TiO_(2)改性钒磷氧催化剂催化醋酸甲醛合成丙烯酸研究  

Study on aldol condensation of acetic acid with formaldehyde to acrylic acid over TiO_(2) modified VPO

作　　者：黄博雅 郭荷芹[1] 贾丽涛[1,3] 肖勇 李德宝[1,3] 张建利[4] HUANG Bo-ya;GUO He-qin;JIA Li-tao;XIAO Yong;LI De-bao;ZHANG Jian-li(State Key Laboratory of Coal Conversion,Institute of Coal Chemistry,Chinese Academy of Science,Taiyuan 030001,China;University of Chinese Academy of Sciences,Beijing 100049,China;Dalian National Laboratory for Clean Energy,Dalian,116023,China;State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering,Ningxia University,Yinchuan 750021,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 [4]宁夏大学省部共建煤炭高效利用与绿色化工国家重点实验室,宁夏银川750021

出　　处：《燃料化学学报》2022年第10期1351-1360,共10页Journal of Fuel Chemistry and Technology

摘　　要：采用有机溶剂热法制备了系列TiO_(2)改性的钒磷氧催化剂,利用TEM、XRD、XPS、NH_(3)-TPD及CO_(2)-TPD对催化剂结构及表面物化性质进行了表征,以醋酸甲醛合成丙烯酸为探针反应对催化剂的反应性能进行了评价。结果表明,与未改性的钒磷氧催化剂相比,TiO_(2)的加入显著改变钒磷氧催化剂的(I_(()V^(5+)/V^(4+)))/I_(V)比值,当TiO_(2)的前驱体为金红石相并且Ti/V物质的量比为2.0时,(I_(V^(5+)/V^(4+)))/I_(V)比值达到最高,因此,该催化剂具有最高的丙烯酸收率(18.0%)和丙烯酸生成速率(6.61 mmol/(g·h)),表明对于TiO_(2)改性的钒磷氧催化剂,V^(5+)与V4+的氧化还原循环在催化醋酸甲醛制丙烯酸反应过程中起主要作用。A class of TiO_(2) modified VPO catalysts were prepared by organic solvent-heating method in the present work.The catalysts were characterized by TEM,XRD,XPS,NH_(3)-TPD and CO_(2)-TPD techniques.The catalytic performances were evaluated in the aldol condensation of acetate acid and formaldehyde to acrylic acid in a fixedbed reactor.The results show that the addition of TiO_(2) significantly changes the proportion of V content forming V^(5+)and V^(4+) ion pair to total V with the unmodified VPO catalyst.As the precursor of TiO_(2) is rutile phase and Ti/V molar ratio is 2.0,the proportion of V content forming V^(5+) and V^(4+) ion pair to total V reaches the maximum,resulting in the best acrylic acid yield(18.0%) and acrylic acid space-time yield(6.61 mmol/(g·h)).It indicates that for the VPO catalyst modified by TiO_(2),the redox cycle of V^(5+) and V^(4+) ion pair plays a major role in the catalytic reaction of formaldehyde and acetate acid to acrylic acid.

关 键 词：TiO_(2)改性钒磷氧催化剂 羟醛缩合 丙烯酸 

分 类 号：O643[理学—物理化学]