芴两步法合成9-芴甲醇在蒽渣提取分离菲中的应用  

Application of fluorene two-step synthesis of 9-fluorenylmethanol in extraction and separation of phenanthrene from anthracene residue

作　　者：郭美鑫 叶翠平[1,2] 师田田 梁美生[1] GUO Meixin;YE Cuiping;SHI Tiantian;LIANG Meisheng(College of Environmental Science and Engineering,Taiyuan University of Technology,Jinzhong 030600,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]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,山西太原030024

出　　处：《煤炭学报》2021年第4期1130-1136,共7页Journal of China Coal Society

基　　金：国家自然科学基金资助项目(21776192,22038008);山西省研究生教育创新基金资助项目(2020SY544)。

摘　　要：来自高温煤焦油的蒽渣富含菲和芴等高附加值成分,是典型工业有机固体废弃物。菲和芴是重要的化工中间体,在光电材料、医药、农药等领域具有广泛应用,由于菲与芴性质相近,采用常规分离方法很难实现有效提取。利用芴两步法合成9-芴甲醇的中间产物9-芴甲醛与菲的溶解性差异,采用反应-分离耦合技术,实现菲提取的同时可联产高附加值的9-芴甲醇。实验以芴为原料,在碱催化下,先将芴转化为9-芴甲醛,再还原成9-芴甲醇。考察了酰基化试剂、还原剂、助剂种类以及反应物配比、温度、时间等对反应的影响。结果表明:酰基化阶段采用一段式温度反应,以二甲基亚砜(DMSO)为溶剂,质量分数20%乙醇钠-乙醇溶液为催化剂、甲酸乙酯为酰基化试剂,芴可高效转化为9-芴甲醛;还原阶段无需转换溶剂,以NaBH4为还原剂,加入可溶性无机金属盐助剂,如BaCl2或CaCl2等,可提高NaBH4的还原能力及产物的选择性,9-芴甲醇的选择性和收率可达100%。其他组分菲、蒽和咔唑不参与芴的反应,可在反应过程中实现与芴的分离。以芴与菲模型混合物为原料,经反应-分离后,菲的纯度为96.90%,收率为98.95%;9-芴甲醇纯度97.68%,收率最高可达91.58%。以蒽渣为原料,由于其他组分在预处理过程中积累,最终得到的菲与9-芴甲醇的纯度分别为83.88%和94.35%,收率分别为64.46%和89.49%。Anthracene residue is a typical industrial organic solid waste,which is mainly rich in phenanthrene and fluorene.As important chemical intermediates,phenathrene and fluorene are widely used in photoelectric materials,medicine,pesticides and other fields.Due to their similar properties,it is difficult to achieve effective extraction by conventional separation methods.The reaction-separation coupling technology was adopted,according to the solubility difference of phenanthrene and the intermediate product,9-formylfluorene of fluorene converting to 9-fluorenylmethanol by two-step method,the extraction of phenanthrene and the co-production of 9-fluorenylmethanol with high value-added were realized.The two-step method for the synthesis of 9-fluorenylmethanol with fluorene as raw material was adopted under alkali catalysis.Firstly the fluorene was acylated into 9-formylfluorene,and then reduced to 9-fluorenylmethanol.The effects of the type of acylation reagent,reducor,and auxiliary,and other factors such as reactant ratio,temperature and time on the conversion of fluorene were investigated.Results show that fluorene can be efficiently converted into 9-formylfluorene in di-methyl sulfoxide(DMSO),with 20%ethanolic sodium ethoxide as catalyst,and with ethyl formate as the acylation reagent.Adding inorganic salt auxiliaries,barium chloride or calcium chloride,before sodium borohydride,the reduction selectivity of 9-fluorenylmethanol can be improved by inhibiting the formation of by-products,the selectivity and yield of 9-fluorenylmethanol is up to 100%.Other components,phenanthrene,anthracene and carbazole do not participate in the reaction of fluorene,and phenanthrene can be separated during the reaction.With the mixture of fluorene and phenanthrene as the raw material,the purity of the obtained phenanthrene is 96.90%,and the yield is 98.95%.The purity and the recovery yield of 9-fluorenylmethanol can reach up to 97.68%and 91.58%,respectively.However,when anthracene residue as the raw material,the purity of phenanthrene

关 键 词：煤焦油 反应-分离耦合技术 9-芴甲醛 无机金属盐助剂 还原选择性 

分 类 号：TQ241.57[化学工程—有机化工] TQ243.4