负载型磷钨酸催化剂、D002型及KRM-30型树脂相比，镧改性负载型磷钨酸催化剂催化改性后的M15甲醇汽油的饱和蒸汽压更低，经过检测，其催化改性后的M15甲醇汽油符合山西省地方标准。采用FT-IR、XRD、NH3-TPD、BET等手段对催化剂进行了表征分析，结果表明磷钨酸与载体二氧化硅表面发生了相互作用，磷钨酸的负载量与焙烧温度对磷钨酸在载体上的分散程度具有直接影响，负载量为30%时，负载型磷钨酸催化剂仍能保持高比表面积和介孔结构。更多还原

【Abstract】 The pressure on energy resources could be released and the dependence on petroleum inour country could be effectively reduced by the application of methanol gasoline which iscompounded with methanol and gasoline. But the most widely used M15 methanol gasoline ishighly volatile which could lead to a high saturated vapor pressure and thus it is easy to causethe problem of air resistance on automobile and the fuelling facilities. The saturated vaporpressure of M15 methanol gasoline could be reduced and the air resistance phenomenon couldbe eliminated or improved by the methanol gasoline catalytic modification technology(namely performing a catalytic reaction for the distilled light component of methanol gasolinein the presence of catalyst), in this way, the amount of main highly volatile component will beconverted and reduced. Supported phosphotungstic acid possesses a high catalytic activity forthe etherification and alkylation of catalytic modification for methanol gasoline. So supportedphosphotungsitc acid is choosed to conduct the catalytic modification for the light componentin M15 methanol gasoline, in this way, the saturated vapor pressure will be reduced and theresisitance phenomenon will be improved.The effect of catalytic modification will be analyzed and evaluated by the method of gaschromatography and saturated vapor pressure determination. And through the orthogonal testsand single-factor test, the technological condition of catalytic modification of supportedphosphotungstic acid catalyst for the light component in M15 methanol gasoline isdetermined as: reaction temperature 85℃, airspeed 1.0h-1and pressure 1.25MPa.The different effect of catalytic modification caused by different preparation conditionswill be examined and the best preparation condition of supported phosphotungstic sodium is determined as: loading 30% and calcination temperature 300℃. Compared with activedcarbon and neutral alumina, the supported phosphotungstic acid with silica as the carrierpossesses a better effect in the catalytic modification for M15 methanol gasoline.Carrier is modified with co-catalysts such as zinc, lanthanum, zirconium and cobalt, andthe effects of catalytic modification of these modified supported phosphotungstic acid catalystfor the light component in M15 methanol gasoline are different. And the best catalytic effectappears with the supported phosphotungstic acid catalyst modified with lanthanum which isprepared under the optional conditions of lanthanum loading 3% and carrier modifiedcalcination temperature 550℃. Compared with the supported phosphotungstic acid catalyst,D002 resin and KRM-30 resin, for M15 methanol gasoline which is modified by this kind ofcatalyst, its saturated vapor pressure is lower and by the testing, its quality is proved to becorresponding with the local standards of Shanxi Province.FT-IR, XRD, NH3-TPD, BET are employed to characterize, and the results show thatphosphotungstic acid interacts with the silica. The disperse degree of phosphotungstic acid onthe carrier is affected directly by the loading amount and calcination temperature ofphosphotungstic acid. The supported phosphotungstic acid catalyst still keeps the largespecific surface area and mesoporous when the loading amount is 30%.更多还原