芴羟甲基化一步法合成9-芴甲醇用于蒽渣中菲的提取分离  

Application of Hydroxymethylation of Fluorene by One-step Method to 9-Fluorenylmethanol in Extraction and Separation of Phenanthrene from Anthracene Residue

作　　者：乔娅斐 刘俊丽 叶翠平[1,2,3] 郭美鑫 李文英 QIAO Yafei;LIU Junli;YE Cuiping;GUO Meixin;LI Wenying(College of Environmental Science and Engineering,Taiyuan University of Technology,Jinzhong 030600,China;Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering,Taiyuan 030000,China;State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology,Taiyuan 030024,China)

机构地区：[1]太原理工大学环境科学与工程学院,山西晋中030600 [2]山西浙大新材料与化工研究院,太原030000 [3]太原理工大学省部共建煤基能源清洁高效利用国家重点实验室,太原030024

出　　处：《太原理工大学学报》2023年第2期241-246,共6页Journal of Taiyuan University of Technology

基　　金：国家自然科学基金资助项目(21776192,22038008);山西浙大新材料与化工研究院资助项目(2021SX-FR003)。

摘　　要：针对芴和菲性质相似用常规分离法分离困难的问题,采用反应-分离耦合技术,以碳酸钾为催化剂,将芴转化为9-芴甲醇,考察了影响芴一步法合成9-芴甲醇的因素,并将其用于蒽渣中菲的提取分离。结果表明:以DMSO+10%乙醇为溶剂,n(芴)∶n(甲醛)∶n(碳酸钾)=1∶1∶0.2,13℃下反应15 min, 9-芴甲醇的收率约为25%,选择性>84%.乙醇能够抑制9-芴负离子的生成,无机盐影响了传质过程,使脱水反应速率降低。以芴和菲的混合物(质量比1∶4)为原料,经5次反应-分离后菲的收率和纯度分别为97.6%和93.2%;9-芴甲醇总收率为66.5%,平均纯度为95.0%.It is difficult to separate fluorene and phenanthene by conventional separation method owing to their similar properties. The reaction-separation coupling technique was adopted to solve the problem, in which fluorene is first converted into 9-fluorenylmethanol. The factors affecting the yield and selectivity of 9-fluorenylmethanol by one-step synthesis with potassium carbonate as catalyst were investigated for the separation of phenanthrene from anthracene residue further. The results showed that with DMSO+10% ethanol as solvent, n(fluorene)∶n(formaldehyde)∶n(potassium carbonate)=1∶1∶0.2, and reaction at 13 ℃ for 15 min, the yield of 9-fluorenemethanol is about 25% and the selectivity is higher than 84%. Ethanol can inhibit the formation of 9-fluorenyl anion, and the inorganic salt affects the mass transfer and slows down the dehydration reaction. Using the mixture of fluorene and phenanthrene with mass ratio of 1∶4 as raw material, the yield and purity of phenanthrene reaches 97.6% and 93.2% after five reaction-separation cycles, respectively;the total yield of 9-fluorenylmethanol is 66.5%, and the average purity is 95.0%.

关 键 词：反应-分离耦合技术 9-芴甲醇 碳酸盐 乙醇 无机盐 

分 类 号：TQ241.5[化学工程—有机化工] TQ243.4