含氮聚合物催化剂的制备及乙炔氢氯化性能研究

Preparation of N⁃Containing Polymer Catalyst and Its Performance in Acetylene Hydrochlorination

乔文强 孙玺 王连杰 张健 秦玉才 宋丽娟

Wenqiang Qiao Xi Sun Lianjie Wang Jian Zhang Yucai Qin Lijuan Song

辽宁石油化工大学 辽宁省石油化工催化科学与技术重点实验室，辽宁 抚顺 113001 中国科学院大连化学物理研究所，辽宁 大连 116023 郑州大学 化学学院，河南 郑州 450001

Key Laboratory of Petrochemical Catalytic Science and Technology，Liaoning Petrochemical University，Fushun Liaoning 113001，China Dalian Institute of Chemical Physics，Chinese Academy of Science，Dalian Liaoning 116023，China School of Chemistry，Zhengzhou University，Zhengzhou Henan 450001，China

以多聚甲醛、1,3,5?三甲基苯和对苯二胺为C源和N源聚合制得CN y 前驱体，经焙烧制成N掺杂C催化剂，并研究经由不同焙烧温度制得的N掺杂C催化剂对乙炔氢氯化反应性能的影响。结果表明，CN y ?700?1催化剂反应活性最高，在乙炔与氯化氢体积比 1.0∶1.1、反应温度280 ℃、乙炔体积空速90 h-1的反应条件下，乙炔转化率可高达89.8%。通过催化剂表征发现，催化剂的活性与比表面积、孔体积和吡咯N相对含量有关，与吡咯N原子结合的碳原子是其活性位点；在一定温度范围内，升高焙烧温度可使催化剂产生较大的比表面积，吡啶N也一定程度转化为吡咯N；催化剂失活的主要原因是积碳。

A nitrogen?doped carbon catalyst was prepared by the calcination of the CN y precursor synthesized by the polymerization of paraformaldehyde,1,3,5?trimethylbenzene and p?phenylenediamine.This paper also investigated the effect of catalyst calcination temperature on the performance of acetylene hydrochlorination.The results indicate that CN y ?700?1 catalyst has the best reaction activity.It has an acetylene conversion of up to 89.8% under the optimized conditions of acetylene?to?hydrogen chloride volume ratio of 1.0∶1.1,reaction temperature of 280 ℃ and GHSV(C2H2) of 90 h-1.The catalyst characterization manifests that the activity of the catalyst is related to the specific surface area,pore volume,and pyrrole nitrogen content.The active site of the catalyst is the carbon atom bonding with the pyrrole nitrogen atom.Increasing the calcination temperature results in a larger specific surface area within a certain temperature range,and the pyridine nitrogen can also be converted to pyrrole nitrogen to a certain extent.The main cause of catalyst deactivation is carbon deposit.

国家自然科学基金项目(21902068)

10.3969/j.issn.1006-396X.2022.03.005