焙烧温度对Ti(SO4)2/CS催化二甲醚直接氧化合成聚甲氧基二甲醚性能的影响  

Effects of calcination temperature on the catalytic performance of Ti(SO4)2/CS for DME direct oxidation to polyoxymethylene dimethyl ethers

作　　者：冯茹 高秀娟[1,2] 杨奇 李明杰 张俊峰 宋法恩[1] 张清德[1,3] 韩怡卓[1] 谭猗生 FENG Ru;GAO Xiu-juan;YANG Qi;LI Ming-jie;ZHANG Jun-feng;SONG Fa-en;ZHANG Qing-de;HAN Yi-zhuo;TAN Yi-sheng(State Key Laboratory of Coal Conversion,Institute of Coal Chemistry,Chinese Academy of Sciences,Taiyuan 030001,China;University of Chinese Academy of Sciences,Beijing 100049,China;Dalian National Laboratory for Clean Energy,Dalian 116023,China)

机构地区：[1]中国科学院山西煤炭化学研究所煤转化国家重点实验室,山西太原030001 [2]中国科学院大学,北京100049 [3]中国科学院洁净能源创新研究院,辽宁大连116023

出　　处：《燃料化学学报》2021年第1期72-79,共8页Journal of Fuel Chemistry and Technology

基　　金：国家自然科学基金(21773283,21373253);中科院创新交叉团队项目(BK2018001);中科院洁净能源创新研究院合作基金(DNL201903);中科院青年创新促进会人才项目(2014155);固体表面物理化学国家重点实验室开放基金(201624)资助。

摘　　要：采用等体积浸渍法制备了活性炭球(CS)负载Ti(SO4)2的双功能催化剂,考察了焙烧温度对Ti(SO4)2/CS催化剂选择氧化二甲醚(DME)直接合成聚甲氧基二甲醚(DMMx)催化性能的影响。结果表明,不同焙烧温度制备的Ti(SO4)2/CS催化剂表现出明显的催化活性差异,280℃焙烧的30%Ti(SO4)2/CS催化剂具有最佳性能,DME转化率为11.7%,DMM1−3的选择性达到75.8%,其中,DMM2,3选择性在30%以上。采用SEM、XRD、Raman、TG、NH3-TPD及XPS等表征手段研究了催化剂的结构及表面性质。焙烧温度改变了活性炭球表面官能团的分布,进而影响了Ti(SO4)2的分散状态,调变了酸中心种类和数量,尤其是弱酸和中强酸的比例,使催化剂表面酸性强弱呈现不同梯度,催化剂的酸性和氧化还原性位达到比较合理的匹配,进一步促进了C−O链的增长。。A series of Ti(SO4)2/activated carbon spheres(CS)bifunctional catalysts were designed and prepared by impregnation method,and the effect of calcination temperature of the catalysts on direct oxidation of dimethyl ether(DME)to polyoxymethylene dimethyl ethers(DMMx)was investigated.The results showed that the performance of Ti(SO4)2/CS catalysts was closely related to the calcination temperature.The 30% Ti(SO4)2/CS catalyst calcined under O2 atmosphere at 280℃exhibited excellent activity over which the conversion of DME reached 11.7% with the selectivity of DMM1−3 up to 75.8%,wherein,the selectivity of DMM2−3 was over 30%.The texture and surface properties of the catalysts were characterized by SEM,XRD,Raman,TG,NH3-TPD and XPS.The suitable amount of weak acid sites and redox sites of the Ti(SO4)2/CS were beneficial to the direct oxidation of DME to DMMx.The calcination temperature changed the distribution of functional groups on the surface of CS which then affected the dispersion form of Ti(SO4)2.The type and amount of acid centers especially the ratio of weak acid and medium strong acid could also be adjusted,which can lead to different gradients of the surface acidity of the catalyst.The reasonable matching of the acidic and redox sites on the catalyst can evidently promote the growth of C−O chain.

关 键 词：二甲醚 直接氧化 聚甲氧基二甲醚 焙烧温度 Ti(SO4)2/CS 

分 类 号：O643[理学—物理化学]