负载型Pd催化剂催化草酸二甲酯脱羰基制备碳酸二甲酯  

Pd-LOADED CATALYST FOR CATALYTIC DECARBONYLATION OF DIMETHYL OXALATE TO PRODUCE DIMETHYL CARBONATE

作　　者：刘鹏 李文松 郭豹 刘继东[1] 吕建华[1] Liu Peng;Li Wensong;Guo Bao;Liu Jidong;LüJianhua(College of Chemical Engineering,Hebei University of Technology,Tianjin 300130)

机构地区：[1]河北工业大学化工学院,天津300130

出　　处：《石油炼制与化工》2024年第8期74-83,共10页Petroleum Processing and Petrochemicals

摘　　要：为开发高效、成本低廉的碳酸二甲酯(DMC)合成工艺,以Naβ(25)、NaZSM-5(25)、NaY(6)、NaY(8)和NaY(10)分子筛为载体,采用浸渍法制备了负载型Pd催化剂,并将其首次用于草酸二甲酯(DMO)脱羰基反应。采用X射线衍射、X射线光电子能谱、透射电镜和傅里叶变换红外光谱等表征方法对催化剂的组成、价态、孔结构、形貌以及晶型进行分析,并对其催化性能进行评价。结果表明,使用Pd/NaY(6)催化剂催化DMO脱羰基合成DMC,在反应温度220℃、反应时间90 min、催化剂用量1.0 g、1,4-二氧六环与DMO质量比4∶1、Pd负载量(w)0.2%的条件下,DMO转化率可达82.59%,DMC选择性可达62.33%。通过对催化剂稳定性的研究发现,经过5次循环再生后,催化剂对DMO脱羰基反应仍具有良好的催化活性。最后,合理推测出Pd/NaY(6)催化剂催化DMO脱羰基合成DMC的反应机理。In order to develop a high efficient and low cost synthetic process for dimethyl carbonate(DMC),supported Pd catalysts were prepared by impregnation method on Naβ(25),NaZSM-5(25),NaY(6),NaY(8),and NaY(10)zeolites,and it was first used in the decarbonylation reaction of dimethyl oxalate(DMO).The composition,valence,pore structure,morphology and crystal of the catalysts were characterized by X-ray diffraction,X-ray photoelectron spectroscopy,transmission electron microscopy and Fourier transform infrared spectroscopy.The results showed that DMC was synthesized by the decarbonylation of DMO over Pd/NaY(6)catalyst.Under the optimum conditions such as a reaction temperature of 220℃,a reaction time of 90 min,a catalyst dosage of 1.0 g,a mass ratio of 1,4-dioxane to DMO of 4∶1,and a Pd loading of 0.2%,the conversion of DMO and the selectivity of DMC were 82.59%and 62.33%,respectively.After five cycles of regeneration,the catalyst showed good catalytic activity for DMO decarboxylation.Finally,the reaction mechanism of DMC synthesis by DMO decarbonylation over Pd/NaY(6)catalyst was reasonably deduced.

关 键 词：分子筛 PD催化剂 草酸二甲酯 脱羰基反应 碳酸二甲酯 

分 类 号：TQ225.52[化学工程—有机化工]