Ca-Zn-Al复合氧化物催化1,2-丙二醇与尿素制碳酸丙烯酯  

Synthesis of Propylene Carbonate From 1,2-Propanediol and Urea Catalyzed by Ca-Zn-Al Composite Oxide

作　　者：王陇豫 卢志凯 柳鑫 罗国华[2] 徐新 刘海燕[1] 孟祥海[1] 徐春明[1] 刘植昌[1] 靳海波[2] WANG Longyu;LU Zhikai;LIU Xin;LUO Guohua;XU Xin;LIU Haiyan;MENG Xianghai;XU Chunming;LIU Zhichang;JIN Haibo(State Key Laboratory of Heavy Oil Processing,China University of Petroleum,Beijing,102249,China;Beijing Key Laboratory of Fuel Cleaning and Efficient Catalytic Emission Reduction Technology,College of New Materials and Chemical Engineering,Beijing Institute of Petrochemical Technology,Beijing 102617,China;Lucky Medical Technologies Co.,Ltd.,Baoding 071000,China;Hebei Medical Imaging Materials and Application Technology Innovation Center,Baoding 071000,China)

机构地区：[1]中国石油大学(北京)重质油全国重点实验室,北京102249 [2]北京石油化工学院新材料与化工学院燃料清洁化及高效催化减排技术北京市重点实验室,北京102617 [3]乐凯医疗科技有限公司,河北保定071000 [4]河北省医用影像材料及应用技术创新中心,河北保定071000

出　　处：《石油学报(石油加工)》2025年第2期443-452,共10页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金项目(22378026)资助。

摘　　要：采用共沉淀法制备了Ca-Zn-Al复合氧化物催化剂,采用XRD、SEM、XRF和NH 3-TPD分析方法对所制备催化剂的晶型晶貌、元素组成及表面酸性进行表征,并对其催化1,2-丙二醇与尿素醇解反应合成碳酸丙烯酯的性能进行了研究。结果表明:催化剂制备过程中沉淀体系的pH值、金属离子比及催化剂焙烧温度对催化剂催化1,2-丙二醇与尿素醇解反应有明显的影响,同时具有较好的稳定性。在沉淀体系n(Ca^(2+))∶n(Zn^(2+))∶n(Al 3+)=1.6∶3∶1、pH=9.5条件下,通过共沉淀得到具有水滑石结构的前驱体,前驱体经900℃焙烧4 h所制得的Ca-Zn-Al复合氧化物催化剂催化1,2-丙二醇与尿素醇解反应具有良好的催化性能。在n(1,2-丙二醇)∶n(尿素)=1.5∶1、温度145℃、压力20 kPa条件下反应4 h,碳酸丙烯酯收率达到93.8%。同时通过温度序列控制方案对该反应过程实现了有效优化,碳酸丙烯酯收率提高至98.3%。Ca-Zn-Al composite oxide catalysts were prepared by co-precipitation method.The crystal form,elemental composition and surface acidity of the catalyst were characterized by XRD,SEM,XRF and NH 3-TPD.Simultaneously,the catalytic performance of propylene carbonate(PC)synthesized from 1,2-propylene glycol(PG)with urea was investigated.The results indicate that the pH,metal ion ratio and catalyst calcination temperature of the precipitation system during catalyst preparation have obvious effects on the alcoholysis reaction of 1,2-propylene glycol with urea,showing good stability.When satisfying the following conditions:the metal ion ratio of n(Ca^(2+))∶n(Zn^(2+))∶n(Al 3+)=1.6∶3∶1 and the pH of 9.5,a precursor with a hydrotalcite structure can be obtained through co-precipitation.The Ca-Zn-Al composite oxide catalyst,prepared by calcining the precursor at 900℃for 4 h,exhibits good catalytic performance for the alcoholysis of 1,2-propylene glycol with urea.Under the conditins of n(PG)∶n(Urea)=1.5∶1,reaction temperature of 145℃,pressure of 20 kPa and reaction time of 4 h,the yield of propylene carbonate(PC)reaches up to 93.8%.Meanwhile,a temperature sequence control scheme is employed to optimize the reaction process,as a result of which PC yield increases to 98.3%.

关 键 词：Ca-Zn-Al催化剂 尿素 1 2-丙二醇 碳酸丙烯酯 醇解反应 

分 类 号：TQ225.52[化学工程—有机化工]