La/Hβ-Al2O3复合材料改善轻汽油醚化活性  

La/Hβ-Al_2O_3 composite materials improve light gasoline etherification activity

作　　者：颜曦明 王宝宇 柯明[3] 张海燕[1] 石海信[1] YAN Ximing;WANG Baoyu;KE Ming;ZHANG Haiyan;SHI Haixin(Guangxi Colleges and Universities Key Laboratory of Beibu Gulf oil and Natural Gas Resource Effective Utilization, College of Chemistry and Chemical Engineering, Qinzhou University, Qinzhou 535011, China;Ocean College, Qinzhou University, Qinzhou 535011, China;State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China)

机构地区：[1]钦州学院石油与化工学院,广西高校北部湾石油天然气资源有效利用重点实验室,钦州535011 [2]钦州学院海洋学院,钦州535011 [3]中国石油大学(北京)重质油国家重点实验室,北京102249

出　　处：《复合材料学报》2018年第12期3466-3473,共8页Acta Materiae Compositae Sinica

基　　金：广西自然科学基金(2017GXNSFBA198145);广西高校北部湾石油天然气资源有效利用重点实验室开放课题基金(2017KLOG04);钦州学院引进人才科研启动基金(2017KYQD231).

摘　　要：采用La3+交换法制备La/Hβ-Al_2O_3复合材料,用于改善轻汽油的低温醚化活性。借助XRD、XRF、BET、FTIR、NH3-TPD、PyIR、FETEM-EDX等分析手段对复合材料的理化性能进行表征,其中XRD、XRF、BET和FTIR的表征结果显示,少量La3+的引入对复合材料的晶相结构和骨架结构无明显破坏作用,而适度的La3+交换反而具有扩孔效果;NH3-TPD和PyIR的分析结果表明,经La3+交换后复合材料的酸量和酸强度有所减弱,但引入的La3+可以形成新的B酸中心,使中强酸比例和B酸中心数目得到提高;FETEM-EDX分析结果证实镧物种主要存在于复合材料中的Hβ分子筛上。对该复合材料的低温醚化活性评价结果显示,La3+交换法可以改善复合催化剂的轻汽油醚化活性,催化剂0.1La/Hβ-Al_2O_3表现出最佳活性,产物甲基叔戊基醚收率最高可达58.13%。对该催化剂进行300h寿命考察,证实其具有较好稳定性及可再生性。The La/Hβ-Al2O3 composite materials were prepared by method of lanthanum ion-exchange and used to improve the low-temperature etherification activity of light gasoline.The physical chemical properties of composite materials were characterized by a series of analytical methods,such as XRD,XRF,BET,FTIR,NH3-TPD,PyIR and FETEM-EDX.The results of XRD,XRF,BET and FTIR show that introduction of a small amount of lanthanum ions has no obvious effect on the crystalline phase and skeleton structure of the composite materials,on the contrary,moderate lanthanum ion exchange has the effect of pore-enlarging.The analysis results of NH3-TPD and PyIR show that acid content and acid strength of the composite materials have been weakened,but the introduction of lanthanum ions can form a new Br?nsted acid site,which increases the ratio of medium strong acid and the amount of Br?nsted acid sites.The results of FETEM-EDX analysis confirm that the lanthanum species are mainly present in the Hβ molecular sieve of composite materials.The evaluation results of etherification activity of this composite material show that the method of lanthanum ion-exchange can improve the light gasoline etherification activity of composite catalyst,in which the sample 0.1 La/Hβ-Al2O3 shows the best activity,and the yield of methyl tertiary amyl ether is up to 58.13%.The 300 h life test results show that it has good stability and reproducibility.

关 键 词：轻汽油 醚化 La3+交换 复合材料 清洁生产 

分 类 号：TE624.4[石油与天然气工程—油气加工工程]